JP4045339B2 - Porphyrin multimers composed of coordinated heteroaromatic ring-substituted porphyrin metal complexes immobilized by covalent bonds and methods for producing them - Google Patents

Description

  The present invention relates to a novel porphyrin dimer or higher porphyrin multimer and a method for producing the same.

  The present invention also relates to a porphyrin dimer and a monomer constituting the porphyrin multimer of the present invention.

  The porphyrin multimer of the present invention is expected to work as an efficient light energy collecting and transmitting element, and its application to an artificial photosynthesis element and an organic solar cell is considered. Porphyrins are also known to work as light-driven electron transfer elements, and porphyrin multimers are expected to be applied as molecular-sized optical / electronic elements.

  Porphyrin is a cyclic tetrapyrrole in which four pyrrole nuclei are cross-linked by four methine groups. Since porphyrin has a large conjugated system composed of 18π electrons, porphyrin multimers are expected to be used as materials for molecular wires, and several examples of their synthesis have been reported.

  For example, Kyoto University's Osuka (see Non-Patent Documents 1 and 2 etc.) and Tokyo Metropolitan University's Sugiura (see Non-Patent Document 3 etc.) have reported methods of extending porphyrin multimers by covalent bonds. This method is economically disadvantageous because it requires a very multi-step synthesis process. Further, in these methods, it is difficult to synthesize multimers having hundreds of porphyrin units.

The present inventor has already found that imidazolyl porphyrin metal complexes form a porphyrin dimer or higher porphyrin multimer by coordinating with each other between molecules (see the following reaction formulas 1 and 2). (See Non-Patent Documents 4 and 5, and Patent Documents 1 and 2). Since these porphyrin multimers have a function as an energy transfer element, application as a molecular electronics element is expected.

The feature of the porphyrin multimer having the imidazolyl porphyrin metal complex as a structural unit is that the porphyrin multimer forms spontaneously only by mixing the imidazolyl porphyrin monomer in a non-polar solvent, and as a result, it is the smallest raw material. Only the porphyrin monomer, which is a structural unit, may be prepared (see the above reaction formulas 1 and 2). This method is economical compared to the methods of Osuka and Sugiura, in which porphyrin multimers are extended by covalent bonds, and it is practical to produce regularly ordered large metal complex multimers with a molecular weight of 500,000. Is possible. However, a porphyrin multimer extended by a coordination bond is cleaved in a polar solvent, so that there is a problem that the applicable medium and environment are limited to nonpolar ones and the application range is narrow. (Reaction formula 1 arrow reaction from right to left). Therefore, it has been desired to fix a porphyrin multimer extended by a coordinate bond and synthesize a stable multimer that can no longer be cut off after polymer formation.
N. Aratani, A. Osuka, YH Kim, DH Jeong, D. Kim, Angew. Chem. Int. Ed. 39, 1458 (2000) A. Tsuda and A. Osuka, Science, 298, 79 (2001) K. Sugiura, H. Tanaka, T. Matsumoto, T. Kawai, Y. Sakata, Chem. Lett. 1999, 1193. Y. Kobuke, H. Miyaji, J. Am. Chem. Soc. 1994, 116, 4111 K. Ogawa, Y. Kobuke, Angew. Chem. Int. Ed. 2000, 39, 4070 JP2001-253883 Japanese Patent Laid-Open No. 2001-213883

  The present invention has been made in order to solve the above-mentioned problems and the like, and is a porphyrin multimer that can exist stably without depending on the surrounding environment such as the polarity of the solvent, and has a high degree of polymerization. It is an object to provide a porphyrin multimer that can be easily produced.

  The present inventors have found that the above-described problems can be solved by using a specific bis-coordinate heteroaromatic ring-substituted porphyrin derivative as a structural unit that forms a porphyrin multimer. The bis-porphyrin derivative means that two mono-derivative molecules in which a coordinating heteroaromatic ring group and a group having a double bond site that can be used for a ring-closing metathesis reaction are bonded to a porphyrin metal complex by a divalent linking group. It is a bonded bis body. In the porphyrin multimer of the present invention, in addition to the formation of a coordination bond between the coordinating heteroaromatic ring group and the central metal, a ring-closing metathesis reaction between groups having a double bond site. A covalent bond is formed. Therefore, this porphyrin multimer can immobilize its structural unit more strongly and can exist stably without depending on the surrounding environment such as the polarity of the solvent. Moreover, this porphyrin multimer has a chain extending method that is less economical than a conventional method of extending a porphyrin multimer chain by a covalent bond, and is an economically large metal with a molecular weight of 500,000. Complex polymers can be provided.

That is, the present invention provides the following porphyrin multimers.
(I) A linear porphyrin multimer (hereinafter referred to as “covalently bonded linear type”) having a coordination heteroaromatic ring-substituted porphyrin metal complex immobilized by a covalent bond represented by the following general formula (1) Also called “multimers”).

（式中、ａ、ｂ及びｄは、各々独立してＨ、アルキル基またはアリール基を表わす。）を表わし、
Ｘは、−Ｏ−、−Ｓ−、＞ＮＲ₁₀₁（ここで、Ｒ₁₀₁は、Ｈまたはアルキル基を表わす。）、ＣＨ₂または単結合を表わし、
Ｙは、＝Ｏ、＝Ｓまたは２Ｈを表わし、
ｍは、０〜４の整数を表わし、
Ｘ₁は、二価の連結基を表し、
Ｚは、５若しくは６員の含窒素配位性ヘテロ芳香族環基を表わし、
Ｍは、典型金属及び遷移金属から選択される金属のイオンを表わし、
Ｑ₁は、単結合または直線状二価の連結基を表わし、
ｐ₁は、２以上の整数を表わす。｝ {Where,
R is an alkyl group or

(Wherein a, b and d each independently represents H, an alkyl group or an aryl group),
X represents —O—, —S—,> NR ₁₀₁ (wherein R ₁₀₁ represents H or an alkyl group), CH ₂ or a single bond;
Y represents = O, = S or 2H;
m represents an integer of 0 to 4,
X ₁ represents a divalent linking group,
Z represents a 5- or 6-membered nitrogen-containing coordinated heteroaromatic ring group,
M represents a metal ion selected from typical metals and transition metals;
Q ₁ represents a single bond or a linear divalent linking group,
p ₁ represents an integer of 2 or more. }

(II) The present invention also provides a linear porphyrin multimeric derivative represented by the following general formula (1-1), which is a derivative of the above-mentioned covalently bonded linear polymer.

{Where,
R, X, Y, m, X ₁ , Z, M, Q ₁ and p ₁ are as defined in the general formula (I) of the above (I),
e and f simultaneously represent H or a hydroxyl group, or e and f are bonded to each other to form an epoxy ring together with C—C to which they are bonded. }

(III) Further, the present invention provides a divalent group (—Q ₂ ) in which the group corresponding to the linking group (—Q ₁ —) for forming a bis body is bent in the above-described covalently bonded linear multimer. -), A cyclic porphyrin multimer (hereinafter, referred to as a structural unit) comprising a coordination heteroaromatic ring-substituted porphyrin metal complex immobilized by a covalent bond represented by the following general formula (2) having a cyclic structure: Also referred to as “covalently linked cyclic multimers”).

{Where,
a represents H, an alkyl group or an aryl group;
X represents —O—, —S—,> NR ₁₀₁ (wherein R ₁₀₁ represents H or an alkyl group), CH ₂ or a single bond;
Y represents = O, = S or 2H;
m represents an integer of 0 to 4,
X ₁ represents a divalent linking group,
Z represents a 5- or 6-membered nitrogen-containing coordinated heteroaromatic ring group,
M represents a metal ion selected from typical metals and transition metals;
Q ₂ represents a bent divalent group,
p ₂ represents an integer of 3 or more. }

(IV) The present invention also provides a linear porphyrin multimer derivative represented by the following general formula (2-1), which is a derivative of the above-described covalently bonded cyclic multimer.

{Where,
X, Y, m, X ₁ , Z, M, Q ₂ and p ₂ are as defined in the general formula (2) of (III) above,
e and f simultaneously represent H or a hydroxyl group, or e and f are bonded to each other to form an epoxy ring together with C—C to which they are bonded. }

  (V) The covalent-bonded linear multimer represented by the general formula (1) of the present invention is a coordinated heteroaromatic ring-substituted porphyrin metal formed by a coordinate bond represented by the following general formula (3) It can be obtained by subjecting a linear porphyrin multimer having a complex as a structural unit (hereinafter also referred to as “coordinated linear multimer”) to a ring-closing metathesis reaction in the presence of a Grubbs complex.

The present invention also provides a method for producing the coordinated linear multimer represented by the general formula (3) and the covalently bonded linear multimer represented by the general formula (1) using the same.

{Where,
a, b and d each independently represent H, an alkyl group or an aryl group;
X represents —O—, —S—,> NR ₁₀₁ (wherein R ₁₀₁ represents H or an alkyl group), CH ₂ or a single bond;
Y represents = O, = S or 2H;
m represents an integer of 0 to 4,
X ₁ represents a divalent linking group,
Z represents a 5- or 6-membered nitrogen-containing coordinated heteroaromatic ring group,
M represents a metal ion selected from typical metals and transition metals;
Q ₁ represents a single bond or a linear divalent linking group,
p ₁ represents an integer of 2 or more. }

  (VI) In addition, the cyclic multimer represented by the general formula (2) includes a coordination heteroaromatic ring-substituted porphyrin metal complex formed by a coordination bond represented by the following general formula (4) as a constituent unit. The cyclic porphyrin multimer (hereinafter, also referred to as “coordination-bonded cyclic multimer”) is obtained by subjecting it to a ring-closing metathesis reaction in the presence of a Grubbs catalyst.

The present invention also provides a coordination-bonded cyclic multimer represented by the general formula (4) and a method for producing the covalently-bonded cyclic multimer represented by the general formula (2) using the coordinate-bonded cyclic multimer.

{Where,
a, b and d each independently represent H, an alkyl group or an aryl group;
X represents —O—, —S—,> NR ₁₀₁ (wherein R ₁₀₁ represents H or an alkyl group), CH ₂ or a single bond;
Y represents = O, = S or 2H;
m represents an integer of 0 to 4,
X ₁ represents a divalent linking group,
Z represents a 5- or 6-membered nitrogen-containing coordinated heteroaromatic ring group,
M represents a metal ion selected from typical metals and transition metals;
Q ₂ represents a bent divalent group,
p ₂ represents an integer of 3 or more. }

  (VII) The coordination bond linear multimer represented by the general formula (3) and the coordination bond cyclic multimer represented by the general formula (4) are cross-linked by the following general formula (5). It can be produced from a bis-coordinate heteroaromatic substituted porphyrin monomer having a moiety.

The present invention relates to a bis-coordinated heteroaromatic substituted porphyrin monomer represented by the following general formula (5), and a coordination represented by the general formula (3) by self-organizing it in a nonpolar solvent. Also provided are methods for producing coordinate-bonded linear multimers and coordination-bonded cyclic multimers represented by the general formula (4). At this time, in the general formula (5), when a single bond or a linear divalent linking group is used as the linking group represented by -Q-, a linear multimer of the general formula (3) is obtained, When a bent divalent group is used as the linking group represented by -Q-, a cyclic multimer of the general formula (4) is obtained.

{Where,
a, b and d each independently represent H, an alkyl group or an aryl group;
X represents —O—, —S—,> NR ₁₀₁ (wherein R ₁₀₁ represents H or an alkyl group), CH ₂ or a single bond;
Y represents = O, = S or 2H;
m represents an integer of 0 to 4,
X ₁ represents a divalent linking group,
Z ₂ represents H, a 5- or 6-membered nitrogen-containing coordinating heteroaromatic ring group, an alkyl group or an aryl group,
M represents a metal ion selected from typical metals and transition metals;
Q represents a single bond or a divalent linking group. }

(VIII) Furthermore, the present invention is also referred to as a coordinating heteroaromatic substituted porphyrin dimer (hereinafter referred to as “covalent bond dimer”) immobilized by a covalent bond represented by the following general formula (6). ).

（式中、Ｄは、アリーレン基及びアルキレン基の少なくとも一方を含む二価の基を表わし、Ｅは、アリーレン基及びアルキレン基の少なくとも一方を含む三価の基を表わし、Ｒ³は、Ｈまたはアセチル基を表わす。）を表わす。｝ {Where,
a represents H, an alkyl group or an aryl group;
X represents —O—, —S—,> NR ₁₀₁ (wherein R ₁₀₁ represents H or an alkyl group), CH ₂ or a single bond;
Y represents = O, = S or 2H;
m represents an integer of 0 to 4,
X ₁ represents a divalent linking group,
Z represents a 5- or 6-membered nitrogen-containing coordinated heteroaromatic ring group,
M represents a metal ion selected from typical metals and transition metals;
R ¹ is H, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,

(In the formula, D represents a divalent group containing at least one of an arylene group and an alkylene group, E represents a trivalent group containing at least one of an arylene group and an alkylene group, and R ³ represents H or Represents an acetyl group). }

(IX) The present invention also provides a covalent dimer derivative represented by the following general formula (6-1), which is a derivative of the covalent dimer represented by the general formula (6).

{Where,
X, Y, m, n, Z, M and R ¹ are as defined in the general formula (6) of (VIII) above,
e and f simultaneously represent H or a hydroxyl group, or e and f are bonded to each other to form an epoxy ring together with C—C to which they are bonded.

  (X) The covalent bond dimer represented by the general formula (6) is a coordinated heteroaromatic substituted porphyrin dimer (hereinafter referred to as “coordinating heteroaromatic substituted porphyrin dimer”) formed by the coordinate bond represented by the following general formula (7). (Also referred to as “coordinated bond dimer”) in the presence of a Grubbs complex.

The present invention also provides a coordination bond dimer represented by the general formula (7) and a method for producing a covalent bond dimer of the general formula (6) using the coordination bond dimer.

（式中、Ｄは、アリーレン基及びアルキレン基の少なくとも一方を含む二価の基を表わし、Ｅは、アリーレン基及びアルキレン基の少なくとも一方を含む三価の基を表わし、Ｒ³は、Ｈまたはアセチル基を表わす。）を表わす。｝ {Where,
a, b and d each independently represent H, an alkyl group or an aryl group;
X represents —O—, —S—,> NR ₁₀₁ (wherein R ₁₀₁ represents H or an alkyl group), CH ₂ or a single bond;
Y represents = O, = S or 2H;
m represents an integer of 0 to 4,
X ₁ represents a divalent linking group,
Z represents a 5- or 6-membered nitrogen-containing coordinated heteroaromatic ring group,
M represents a metal ion selected from typical metals and transition metals;
R ¹ is H, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,

(In the formula, D represents a divalent group containing at least one of an arylene group and an alkylene group, E represents a trivalent group containing at least one of an arylene group and an alkylene group, and R ³ represents H or Represents an acetyl group). }

(XI) The present invention also provides a monomer of the general formula (8) and a method for producing a coordination bond dimer of the general formula (7) using the monomer.

（式中、ａ、ｂ及びｄは、各々独立してＨ、アルキル基またはアリール基を表わす。）を表わし、
Ｘは、−Ｏ−、−Ｓ−、＞ＮＲ₁₀₁（ここで、Ｒ₁₀₁は、Ｈまたはアルキル基を表わす。）、ＣＨ₂または単結合を表わし、
Ｙは、＝Ｏ、＝Ｓまたは２Ｈを表わし、
ｍは、０〜４の整数を表わし、
Ｘ₁は、二価の連結基を表し、
Ｚ₂は、Ｈ、５若しくは６員の含窒素配位性ヘテロ芳香族環、アルキル基またはアリール基を表わし、
Ｍ₂は、２Ｈまたは典型金属及び遷移金属から選択される金属のイオンを表わし、
Ｒ¹は、Ｈ、アルキル基、アルケニル基、アルキニル基、アリール基、

（式中、Ｄは、アリーレン基及びアルキレン基の少なくとも一方を含む二価の基を表わし、Ｅは、アリーレン基及びアルキレン基の少なくとも一方を含む三価の基を表わし、Ｒ³は、Ｈまたはアセチル基を表わす。）を表わす。｝ {Where,
R is an alkyl group or

(Wherein a, b and d each independently represents H, an alkyl group or an aryl group),
X represents —O—, —S—,> NR ₁₀₁ (wherein R ₁₀₁ represents H or an alkyl group), CH ₂ or a single bond;
Y represents = O, = S or 2H;
m represents an integer of 0 to 4,
X ₁ represents a divalent linking group,
Z ₂ represents H, a 5- or 6-membered nitrogen-containing coordinating heteroaromatic ring, an alkyl group or an aryl group,
M ₂ represents 2H or an ion of a metal selected from typical metals and transition metals,
R ¹ is H, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,

(In the formula, D represents a divalent group containing at least one of an arylene group and an alkylene group, E represents a trivalent group containing at least one of an arylene group and an alkylene group, and R ³ represents H or Represents an acetyl group). }

(XII) The present invention also relates to a linear porphyrin multimer comprising a coordination heteroaromatic ring-substituted porphyrin metal complex formed by a coordination bond represented by the following general formula (3-A) I will provide a.

(In the formula, R ₄ represents a hydrogen atom or an alkyl group, and X, Y, m, X ₁ , Z, M, Q ₁ and p ₁ are as defined in the general formula (3).)

(XIII) Furthermore, the present invention provides a cyclic porphyrin multimer having a coordination heteroaromatic ring-substituted porphyrin metal complex formed by a coordination bond represented by the following general formula (4-A) as a structural unit. .

(In the formula, R ₄ represents a hydrogen atom or an alkyl group, and X, Y, m, X ₁ , Z, M, Q ₂ and p ₂ are as defined in the general formula (4).

(XIV) Furthermore, the present invention provides a bis-coordinated heteroaromatic substituted porphyrin monomer having a cross-linked portion represented by the following general formula (5-A).

(Wherein R ₄ represents a hydrogen atom or an alkyl group, and X, Y, m, X ₁ , Z ₂ , M and Q are as defined in the general formula (5).

（式中、ａ、ｂ及びｄは、各々独立してＨ、アルキル基またはアリール基を表わす。）を表わす。 First, the covalently bonded linear multimer of the general formula (1) of the present invention will be described in detail.
In the general formula (1), R is an alkyl group or

(Wherein a, b and d each independently represent H, an alkyl group or an aryl group).

  Here, the alkyl group refers to a linear, branched or cyclic monovalent aliphatic group (hereinafter, the same applies when other substituents are alkyl groups). The aryl group refers to a monovalent aromatic hydrocarbon group, and may be a single ring or a condensed ring having two or more rings (hereinafter, the same applies when other substituents are aryl groups). These alkyl groups and aryl groups can have a substituent, if possible (hereinafter, the same applies to groups other than alkyl groups and aryl groups).

  The number of carbon atoms of the alkyl group represented by a, b, and d indicates that the double bond between the carbon atom to which a is bonded and the carbon atom to which b and d are bonded can be subjected to a ring-closing metathesis reaction. No, it can be selected in consideration of the ease of synthesis of the raw material compound, the function expected of the product, etc., but it is usually 1 to 8, preferably about 1 to 2.

  The number of carbon atoms of the aryl group represented by a, b and d can also be selected from the same viewpoint, and is usually 6 to 20 (for example, phenyl, naphthyl, anthracenyl, pyrenyl, naphthacenyl), 6 to 10 The degree is preferred.

  In the general formula (1), the alkyl group represented by R is the same as described for a, b and d above.

In the general formula (1), X represents —O—, —S—,> NR ₁₀₁ (where R ₁₀₁ represents H or an alkyl group), CH ₂ or a single bond.

The number of carbon atoms of the alkyl group represented by R ₁₀₁ is not particularly limited, but is preferably about 1 to 4.

  In the general formula (1), X is preferably —O— in consideration of easiness of synthesis of the raw material compound, functions expected of the product, and the like.

  In the general formula (1), Y represents ═O, ═S or 2H. Here, Y being 2H means a state in which two hydrogen atoms are bonded to the carbon atom to which Y is bonded by a single bond.

  Y is preferably ═O in consideration of the ease of synthesis of the raw material compound, the function expected of the product, and the like.

In the general formula (1), X ₁ represents a divalent linking group. The divalent linking group represented by X ₁ includes a divalent chain aliphatic hydrocarbon group {for example, — (CH ₂ ) _n — (n represents an integer of 0 to 6. n is a raw material. In view of the ease of synthesis of the compound, the function expected of the product, etc., 2 is preferable.)} Or a divalent aromatic group (for example, 1,4-phenylene, 1,3-phenylene) However, it is not limited to these.

  In the general formula (1), Z represents a 5- or 6-membered nitrogen-containing coordinated heteroaromatic ring group. Here, the 5- or 6-membered nitrogen-containing coordinating heteroaromatic ring group is a 5- or 6-membered heterocycle having at least one nitrogen atom, and is particularly limited as long as it has aromaticity. There is no. As hetero atoms other than nitrogen, oxygen, sulfur and the like can be contained. When structural isomers exist in the nitrogen-containing coordinating heteroaromatic ring group, those structural isomers are included.

The 5-membered nitrogen-containing coordinating heteroaromatic ring group and the 6-membered nitrogen-containing coordinating heteroaromatic ring group include the following imidazolyl group, oxazolyl group, thiazolyl group, and pyridyl group. It is not limited to.

In the imidazolyl group, the alkyl group represented by R ² can usually have 1 to 10 carbon atoms, considering the ease of synthesis of the raw material compound, the function expected of the product, and the like. Is preferred.

  In the general formula (1), Z is preferably an imidazolyl group in consideration of the strength of the bond with the central metal of the porphyrin metal complex.

  In the general formula (1), M represents a metal ion selected from a typical metal and a transition metal. Here, typical metals refer to 1A, 2A, 2B, 3B-7B and Group 0 metals in the long periodic table, specifically, Mg, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi, etc. can be mentioned. The transition metal refers to a metal of group 3A to 7A, 8 and 1B, specifically, Sc, Y, lanthanoid (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho , Er, Tm, Yb, Lu), Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, etc. can be mentioned. The valence of these metals is not particularly limited as long as it can be the central metal of the porphyrin metal complex, but is usually II or III.

  M is not particularly limited as long as it can form a coordination bond with Z described above, but from the viewpoint of reactivity, bond strength, expected function of the product, etc., Zn, Mg, Co and Fe or the like is preferable.

In the general formula (1), Q ₁ represents a single bond or a linear divalent linking group.

  The linear divalent linking group can be selected in consideration of the functions expected of the product (electron or energy conductivity, strength for bonding porphyrin rings, ability to maintain configuration, etc.). .

  Here, the linear divalent linking group is a divalent linking group in which (a) the direction of the bond at both ends is linear or (b) the direction of the bond at both ends is arranged in parallel to each other. Say. Here, the direction of the joints at both ends does not necessarily mean that it is a geometrically perfect straight line. Similarly, “parallel” does not necessarily mean that the plane is geometrically completely parallel. Therefore, the multimer constituted by the linear divalent linking group is not cyclic and may be a substantially linear chain as a whole multimer. In particular, when the multimer composed of the linear divalent linking group is relatively long, the orientation of the bond at both ends of the linear divalent group is geometrically perfectly linear or complete. The chain multimers can be formed if they are not parallel to each other but are substantially linear or substantially parallel. Hereinafter, in the present specification, such a substantially linear state or a substantially parallel state is simply expressed as a straight line or a parallel state, respectively.

(A) Specific examples of the group in which the direction of the bond at both ends are linearly arranged include a divalent saturated or unsaturated aliphatic hydrocarbon group {for example, an alkyl group having 1 to 3 carbon atoms ( —CH ₂ — etc.), —C≡C—}; a divalent saturated or unsaturated hydrocarbon ring group {for example, a monocyclic or condensed ring having about 3 to 20 carbon atoms (1,3-cyclobutylene ( Trans isomer), 1,4-phenylene, 2,7-pyrenylene, etc.}}; a divalent saturated or unsaturated heterocyclic group (for example, a 6-membered heterocyclic ring, wherein N, S, One or more containing O, P, etc. (2,5-pyridine, etc.); porphyrin or porphyrin metal complex {for example, 5,15-porphyrin or 5,15-porphyrin metal complex (wherein the metal is represented by the general formula (1 ) As defined by M. Also in the 10-position and 2 -. The position, in which the substituents may be bonded)} can be exemplified.

Two or more of the divalent groups in which the orientations of the bonds at both ends are linearly arranged can be used. When two or more divalent groups are combined, the same groups (so-called bis form) or different groups may be used, but the combination of the same groups is preferable from the viewpoint of easiness of synthesis of the raw material compound. In addition, when two or more divalent groups are combined, a group in which the orientation of the bonding hands at both ends, such as -O- and -C (= O)-, can be arranged linearly can be interposed. Even if the direction of the joints at both ends of the group finally represented by Q ₁ is linearly arranged, it may be present.

Other examples in the case of combining two or more divalent groups include: -Q ₃ -Q ₄ -Q _3- {where Q ₃ and Q ₄ are each independently the groups listed in (a) above. Represents a divalent group containing. } Is included. In particular, as the Q _4, 5,15 using porphyrin or 5,15 porphyrin metal complex, and the use of 1,4-phenylene or 1,3-phenylene as the Q _3, having a linking group Multimers may form complexes with other functional molecules (eg, molecules having electron accepting properties such as quinones, imides, fullerenes, polypeptides, proteins, oligosaccharides, DNA). it can. This complex will be described later.

Examples of substituents which can be attached to the 10- position and 20-position of the porphyrin ring of 5,15 porphyrin or porphyrin metal _{complex, -X 1 -C (= Y)} -X- (CH 2) m -R ₄ (X ₁ , Y, X, m and R ₄ are as defined in the general formula (3-A)).

  (A) A group in which the orientation of the bond at both ends is arranged in parallel to each other includes a divalent saturated or unsaturated linear hydrocarbon group {for example, a linear alkyl group having 3 to 5 carbon atoms ( n-propylene, etc.), -C = C- (trans isomer)}; divalent aromatic hydrocarbon ring group {for example, condensed ring having about 20 to 20 carbon atoms (2,6-naphthylenyl, 1,6- Pyrenylene, etc.)}.

  In addition, if the direction of the joints at both ends is arranged linearly or parallel to each other as a result, the orientation of the joints at both ends explained as (a) above is linearly arranged (a) It may be a combination with a group in which the directions of the bonding hands at both ends described in the above are arranged in parallel to each other.

Furthermore, if the orientations of the bonds at both ends are arranged linearly or parallel to each other as a result, the group {for example, divalent ferrocene (ferrocenyl)} whose bond orientation is freely changed, and the above A combination with the group described as (a) or (b) may be used. As an example of such a combination, in the above-described -Q ₃ -Q ₄ -Q _3- , Q ₃ is ferrocenyl and Q ₄ is 5,15-porphyrin or a porphyrin metal complex. .

Further, if the direction of the bonding hands at both ends is arranged linearly or parallel to each other as a result, a combination of the bent divalent group described later and the group described as (a) or (b) above There may be. As an example of such a combination, in the above-described -Q ₃ -Q ₄ -Q _3- , Q ₃ is 1,3-phenylene and Q ₄ is 5,15-porphyrin or a porphyrin metal complex. Can be mentioned.

Specific examples of the divalent linking group in which the direction of the bond at both ends are arranged linearly (a) or parallel to each other (a) are given below, but the group represented by Q ₁ is limited to these. It is not a thing.

In addition, examples of the divalent linking group in which the direction of the bond at both ends is linear or parallel to each other are given as a result, but the group represented by Q ₁ is not limited thereto.

In general formula (1), Q ₁ is a single bond or an alkynylene group {(—C≡C—) _n (where n is a value) in consideration of bond strength, stability, ease of synthesis of raw material compounds, and the like. , Represents an integer of 1 to 3)}.

In the general formula (1), p ₁ represents an integer of 2 or more. The value of p ₁ can be appropriately selected according to the use of the covalently bonded linear multimer of the present invention, and there is no particular upper limit, but at this stage, p ₁ is produced up to about 100. It is possible.

  In the general formula (1), the wavy line coming out of the substituent X means the presence of both trans and cis isomers (hereinafter, the same applies to other general formulas). In addition, when there are two or more moieties constituting trans and cis stereoisomerism in one molecule as in general formula (1), these covalent isomers in general formula (1) have these stereoisomers. Various stereoisomers are conceivable depending on the combination of the parts constituting the body. In the present invention, the covalently bonded multimer of the general formula (1) includes all of these possible isomers alone and mixtures thereof (hereinafter, even in compounds represented by other general formulas, Same if isomers are present).

  In the general formula (1), a plurality of characters of the same type are used. These may be different from each other, but the same character is preferable in consideration of easiness of synthesis and the like (hereinafter referred to as other characters). The same applies to general formulas.)

が、アルカン：

、ヒドロキシ体：

またはエポキシ体：

になったものである。 The multimer represented by the general formula (1-1) of the present invention is a derivative of the covalently bonded linear multimer of the general formula (1), and is a covalent bond (alkene) of the repeating unit portion of the general formula (1). portion):

But Alkane:

, Hydroxy form:

Or epoxy:

It has become.

  Next, the covalently bonded cyclic multimer represented by the general formula (2) of the present invention will be described in detail.

In the covalently bonded cyclic multimer of the general formula (2) according to the present invention, two porphyrins are not linear as in the general formula (1) but a bent divalent group as a crosslinking group represented by Q _2. It is characterized by that.

In general formula (2), the bent divalent linking group has the same functions as expected in the product (electron or energy conductivity, porphyrin rings, as in the case of selecting Q ₁ in general formula (1). Can be selected in consideration of the strength of bonding, the ability to maintain the configuration, and the like.

The bent divalent group represented by Q ₂ refers to a divalent group having an angle where the direction of the bond at both ends is not linear or parallel to each other. When the angle formed by the joints at both ends is about 60 ° to 145 °, it is easy to make an annular structure. Specific examples of such groups include unsaturated linear hydrocarbons {for example, carbon number 2 (-C = C- (cis form), etc.)}; saturated or unsaturated carbocycles {for example, carbon atoms About 3 to 20 monocyclic or condensed rings (cyclopropenyl, 1,3-phenylene, 3,6-naphthylene, etc.)}; and saturated or unsaturated heterocycles (for example, 5- to 6-membered heterocycles, Examples of the hetero atom include one or more of N, S, O, P, etc. (1,3-phenyl, 3,5-pyridylene, etc.) The saturated or unsaturated heterocycle includes a benzene ring. An aromatic hydrocarbon such as may be condensed, and a bond may come out from the condensed ring.

Another example of the bent divalent group represented by Q ₂ is -Q ₃ -Q ₄ -Q _3- (described above as an example of Q ₁ (linear divalent linking group)) , Q ₃ is ferrocenyl, and Q ₄ is 5,15-porphyrin or a porphyrin metal complex). As described above, since ferrocene can freely rotate between the iron atom and the upper and lower cyclopentadienyl groups, by using ferrocene as Q ₃ , the angle between the porphyrins at both ends and the porphyrin of the linking group can be determined. It can rotate without limitation up to about 10 ° to 350 °. The 5,15-porphyrin or porphyrin metal complex represented by Q ₄ is also in Q ₁ (linear divalent linking group) as described above, even when it is used in the bent divalent group represented by Q ₂ . It is synonymous with 5,15-porphyrin or a porphyrin metal complex.

Specific examples of the bent divalent linking group are given below, but the group represented by Q ₂ is not limited thereto.

  In the covalently bonded cyclic multimer of the general formula (2), a, X, Y, m, n, Z and M have the same meanings as defined in the general formula (1).

In the general formula (2), p ₂ represents an integer of 3 or more. The value of p ₂ can be appropriately selected according to the use of the covalently bonded cyclic multimer of the present invention, and there is no upper limit in particular, and it is considered that up to about 20 can be produced. , P ₂ of about 6 can be produced.

  The multimer represented by the general formula (2-1) of the present invention is a derivative of the covalently bonded cyclic multimer of the general formula (2), and the covalent bond (alkene moiety) of the repeating unit portion of the general formula (2) Is the same as the multimer of the general formula (2) except that it becomes an alkane, a hydroxy form or an epoxy form (the alkane, hydroxy and epoxy form are the same as those described in the general formula (1-1)). Synonymous).

  Next, the coordination bond linear multimer represented by the general formula (3) and the coordination bond cyclic multimer represented by the general formula (4) of the present invention will be described.

  The coordination bond linear multimer represented by the general formula (3) is one in which the repeating unit portion of the general formula (1) is not covalently bonded by a ring-closing metathesis reaction, and each substituent is represented by the general formula (1). The ring-closing metathesis reaction will be described later.

  The coordination-bonded cyclic multimer represented by the general formula (4) is one in which the repeating unit portion of the general formula (2) is not covalently bonded by a ring-closing metathesis reaction, and each substituent is represented by the general formula (2). It is synonymous with what has been defined.

  Next, the bis-coordinate heteroaromatic substituted porphyrin monomer having a cross-linked portion represented by the general formula (5) will be described.

  The bis-coordinating heteroaromatic substituted porphyrin monomer represented by the general formula (5) includes the above-described coordination-bonded linear multimer of the general formula (3) and the coordination-bonded cyclic polymer of the general formula (4). It can be used as a synthetic intermediate of the body.

  In the general formula (5), the substituents a, b, d, X, Y, m, and n are as defined in the general formula (1).

Z ₂ represents H, a 5- or 6-membered nitrogen-containing coordinated heteroaromatic ring group, an alkyl group, or an aryl group. The 5- or 6-membered nitrogen-coordinating heteroaromatic ring group represented by Z _{2 has the same} meaning as Z in the general formula (1). The carbon number of the alkyl group and aryl group represented by Z ₂ is about 1 to 4 and 6 to 10 respectively.

Q represents a single bond or a divalent linking group, the number of atoms of carbon, preferably carbon atoms, etc., same as those described for Q ₂ in Q ₁ and of the general formula (1) (2) It is.

  Coordination bond linear multimer represented by general formula (3-A), coordination bond cyclic multimer represented by general formula (4-A), and bridge represented by general formula (5-A) The bis-coordinated heteroaromatic substituted porphyrin monomer having a moiety is a hydrogen atom or an alkyl group in the side chain terminal olefin part in general formula (3), general formula (4) and general formula (5), respectively. Except having been replaced with, it is the same as those represented by the general formula (3), the general formula (4) and the general formula (5).

In General Formula (3-A), General Formula (4-A), and General Formula (5-A), R ₄ represents a hydrogen atom or an alkyl group. The alkyl group represented by R ₄ is not particularly limited as long as it has 1 or more carbon atoms. The total number of carbon atoms of the alkyl group represented by — (CH ₂ ) _m —R ₄ contained in the side chain can be about 1 to 18, but from the viewpoint of synthesis, — (CH ₂ ) _m— R ₄ preferably has a small number of carbon atoms, and can be, for example, methyl or ethyl.

  Next, the covalent bond dimer represented by the general formula (6) and the coordination bond dimer represented by the general formula (7) will be described.

  The covalent bond dimer represented by the general formula (6) and the coordination bond dimer represented by the general formula (7) both have a sulfur atom-containing group at the terminal thereof, so that, for example, an electrode such as gold It is possible to provide a part to be joined to the slab. For polyphyrin having a sulfur atom-containing group at the terminal, Japanese Patent Application No. 2000-68766 by the same applicant as this application can be referred to.

  In the general formula (6), a, X, Y, m, n, Z, and M have the same meaning as defined in the general formula (1).

（式中、Ｄは、アリーレン基及びアルキレン基の少なくとも一方を含む二価の基を表わし、Ｅは、アリーレン基及びアルキレン基の少なくとも一方を含む三価の基を表わし、Ｒ³は、Ｈまたはアセチル基を表わす。）を表わす。 R ¹ is H, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,

(In the formula, D represents a divalent group containing at least one of an arylene group and an alkylene group, E represents a trivalent group containing at least one of an arylene group and an alkylene group, and R ³ represents H or Represents an acetyl group).

  The divalent group containing at least one of the arylene group and the alkylene group represented by D is a divalent group having an arylene group and / or an alkylene group at both ends, and usually, A group in which one or more ether groups, a carbonyl group, or a functional group containing a hetero atom (for example, an ester group or an amide group) is interposed, is not necessary. The group intervening between these both terminal groups is a group that can be used when linking the porphyrin ring and the sulfur atom-containing group when synthesizing the compound of the general formula (6). The number of carbon atoms of the arylene group and the alkylene group is not particularly limited, but it is usually 1 to 18 for an alkylene group and 6 to 13 for an arylene group.

  The trivalent group containing at least one of an arylene group and an alkylene group represented by E refers to a group obtained by removing one hydrogen atom from the group represented by D described above.

Further, the number of carbon atoms of the alkyl group, alkenyl group, alkynyl group and aryl group represented by R ¹ is preferably about 1 to 18, 2 to 18, 2 to 18, and 6 to 16, respectively.

In the coordination bond dimer represented by the general formula (7), X, Y, M, Z, R ¹ , m, n and a have the same definitions as those defined in the general formula (6). Moreover, b and d are synonymous with what was prescribed | regulated by General formula (1).

  The dimer represented by the general formula (6-1) of the present invention is a derivative of the covalent bond dimer of the general formula (6), and bonds the substituents extending from the porphyrin ring of the general formula (6). Is the same as the multimer of the general formula (6) except that the covalent bond (alkene moiety) is an alkane, hydroxy or epoxy (the alkane, hydroxy and epoxy are represented by the general formula (1 -1) and the same meaning as described above).

  Next, the coordination heteroaromatic substituted porphyrin metal complex monomer represented by the general formula (8) will be described.

  The monomer represented by the general formula (8) can be used as a synthetic intermediate for the coordination bond dimer represented by the general formula (7).

In the general formula ^{(8), R 1, X} , Y, m and n have the same meanings as those defined by the general formula (7). Specific examples of the alkyl group, alkenyl group, alkynyl group and aryl group represented by R ¹ include a monovalent group derived from the above-described divalent linking group represented by Q ₁ or Q _2. . Here, the monovalent group derived from a divalent linking group means one in which one bond of the divalent linking group is a hydrogen atom or a substituent (for example, trimethylsilyl).

Z ₂ represents H, a 5- or 6-membered nitrogen-containing coordinated heteroaromatic ring, an alkyl group, or an aryl group. The 5- or 6-membered nitrogen-containing coordinating heteroaromatic ring represented by Z ₂ , the alkyl group, and the aryl group have the same meanings as defined in the general formula (5).

M ₂ represents 2H or an ion of a metal selected from typical metals and transition metals. The typical metal and transition metal of M _{2 have} the same meaning as M in the general formula (1).

The porphyrin multimer of the present invention is expected to work as an efficient light energy collecting and transmitting element, and its application to an artificial photosynthesis element and an organic solar cell is considered. Porphyrins are also known to work as light-driven electron transfer elements, and porphyrin multimers are expected to be applied as molecular-sized optical / electronic elements. The relationship between the structure and function of these porphyrin multimers of the present invention will be described below when 5,15-porphyrin is used as the divalent linking group represented by Q ₁ and Q ₂ of the porphyrin multimer of the present invention. Will be described as an example.

When 5,15-porphyrin is used as the divalent linking group, the following new function is produced by appropriately selecting a group represented by M ₂ of the porphyrin.

1. When 2H (metal-free) is selected as M ₂ of the linking group and Zn or Mg is selected as the central metal of the porphyrins at both ends, the linking group site has a lower energy rank than the terminus, so the end to the linking group site. Energy transfer occurs.

2. Select the trivalent metals Co (III), Mnn (III), Fe (III), Ru (III), Cr (III), Au (III), etc. with low energy ranking as M ₂ of the linking group, When Zn or Mg is selected as the central metal of the porphyrin ring, electron transfer occurs from the terminal to the linking base.

3. Pd (II), Ni (II), Cu (II), Cd (II), which tends to cause intersystem crossing (interconversion between singlet excited state and triplet excited state) as M ₂ of the linking group, When Ag (II) is selected and Zn or Mg is selected as the central metal of the porphyrin ring at both ends, singlet oxygen can be efficiently generated by irradiation with visible light in the presence of oxygen.

4). When a coordinating metal such as Zn, Mg, Co, Fe, or Ru is used as M ₂ of the linking group, an arbitrary coordinating molecule can be introduced into the linking group site.

  Hereinafter, 4 will be described in more detail.

As a specific example of 4, for example, in the case of the following molecules, zinc porphyrins at both ends are used to form a chain, helical, or cyclic porphyrin multimer by complementary coordination bonds.

In the above case, the site where the connecting part porphyrin can be coordinated remains. Various functional molecules capable of coordination can be attached to this site. Examples of functional molecules include electron-accepting quinones, imides, and fullerenes as shown below. It can also interact with polypeptides having coordinating functional groups, proteins, oligosaccharides, and the like.

Further, when a divalent linking group having no angle limitation is used, the structure can be changed in accordance with a coordinated functional molecule having a complicated structure as shown below.

  Specific examples of the linking group having no angle limitation include divalent ferrocene. Ferrocene can freely rotate between the iron atom and the upper and lower cyclopentadienyl groups. Therefore, when this is used as a part of the linking group, the angle formed by the porphyrins at both ends and the porphyrin forming the linking group can rotate without limitation from about 10 degrees to about 350 degrees. Examples of functional molecules having a complex structure and capable of coordination include polypeptides and oligosaccharides. The structure changes depending on the combination of the type, number, and order of the nucleic acids, amino acids, and sugars that make up each, but the freely rotatable porphyrin multimer changes simultaneously with the structure to spontaneously form the most stable structure. can do.

  Next, although the manufacturing method of each compound of General formula (1)-(8) of this invention is demonstrated in detail using some typical compounds as an example, this invention is not limited to these. In addition, compounds other than those exemplified here and compounds of the general formulas (3-A), (4-A) and (5-A) are also used by those skilled in the art, reaction temperature, pressure, time, atmosphere. It can be produced by appropriately selecting reaction conditions such as a solvent and a catalyst.

Each compound of the general formulas (5), (3), and (1) can be sequentially produced using the coordination heteroaromatic substituted porphyrin metal complex monomer of the general formula (8) as a synthetic intermediate. In the following scheme 1, in general formula (8), R = methyl, Z ₂ = 1-methyl-2-imidazolyl, R ¹ = 1-trimethylsilylethynyl, M ₂ = 2H, X = Y = O, m = 0 N = 2, and in General Formula (3), M = Zn, Q ₁ = (ethynyl) ₂ , and a = b = d = H =, a synthesis example is shown. It is not limited to. A synthesis example of compound A-6b used as a starting material in this scheme 1 is shown in scheme 3 described later. Note that according to this method, the compound of the general formula (1) and (3) generates as different mixtures of polymerization degree represented by p ₁ -1. From these mixtures, components having a single degree of polymerization can be separated by size exclusion column chromatography or the like. In addition, the degree of polymerization represented by p ₁ -1 can be adjusted by the amount of the intermediate product compound B-5, the amount of the Grubbs complex, the reaction time, and the like.

  Here, the Grubbs complex is a general term for ruthenium carbene complexes developed by Grubbs et al. And exhibiting activity in the olefin metathesis reaction. When this complex is used, even when an olefin compound having various functional groups such as ester, ketone, and amide is used as a reaction substrate, the reaction proceeds selectively only with the olefin moiety (Review by Grubbs et al. (TM Trnka, RH Grubbs, Acc. Chem. Res. 34, 18 (2001))).

  In Scheme 1, the reaction from compound B-6 to compound B-7 is a reaction known as a ring-closing metathesis reaction, and details thereof are described in the above-mentioned Grubbs et al. In summary, a compound having two alkenyl groups undergoes an olefin metathesis reaction to form a cyclic compound.

In addition, the group represented by R of both terminal porphyrins of the compounds B-6 and B-7 has the same meaning as the substituent R defined in the general formula (1). Nonlimiting examples thereof include -CH = CH _2.

  In the linear porphyrin multimer derivative represented by the general formula (1-1) of the present invention, the alkane body is obtained by converting the alkene part of the covalently bonded linear multimer of the general formula (1) into a metal catalyst (for example, platinum , Palladium, rhodium, iridium, Raney nickel and the like, and chlorotristriphenylphosphine rhodium (Wilkinson catalyst) and the like in the presence of hydrogen). As a general reference for hydrogenation, “Experimental Chemistry Course (Maruzen) 4th edition, Volume 26, pages 251-266” can be cited. ).

Further, the hydroxy form is obtained by converting the alkene part of the covalently bonded linear multimer of the general formula (1) in the presence of a catalyst such as osmium tetroxide (OsO ₄ ), for example, N-methylmorpholine N-oxide, It is obtained by oxidizing using an oxidizing agent such as hydrogen peroxide. As a general reference for hydroxylation, “Experimental Chemistry Course (Maruzen) 4th Edition, Volume 23, pages 79-113” can be cited.

  Furthermore, an epoxy body is obtained by oxidizing the alkene part of the covalently bonded linear multimer of the general formula (1) using an oxidizing agent such as m-chloroperbenzoic acid. It can also be obtained by oxidation using an oxidizing agent such as t-butyl hydroperoxide in the presence of a metal catalyst such as borate ester, vanadium, or molybdenum. As a general reference for hydroxylation, “Experimental Chemistry Course (Maruzen) 4th Edition, Volume 23, pages 237-267” can be cited.

Both compounds of general formulas (4) and (2) can also be sequentially produced using the coordination heteroaromatic substituted porphyrin metal complex monomer of general formula (8) as a synthetic intermediate. In the following scheme 2, in the general formula (8), R == methyl, Z ₂ = 1-methyl-2-imidazolyl, R ¹ = 3- _{formylphenyl, M 2 = 2H, X =} Y = O, m = In the general formula (4), M = Zn, Q ₂ = 1,3-phenyl, and a = b = d = H, a synthesis example is shown; It is not limited to examples. Note that according to this method, the compound of the general formula (2) and (4) are produced as different mixtures of polymerization degree represented by p _2. From these mixtures, components having a single degree of polymerization can be separated by size exclusion column chromatography or the like. The degree of polymerization represented by p ₂ can be adjusted by the angle formed by the substituents attached to the bent divalent group. For example, in the example shown in Scheme 2, since the angle formed by the substituent is 120 °, the cyclic structure can be a pentagon or a hexagon, that is, p ₂ is 5 or 6.

  In the chain porphyrin multimer derivative represented by the general formula (2-1) of the present invention, the alkane body is obtained by hydrogenating the alkene part of the covalently bonded cyclic multimer of the general formula (2). The hydrogenation conditions can be the same as those described for the alkane form of the general formula (1-1).

  Moreover, a hydroxy body is obtained by oxidizing the alkene part of the covalent bond linear multimer of General formula (1). The oxidation conditions can be the same as described for the hydroxy form of the general formula (1-1).

  Furthermore, an epoxy body is obtained by oxidizing the alkene part of the covalent bond linear multimer of the general formula (1). The oxidation conditions can also be the same as those described for the epoxy compound of the general formula (1-1).

Both compounds of general formulas (7) and (6) can also be sequentially produced using the coordination heteroaromatic substituted porphyrin metal complex monomer of general formula (8) as a synthetic intermediate. In the following scheme 3, in general formula (8), R == methyl, Z ₂ = 1-methyl-2-imidazolyl, R ¹ = C ₇ H ₁₅ , 1-trimethylsilylethynyl, 1-methyl-2-imidazolyl or A synthesis example is shown in which phenyl, M ₂ = 2H, X = Y = O, m = 0, n = 2, and M = Zn and a = b = d = H in the general formula (7). The present invention is not limited to this synthesis example.

  In the porphyrin dimer derivative represented by the general formula (6-1) of the present invention, the alkane body is obtained by hydrogenating the alkene part of the covalent bond dimer of the general formula (6). The hydrogenation conditions can be the same as those described for the alkane form of the general formula (1-1).

  Moreover, a hydroxy body is obtained by oxidizing the alkene part of the covalent bond linear multimer of General formula (1). The oxidation conditions can be the same as described for the hydroxy form of the general formula (1-1).

  Furthermore, an epoxy body is obtained by oxidizing the alkene part of the covalent bond linear multimer of the general formula (1). The oxidation conditions can also be the same as those described for the epoxy compound of the general formula (1-1).

  Hereinafter, the present invention will be specifically described by way of examples, but is not limited thereto.

<Example 1: Corresponding to Scheme 3>
meso- (methoxycarbonylethyl) dipyrromethane (A-4)
Using methods similar to those in the literature (Y. Tomohiro, A. Satake, Y. Kobuke, J. Org. Chem. 2001, 66, 8442-8446), methoxycarbonylpropanal (11.6 g, 0.1 mol) and pyrrole ( 280 mL, 4 mol) was synthesized by stirring in the presence of trifluoroacetic acid (1.4 mL, 10 mmol). Purification by silica gel chromatography (hexane / EtOAc 5/1) gave 17 g (73%) of meso- (methoxycarbonylethyl) dipyrromethane A-4.

¹ H NMR (600 MHz, CDCl ₃ ) δ 2.22-2.26 (m, 2H), 2.29-2.33 (m, 2H), 3.63 (s, 3H), 3.99 (t, J = 7.2 Hz, 1H), 6.05- 6.07 (m, 2H, pyH4), 6.12-6.14 (m, 2H, pyH5), 6.58-6.62 (m, 2H, pyH2), 7.78 (br, 2H, NH); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 29.5, 31.9, 36.9, 51.6, 105.8, 108.1, 117.3, 132.4, 174.0.

Sn catalyst A-7
Synthesized according to the method of Otera et al. Junzo Otera, Nobuhisa Dan-oh, Hitosi Nozaki, J. Org. Chem. 1991, 56, 5307-5311
Grubbs catalyst A-10
Fluka 09587 (manufactured by Fluka) (Benzylidene-bis (tricyclohexyiphosphine) -dichlororuthenium) was purchased from Wakken and used.

5,15-Bis (methoxycarbonylethyl) -10- (n-heptyl) -20- (1'-methyl-2'-imidazolyl) porphyrin (A-6a)
1 L chloroform to meso- (methoxycarbonylethyl) dipyrromethane A-4 1 (1 g, 4.3 mmol), 1-methyl-2-formylimidazole A-3 (240 mg, 2.2 mmol), 1-octanal A-5a (280 mg, 2.2 mmol) was added, the reaction solution was substituted with N ₂ , and trifluoroacetic acid (1.2 mL, 8.6 mmol) was added. After stirring at room temperature for 4 hours, 2,3,5,6-tetrachloro-1,4-benzoquinone (chloranil, 1.6 g, 6.5 mmol) was added. The reaction mixture was stirred for 3 hours, saturated aqueous sodium hydrogen carbonate was added, and the mixture was extracted with chloroform. After drying the organic layer with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained crude product was fractionated by silica gel chromatography (eluent: chloroform / acetone (9: 1)) to obtain A-6a in a yield of 82 mg and 6%.

¹ H NMR (600 MHz, CDCl ₃ ) δ -2.71 (s, 2H; inner proton), 0.91 (t, J = 7 Hz, 3H; C7), 1.34-1.36 (m, 4H; C6, C5), 1.52 -1.54 (m, 2H, C4), 1.78-1.80 (m, 2H, C3), 2.45-2.55 (m, 2H; C2), 3.38 (s, 3H; NCH ₃ ), 3.45-3.52 (m, 4H; ester β), 3.75 (s, 6H; COO Me ), 4.98-5.00 (m, 2H; C1), 5.23-5.30 (m, 4H; ester α), 7.45 (br.s, 1H; imidazole ring), 7.67 (br.s, 1H; imidazole ring), 8.74 (d, J = 4.2 Hz, 2H, Porβ), 9.44 (d, J = 4.2 Hz, 2H, Porβ), 9.51 (d, J = 4.2 Hz, 2H, Porβ), 9.56 (d, J = 4.2 Hz, 2H, Porβ); ¹³ C NMR (150 MHz, CDCl ₃ )
δ 14.2 (C7), 22.8 (C6), 29.6 (C4), 30.5 (ester α), 30.7 (C3), 32.0 (C5), 34.6 (NCH ₃ ), 36.1 (C2), 39.1 (C1), 41.8 ( ester β), 52.0 (COO Me ), 104.0 (meso), 116.9 (meso), 121.5 (meso), 122.1 (imidazole), 126-132 (br, 4 carbons (Porβ)), 128.5 (imidazole), 148.7 ( Im NC = N), 173.2 (C = O) .Other 4 carbons (Porα) could not be observed by boarding .; UV-Vis (CHCl ₃ ): 652 (Abs .; 0.0188), 594 (0.0260), 551 ( 0.0366), 516 (0.0856), 418 (1.3949) nm; Fluorescence (EX = 418 nm, CHCl ₃ ): 723, 620 nm; MALDI-TOF Mass C ₃₉ H ₄₄ N ₆ O ₄ Calcd: 660.34; Found: 661.9 ( M + H) ⁺ .
5,15-Bis (methoxycarbonylethyl) -10- (1'-trimethylsilylethynyl) -20- (1``-methyl-2 ''-imidazolyl) porphyrin (A-6b)

  Using the same method as A-6a, this compound was deoxygenated chloroform (3 L) to meso- (methoxycarbonylethyl) dipyrromethane A-4 (3 g, 13 mmol), 1-methyl-2-formylimidazole. Add A-3 (1.4 g, 13 mmol), 1-trimethylsilyl-ethynyl aldehyde A-5b (0.8 mg, 6.5 mmol), trifluoroacetic acid (3.7 mL, 26 mmol), chloranil (4.8 g, 20 mmol). Was synthesized. The obtained crude product was fractionated by silica gel chromatography (eluent: chloroform / methanol (9: 1)) to obtain A-6b in a yield of 120 mg and 3%.

¹ H NMR (600 MHz, CDCl ₃ ) δ -2.78 (s, 2H; inner proton), 0.67 (s, 9H; TMS), 3.33 (s, 3H; NCH ₃ ), 3.43 (t, J = 7.2 Hz, 4H; ester β), 3.7 (s, 6H; COO Me ), 5.17-5.19 (m, 4H; ester α), 7.46 (br.s, 1H; imidazole ring), 7.70 (br.s, 1H; imidazole ring ), 8.71 (d, J = 4.2 Hz, 2H; Porβ), 9.34 (d, J = 4.2 Hz, 2H; Porβ), 9.41 (d, J = 4.2 Hz, 2H; Porβ), 9.70 (d, J = 4.2 Hz, 2H; Porβ); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 0.4 (TMS), 30.2 (ester α), 34.6 (NCH ₃ ), 41.7 (ester β), 52.0 (COO Me ), 100.1 ( TMS- C ≡C-), 102.5 (meso), 106.4 (meso), 107.1 (TMS-C≡ C- ), 118.3 (meso), 121.7 (imidazole ring), 128.2 (Porβ), 128.3 (imidazole ring), 128.4 (Porβ), 131.2 (Porβ), 131.9 (Porβ), 144-147 (br, 4 carbons (Porα)), 148.4 (Im NC = N), 173.0 (C = O); UV-Vis (CHCl ₃ ) : 665 (Abs .; 0.0651), 608 (0.0553), 566 (0.1405), 527 (0.1086), 427 (2.3982) nm; Fluorescence (EX = 427 nm, CHCl ₃ ): 740, 668 nm; MALDI-TOF Mass C ₃₇ H ₃₈ N ₆ O ₄ Si Calcd: 658.27; Found: 659.2 (M + H) ⁺ .

5,15-Bis (methoxycarbonylethyl) -10,20-bis (1'-methyl-2'-imidazolyl) porphyrin (A-6c)
Using the same method as A-6a, this compound was meso- (methoxycarbonylethyl) dipyrromethane A-4 (1 g, 4 mmol), 1-methyl-2-formylimidazole in deoxygenated chloroform (1 L). Synthesized by adding A-3 (450 mg, 4 mmol), trifluoroacetic acid (1.7 mL, 12 mmol), chloranil (3 g, 12 mmol). The obtained crude product was fractionated by silica gel chromatography (eluent: chloroform / methanol (9: 1)) to obtain A-6c in a yield of 260 mg, 10%. The compound exists as a trans, cis tautomer (1: 1) mixture with two N-methylimidazole groups. In NMR, peaks derived from imidazole groups are observed separately.

¹ H NMR (600 MHz, CDCl ₃ ) δ -2.82 (s, 2Hx1 / 2; inner proton), -2.78 (s, 2Hx1 / 2; inner proton), 3.43 (s, 3H; NCH ₃ ), 3.48 (dd , J = 7, 7 Hz, 4H; ester β), 3.73 (s, 6Hx1 / 2; COO Me ), 3.74 (s, 6Hx1 / 2; COO Me ), 5.30-5.34 (m, 4H; ester α), 7.46 (d, J = 1 Hz, 2Hx1 / 2; imidazole ring), 7.48 (d, J = 1 Hz, 2Hx1 / 2; imidazole ring), 7.66 (d, J = 1 Hz, 2Hx1 / 2; imidazole ring) , 7.68 (d, J = 1 Hz, 2Hx1 / 2; imidazole ring), 8.83 (d, J = 4.2 Hz, 4Hx1 / 2; Porβ), 8.84 (d, J = 4.2 Hz, 4Hx1 / 2; Porβ), 9.49 (d, J = 4.2 Hz, 4Hx1 / 2; Porβ), 9.50 (d, J = 4.2 Hz, 4Hx1 / 2; Porβ); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 30.1 & 30.2 (ester α) , 34.6 & 34.7 (NCH ₃ ), 41.7 & 41.8 (ester β), 52.0 (COO Me ), 106.0 (meso), 118.1 (meso), 121.7 & 121.9 (imdazole ring), 128. 2 & 128.8 (imidazole ring) , 131.1 & 131.4 (Porβ), 146.5-149.2 (br, 4 carbons (Porα)), 148.1 & 148.5 (Im NC = N), 172.9 & 173.0 (C = O); UV-Vis (CHCl ₃ ): 654 ( Abs .; 0.028), 592 (0.0189), 547 (0.0221), 514 (0.0602), 416 (0.8753) nm; Fluorescence (EX = 416 nm, CHCl ₃ ): 718, 657 nm; MALDI-TOF Mass C ₃₆ H ₃₄ N ₈ O ₄ Calcd: 642.27; Found: 643.2 (M + H) ⁺ .

5,15-Bis (methoxycarbonylethyl) -10- (phenyl) -20- (1'-methyl-2'-imidazolyl) porphyrin (A-6d)
Using the same method as A-6a, this compound was meso- (methoxycarbonylethyl) dipyrromethane A-4 (1 g, 4 mmol), 1-methyl-2-formylimidazole in deoxygenated chloroform (1 L). Synthesized by adding A-3 (220 mg, 2 mmol), benzaldehyde A-6d (0.2 mL, 2 mmol), trifluoroacetic acid (0.9 mL, 6 mmol), chloranil (1.5 g, 6 mmol). The obtained crude product was fractionated by silica gel chromatography (eluent: chloroform / acetone (9: 1)) to obtain A-6d in a yield of 73 mg and a yield of 6%. ¹ H NMR (600 MHz, CDCl ₃ ) δ -2.73 (s, 2H; inner proton), 3.40 (s, 3H; NCH ₃ ), 3.50 (t, J = 8 Hz, 4H; ester β), 3.75 (s , 6H; COO Me ), 5.32 (t, J = 8 Hz, 4H), 7.48 (s, 1H; imidazole ring), 7.68 (s, 1H; imidazole ring), 7.74-7.82 (m, 3H; Ph), 8.10 (d, J = 7 Hz, 1H; Ph), 8.22 (d, J = 7 Hz, 1H; Ph), 8.81 (d, J = 4.2 Hz, 2H; Porβ), 8.89 (d, J = 4.2 Hz , 2H; Porβ), 9.43 (d, J = 4.2 Hz, 2H; Porβ), 9.49 (d, J = 4.2 Hz, 2H; Porβ); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 30.4 (ester α) , 34.6 (NCH ₃ ), 41.8 (ester β), 52.0 (COO Me ), 104.8 (meso), 117.5 (meso), 121.3 (meso), 121.5 (imdazole ring), 126.66 (Ph), 126.73 (Ph), 127.4 (Porβ), 128.0 (imidazole ring), 128.5 (C; Ph), 128.9 (Porβ), 131.1 (Porβ), 132.7 (Porβ), 134.4 (Ph), 142.3 (Ph), 144.2-149.5 (br, 4 carbons (Porα)), 148.7 (Im NC = N), 173.1 (C = O); UV-Vis (CHCl ₃ ): 647 (Abs .; 0.0224), 590 (0.0384), 548 (0.0415), 515 (0.1159 ), 417 (1.9670) nm; Fluorescence (EX = 417 nm, CHCl ₃ ): 717, 652 nm; MALDI-TOF Mass C ₃₈ H ₃₄ N ₆ O ₄ Calcd: 6 38.26; Found: 639.8 (M + H) ⁺ .

5,15- (allyloxycarbonylethyl) -10- (n-heptyl) -20- (1'-methyl-2'-imidazolyl) porphyrin (A-8a)
After substituting porphyrin A-6a (100 mg, 0.15 mmol) and allyl alcohol (0.2 mL, 3 mmol) in toluene (3 mL) with N ₂ , add tin catalyst A-7 (1 mg, 2 μmol) 4 Reflux at 120 ° C. for hours. The completion of the reaction was confirmed by MALDI-TOF Mass, water was added to the reaction solution, and the mixture was extracted with chloroform. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was fractionated by silica gel chromatography (eluent: chloroform / methanol (10: 1)) to obtain A-8a in a yield of 90 mg and a yield of 90%. ¹ H NMR (600 MHz, CDCl ₃ ) δ -2.81 (s, 2H; inner proton), 0.91 (t, J = 7 Hz, 3H; C7), 1.34-1.35 (m, 4H; C6, C5), 1.45 -1.57 (m, 2H; C4), 1.78 (tt, J = 7, 7 Hz, 2H; C3), 2.49 (tt, J = 7, 7 Hz, 2H; C2), 3.34 (s, 3H; NCH ₃ ), 3.50 (t, J = 8 Hz, 4H; ester β), 4.68 (d, J = 6 Hz, 4H; O-CH ₂ -C = C), 4.93 (t, J = 7 Hz, 2H; C1 ), 5.21 (d, J = 11 Hz, 2H; -C = CH ₂ ), 5.26 (t, J = 8 Hz, 4H; ester α), 5.32 (d, J = 18 Hz, 2H; -C = CH ₂ ), 5.92 (ddt, J = 6, 11, 18 Hz, 2H; -CH = C), 7.45 (s, 1H; imidazole ring), 7.68 (s, 1H; imidazole ring), 8.73 (d, J = 4.2 Hz, 2H; Porβ), 9.41 (d, J = 4.2 Hz, 2H; Porβ), 9.47 (d, J = 4.2 Hz, 2H; Porβ), 9.51 (d, J = 4.2 Hz, 2H; Porβ); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 14.2 (C7), 22.8 (C6), 29.4 (C4), 30.4 (C3), 30.7 (ester α), 32.0 (C5), 34.6 (NCH ₃ ), 36.0 ( C2), 39.1 (C1), 41.9 (ester β), 65.6 (O- C -C = C), 103.8 (meso), 116.9 (meso), 118.6 (OC- C = C), 121.6 (meso), 122.1 (imidazole ring), 126.3-129.5 (br, 4 carbons (Porβ)), 128.3 (imidazole ring), 132.2 (OCC = C ), 148.7 (Im NC = N), 172.4 (C = O) Other 4 carbons (Porα) could not observed by boarding .; UV-Vis (CHCl ₃ ): 647 (Abs .; 0.0024), 589 (0.0035), 553 (0.0051 ), 517 (0.0100), 417 (0.1438) nm; Fluorescence (EX = 417 nm, CHCl ₃ ): 722, 655 nm; MALDI-TOF Mass C ₄₃ H ₄₈ N ₆ O ₄ Calcd: 712.37; Found: 713.6 (M + H) ⁺ .

5,15- (allyloxycarbonylethyl) -10- (1'-trimethylsilyl-ethynyl) -20- (1'-methyl-2'-imidazolyl) porphyrin (A-8b)
This compound was prepared in the same manner as 2a by using porphyrin A-6b (70 mg, 0.1 mmol), allyl alcohol (0.1 mL, 2 mmol), tin catalyst A-7 (1 mg) in a toluene (10 mL) solution. , 2 μmol). The obtained crude product was fractionated by silica gel chromatography (eluent: chloroform / methanol (9: 1)) to obtain A-8b in a yield of 62 mg and a yield of 88%.

¹ H NMR (600 MHz, CDCl ₃ ) δ -2.67 (s, 2H; inner proton), 0.66 (s, 9H; TMS), 3.35 (s, 3H; NCH ₃ ), 3.48 (t, J = 7 Hz, 4H; ester β), 4.67 (d, J = 6 Hz, 4H; O-CH ₂ -C = C), 5.19 (d, J = 11 Hz, 2H; -C = CH ₂ ), 5.24 (t, J = 8 Hz, 2H; ester α), 5.30 (d, J = 19 Hz, 2H; -C = CH ₂ ), 5.89 (ddt, J = 6, 11, 19 Hz, 2H; -CH = C), 7.45 (s, 1H; imidazole ring), 7.68 (s, 1H; imidazole ring), 8.74 (d, J = 4.2 Hz, 2H; Porβ), 9.39 (d, J = 4.2 Hz, 2H; Porβ), 9.44 (d , J = 4.2 Hz, 2H; Porβ), 9.71 (d, J = 4.2 Hz, 2H; Porβ); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 0.44 (TMS), 30.2 (ester α), 34.5 (NCH ₃ ), 41.8 (ester β), 65.6 (O- C -C = C), 100.1 (TMS- C ≡C-), 102.5 (meso), 106.7 (meso), 107.1 (TMS-C≡ C- ), 118.3 (meso), 118.6 (OCC = C ), 121.6 (imdazole ring), 128.3 (Porβ), 128.4 (imidazole ring), 128.5 (Porβ), 131.3 (Porβ), 131.8 (Porβ), 132.1 (OC- C = C), 144.5-148.2 (4 carbons (Porα)), 148.5 (Im NC = N), 172.3 (C = O); UV-Vis (CHCl ₃ ): 665 (Abs .; 0.0633), 607 (0.0452), 565 (0.1344), 527 (0.1030), 427 (2.342 3) nm; Fluorescence (EX = 427 nm, CHCl ₃ ): 740, 668 nm; MALDI-TOF Mass C ₄₁ H ₄₂ N ₆ O ₄ Si Calcd: 710.30; Found: 711.0 (M + H) ⁺ .

5,15- (allyloxycarbonylethyl) -10,20-bis (1'-methyl-2'-imidazolyl) porphyrin (A-8c)
This compound was prepared in the same manner as A-8a using porphyrin A-6c (100 mg, 0.2 μmol), allyl alcohol (0.2 mL, 3 mmol), tin catalyst A-7 ( It was synthesized by adding 1 mg, 2 μmol). The obtained crude product was fractionated by silica gel chromatography (eluent: chloroform / methanol (9: 1)) to obtain A-8c in a yield of 99 mg and 92%. The compound exists as a trans, cis tautomer (1: 1) mixture with two N-methylimidazole groups. In NMR, peaks derived from imidazole groups are observed separately.

¹ H NMR (600 MHz, CDCl ₃ ) δ -2.76 (s, 2Hx1 / 2; inner proton), -2.75 (s, 2Hx1 / 2; inner proton), 3.37 (s, 6Hx1 / 2; NCH ₃ ), 3.46 (s, 6Hx1 / 2; NCH ₃ ), 3.55-3.60 (m, 4H; ester β), 4.70-4.72 (m, 4H; O-CH ₂ -C = C), 5.21-5.24 (m, 2H;- C = CH ₂ ), 5.31-5.40 (m, 4H; ester α), 5.90-5.98 (m, 4H; -CH = C), 7.49 (d, J = 1 Hz, 2Hx1 / 2; imidazole ring), 7.50 (d, J = 1 Hz, 2Hx1 / 2; imidazole ring), 7.69 (d, J = 2 Hz, 2Hx1 / 2; imidazole ring), 7.71 (d, J = 1 Hz, 2Hx1 / 2; imidazole ring), 8.87 (d, J = 5 Hz, 4Hx1 / 2; Porβ), 8.88 (d, J = 5 Hz, 4Hx1 / 2; Porβ), 9.54 (d, J = 5 Hz, 4Hx1 / 2; Porβ), 9.55 ( d, J = 5 Hz, 4Hx1 / 2; Porβ); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 30.2 (ester α), 34.6 & 34.7 (NCH ₃ ), 41.9 (ester β), 65.6 (O- C -C = C), 106.4 & 106.5 (meso), 118.0 & 118.1 (meso), 118.6, (OCC = C ) 121.66 & 121.71 (imidazole ring), 128.5 & 128.6 (imdazole ring), 128.8 (Porβ), 131.5 ( Porβ) 132.1 (OC- C = C), 145.5-149.0 (br, 4 carbons (Porα)), 148.4 & 148.5 (Im NC = N), 172.2 (C = O); UV-Vis (CHCl ₃ ): 653 (Abs. 0.0181), 591 (0.0153), 548 (0.0170), 514 (0.0376), 417 (0.04710) nm; Fluorescence (EX = 417 nm, CHCl ₃ ): 717, 657 nm; MALDI-TOF Mass C ₄₀ H ₃₈ N ₈ O ₄ Calcd : 694.30; Found: 695.7 (M + H) ⁺ .

5,15- (allyloxycarbonylethyl) -10- (phenyl) -20- (1'-methyl-2'-imidazolyl) porphyrin (A-8d)
This compound was prepared in the same manner as A-8a using porphyrin A-6d (60 mg, 94 μmol), allyl alcohol (0.1 mL, 2 mmol), tin catalyst A-7 ( It was synthesized by adding 1 mg, 2 μmol). The obtained crude product was fractionated by silica gel chromatography (eluent: chloroform / methanol (9: 1)) to obtain A-8d in a yield of 55 mg and a yield of 85%.

¹ H NMR (600 MHz, CDCl ₃ ) δ -2.73 (s, 2H; inner proton), 3.39 (s, 3H; NCH ₃ ), 3.53 (t, J = 8 Hz, 4H; ester β), 4.69 (d , J = 6 Hz, 4H; O-CH ₂ -C = C), 5.19 (d, J = 10 Hz, 2H; -C = CH ₂ ), 5.30 (t, J = 8 Hz, 4H; ester α) , 5.32 (d, J = 16 Hz, 2H; -C = CH ₂ ), 5.90 (ddt, J = 6, 10, 16 Hz, 4H; -CH = C), 7.47 (s, 1H; imidazole ring), 7.68 (s, 1H; imidazole ring), 7.73-7.82 (m, 3H; Ph), 8.11 (d, J = 7 Hz, 1H; Ph), 8.21 (d, J = 7 Hz, 1H; Ph), 8.81 (d, J = 4.8 Hz, 2H; Porβ), 8.89 (d, J = 4.8 Hz, 2H; Porβ), 9.44 (d, J = 4.8 Hz, 2H; Porβ), 9.50 (d, J = 4.8 Hz, 2H; Porβ); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 30.4 (ester α), 34.6 (NCH ₃ ), 41.9 (ester β), 65.6 (O- C -C = C), 104.8 (meso), 117.4 (meso), 118.5 (OCC = C ), 121.2 (meso), 121.5 (imidazole ring), 126.6 (Ph), 126.7 (Ph), 127.5 (Porβ), 128.0 (imidazole ring), 128.5 (C; Ph) , 128.9 (Porβ), 131.1 (Porβ), 132.1 (OC- C = C), 132.7 (Porβ), 134.3 (Ph), 142.2 (Ph), 144.4-149.2 (4 carbons (Porα)), 148.6 (Im NC = N), 172.2 (C = O); UV-Vis (CHCl ₃ ): 647 (Abs. 0.0230), 590 (0.0392), 549 (0.0424), 515 (0.1201), 417 (2.0850) nm; Fluorescence (EX = 417 nm, CHCl ₃ ): 718, 652 nm; MALDI-TOF Mass C ₄₂ H ₃₈ N ₆ O ₄ Calcd: 690.30; Found: 691.2 (M + H) ⁺ .

5,15- (allyloxycarbonylethyl) -10- (n-heptyl) -20- (1'-methyl-2'-imidazolyl) porphyrinatozinc (A-9a)
A saturated methanol (5 mL) solution of zinc acetate was added to a solution of porphyrin A-8a (80 mg, 0.12 mmol) in chloroform (15 mL). After stirring at room temperature for 1 hour, water was added to the reaction solution, and the mixture was extracted with chloroform. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain A-9a in a yield of 88 mg.

¹ H NMR (600 MHz, CDCl ₃ ) δ 0.98 (t, J = 7 Hz, 3H; C7), 1.43-1.48 (m, 4H; C6, C5), 1.64 (s, 3H; NCH ₃ ), 1.67 ( tt, J = 7, 7 Hz, 2H; C4), 1.97 (d, J = 1.8 Hz, 1H; imdiazole ring), 2.00 (tt, J = 7, 7 Hz, 2H; C3), 2.75 (tt, J = 7, 7 Hz, 2H; C2), 3.64-3.75 (m, 2H; ester β), 3.80-3.86 (m, 2H; ester β), 4.85 (ddd, J = 6, 12.6, 24.6 Hz, 4H; O-CH ₂ -C = C), 5.25 (t, J = 7 Hz, 2H; C1), 5.32 (dd, J = 1.8, 10.2 Hz, 2H; -C = CH ₂ ) 5.40 (d, J = 4.2 Hz, 2H; Porβ4), 5.40-5.50 (m, 4H; ester α), 5.46 (s, 1H; imidazole ring), 6.07 (ddt, J = 6, 10.8, 16.8 Hz, 4H; -CH = C), 8.87 (d, J = 4.2 Hz, 2H; Porβ3), 9.66 (d, J = 4.2 Hz, 2H; Porβ), 9.73 (d, J = 4, 2 Hz, 2H; Porβ); ¹³ C NMR (150 MHz , CDCl ₃ ) δ 14.3 (C7), 22.9 (C6), 29.7 (C4), 30.9 (ester α), 32.2 (C3), 32.7 (NCH ₃ ), 36.3 (C1), 39.8 (C2), 42.7 (ester β), 65.5 (O- C -C = C), 95.8 (meso), 116.8 (meso), 117.8 (OCC = C ), 118.4 (imidazole ring), 121.6 (meso), 122.8 (imidazole ring), 127.2 ( Porβ4), 128.3 (Porβ1), 128.9 (Porβ3), 129.5 (Porβ2), 132 .6 (OC- C = C), 146.1 (Im NC = N), 148.6 (C), 149.2 (C), 149.5 (C), 150.1 (C), 172.9 (C = O); UV-Vis (CHCl ₃ ): 616 (Abs. 0.0044), 568 (0.0104), 434 (0.1165), 416 (0.1052) nm; Fluorescence (EX = 434 nm, CHCl ₃ ): 673, 620, (EX = 416 nm, CHCl ₃ ) : 673, 619 nm; MALDI-TOF Mass C ₄₃ H ₄₆ N ₆ O ₄ Zn Calcd: 774.29; Found: 775.4 (M + H) ⁺ .

5,15- (allyloxycarbonylethyl) -10- (1'-trimethylsilylethynyl) -20- (1``-methyl-2 ''-imidazolyl) porphyrinatozinc (A-9b)
This compound was synthesized by adding a saturated methanol (3 mL) solution of zinc acetate to a chloroform (12 mL) solution of porphyrin A-8b (50 mg, 70 μmol) using the same method as A-9a. . The organic layer was distilled off under reduced pressure to obtain A-9b in a yield of 54 mg. ¹ H NMR (600 MHz, CDCl ₃ ) δ 0.74 (s, 9H; TMS), 1.66 (s, 3H; NCH ₃ ), 2.02 (d, J = 2 Hz, 1H; imidazole ring), 3.70 (ddd, J = 7.2, 10.2, 17 Hz, 2H; ester β), 3.81 (ddd, J = 6, 10.2, 17 Hz, 2H; ester β), 4.80 (dd, J = 6, 12.6 Hz, 2H; O-CH ₂ -C = C), 4.86 (dd, J = 6, 12.6 Hz, 2H; O-CH ₂ -C = C), 5.31 (d, J = 10.8 Hz, 2H; -C = CH ₂ ), 5.44 (d , J = 2 Hz, 1H; imidazole ring), 5.45 (d, J = 4.2 Hz, 2H; Porβ4), 5.48 (d, J = 16.2 Hz, 2H; -C = CH ₂ ), 6.06 (ddt, J = 6, 10.8, 16.2 Hz, 2H; -CH = C), 8.86 (d, J = 4.2 Hz, 2H; Porβ3), 9.65 (d, J = 4.2 Hz, 2H; Porβ1), 9.92 (d, J = 4.2 Hz, 2H; Porβ2); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 0.7 (TMS), 30.9 (ester α), 32.7 (NCH ₃ ), 42.7 (ester β), 65.6 (O- C -C = C ), 98.7 (meso), 99.9 (TMS-C≡ C- ), 100.4 (TMS- C ≡C-), 109.2 (meso), 118.2 (OCC = C ), 118.4 (imidazole ring), 118.5 (meso), 121.9 (imidazole ring), 127.9 (Porβ4), 128.8 (Porβ1), 129.3 (Porβ3), 131.9 (Porβ2), 132.5 (OC- C = C), 145.5 (Im NC = N), 147.8 (C), 150.0 ( C), 150.5 (C), 152.0 (C), 172.7 (C = O) ; UV-Vis (CHCl ₃ ): 637 (Abs .; 0.1747), 579 (0.0830), 445 (1.2834), 426 (0.7554) nm; Fluorescence (EX = 426 nm, CHCl ₃ ): 698, 640 nm; MALDI -TOF Mass C ₄₁ H ₄₀ N ₆ O ₄ SiZn Calcd: 772.22; Found: 773.6 (M + H) ⁺ .

5,15- (allyloxycarbonylethyl) -10- (N-methyl-imidazolyl) -20- (N-methyl-imidazolyl) porphyrinatozinc (A-9c)
This compound was synthesized using a method similar to A-9a by adding a saturated methanol (5 mL) solution of zinc acetate to a chloroform (15 mL) solution of porphyrin A-8c (80 mg, 0.11 mmol). . The organic layer was distilled off under reduced pressure to obtain A-9c in a yield of 87 mg.

¹ H NMR (600 MHz, CDCl ₃ ) δ 1.64 (s, 3H; NCH ₃ (coordination)), 2.21 (d, J = 2.4 Hz, 1H; imidazole ring (coordination)), 3.27 (s, 3H; NCH ₃ (Free)), 3.68-3.76 (m, 2H; ester β), 3.80-3.90 (m, 2H; ester β), 4.78-4.90 (m, 4H; O-CH ₂ -C = C), 5.31 (dd , J = 1.2, 10.2 Hz, 2H; -C = CH ₂ ), 5.47 (dd, J = 1.2, 16.8 Hz, 2H; -C = CH ₂ ), 5.50 (br, 1H; Im ring), 5.52 (d , J = 4.2 Hz, 2H; Porβ4), 5.45-5.55 (m, 4H; ester α), 6.03-6.10 (m, 2H; -CH = C), 7.52 (d, J = 1.8 Hz, 1H; imdiazole ring (free)), 7.80 (d, J = 1.8 Hz, 1H; imidazole ring (free)), 8.96 (d, J = 4.2 Hz, 2H; Porβ3), 8.97 (d, J = 4.2 Hz, 2H; Porβ1) , 9.67 (d, J = 4.2 Hz, 2H; Porβ2); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 30.9 (ester α), 32.6 (NCH ₃ (free)), 34.5 (NCH ₃ (coordination)), 42.7 (ester β), 65.5 (O- C -C = C), 98.2 (br, meso), 98.3 (meso), 117.8 (meso), 118.4 (imidazole ring (coordination)), 118.5 (-C = CH ₂ ), 121.2 (imidazole ring (free)), 122.2 (imidazole ring (coordination)), 128.1 (imidazole ring (free)), 128.9 (Porβ4), 129.6 (Po rβ2,3), 131.4 (Porβ1), 132.5 (OC- C = C), 145.2 (Im NC = N), 147.9 (C), 150.0 (C), 150.1 (C), 150.2 (C) 150.9 (C) , 172.9 (C = O); UV-Vis (CHCl ₃ ): 618 (Abs .; 0.0327), 564 (0.0527), 435 (0.5798), 412 (0.4772) nm; Fluorescence (EX = 412 nm, CHCl ₃ ) : 679, 624 nm; MALDI-TOF Mass C ₄₀ H ₃₆ N ₈ O ₄ Zn Calcd: 756.22; Found: 756.9 (M + H) ⁺ .

5,15- (allyloxycarbonylethyl) -10- (phenyl) -20- (1'-methyl-2'-imidazolyl) porphyrinatozinc (A-9d)
This compound was synthesized by adding a saturated methanol (2 mL) solution of zinc acetate to a chloroform (9 mL) solution of porphyrin A-8d (30 mg, 43 μmol) using the same method as A-9a. . The organic layer was distilled off under reduced pressure to obtain A-9d in a yield of 33 mg.

¹ H NMR (600 MHz, CDCl ₃ ) δ 1.67 (s, 3H; NCH ₃ ), 2.13 (d, J = 2 Hz, 1H; imidazole ring), 3.71 (ddd, J = 6.6, 10.8, 16.8 Hz, 2H ; ester β), 3.85 (ddd, J = 6.6, 10.8, 16.8 Hz, 2H; ester β), 4.84 (ddt, J = 1.2, 6, 12 Hz, 2H; O-CH ₂ -C = C), 4.87 (ddt, J = 1.2, 6, 12 Hz, 2H; O-CH ₂ -C = C), 5.31 (dd, J = 1.8, 10.2 Hz, 2H; -C = CH ₂ ), 5.46 (dd, J = 1.8, 16.2 Hz, 2H; -C = CH ₂ ), 5.47 (d, J = 4.2 Hz, 2H; β4), 5.46-5.51 (m, 4H; ester α), 5.53 (d, J = 2.4 Hz, 1H ; imidazole ring), 6.06 (ddt, J = 6, 10.2, 16.2 Hz, 2H; -CH = C), 7.77 (dd, J = 6.6, 8.4 Hz, 1H; Ph), 7.87 (t, J = 8.4 Hz , 1H; Ph), 7.94 (dd, J = 7.8, 8.4 Hz, 1H; Ph), 8.13 (d, J = 7.8 Hz, 1H; Ph), 8.67 (d, J = 6.6 Hz, 1H; Ph), 8.94 (d, J = 4.2 Hz, 2H; Porβ3), 9.06 (d, J = 4.2 Hz, 2H; Porβ1), 9.61 (d, J = 4.2 Hz, 2H; Porβ2); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 30.9 (ester α), 32.7 (NCH ₃ ), 42.7 (ester β), 65.6 (O- C -C = C), 96.4 (meso), 117.5 (meso), 118.0 (OCC = C ), 118.4 (imidazole ring), 121.5 (imidzole ring), 122.0 (meso), 126.3 (Ph), 126.5 (Ph), 127.4 (Ph), 127.6 (Porβ4), 128.1 (Porβ3), 128.9 (Porβ1), 132.5 (OC- C = C), 132.7 (Porβ2), 134.7 (Ph), 134.8 (Ph), 143.9 (C), 146.0 (Im NC = N), 148.3 (C), 149.5 (C), 149.6 (C), 150.7 (C), 172.8 (C = O); UV-Vis (CHCl ₃ ): 616 (Abs .; 0.0107), 565 (0.0198), 435 (0.1510), 413 (0.1400) nm; Fluorescence (EX = 413 nm, CHCl ₃ ): 674, 619 nm; MALDI-TOF Mass C ₄₂ H ₃₆ N ₆ O ₄ Zn Calcd: 752.21; Found: 753.4 (M + H) ⁺ .

Metathesis C7 (A-11a)
A solution of porphyrin A-9a (80 mg, 0.1 mmol) in chloroform (15 mL) was substituted with N _{2, and} then a ruthenium carbene complex (Grubbs complex A-10) (1 mg, 10 μmol) was added. After stirring at room temperature for 3 hours, completion of the reaction was confirmed by MADLI-TOF Mass. Water was added to the reaction solution and extracted with chloroform. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was fractionated by silica gel chromatography (eluent: chloroform / acetone (9: 1)) to obtain A-11a in a yield of 73 mg and a yield of 95%.

  The ultraviolet-visible absorption spectrum of the obtained compound is shown in FIG. A dimer formed only by a conventional coordination bond has been dissociated into monomers in a solvent having high polarity such as chloroform solvent containing methanol or pyridine. On the other hand, dimers immobilized by covalent bonds maintain the dimer structure even in those solvents, and it can be seen that the stability has been dramatically improved.

(Note) For A-11a is having two olefinic sites, the olefin site trans / trans, trans / cis, but the possibility of three isomers of cis / cis is considered, two from ¹ H NMR As an isomer (isomer ratio 4/1). These cannot be separated by chromatography or the like, and it is unclear whether they are two kinds of mixtures or three kinds of mixtures. In NMR, the part where the signal was separated into 1 to 4 was assigned as trans, cis for convenience. In the macrocycles with more than 16-membered rings, the trnas body is energetically stable, so the main product is trans. The UV-visible absorption spectrum and fluorescence spectrum were measured using these mixtures. However, since there is no difference in the arrangement of the two porphyrins, it is considered that these electronic properties are hardly different between the mixtures.

¹ H NMR (600 MHz, CDCl ₃ ) δ 0.99 (trans &cis; t, J = 7.2 Hz, 6H; C7), 1.43-1.48 (trans &cis; m, 8H; C6, C5), 1.64 (trans &cis; s, 6H; NCH ₃ ), 1.65-1.69 (trans &cis; m, 4H; C4), 1.94 (trans &cis; br, 2H; CH (imidazole ring)), 1.97-2.03 (trans &cis; m, 4H; C3), 2.70-2.77 (trans &cis; m, 4H; C2), 3.60-3.74 (trans; m, 4Hx4 / 5; ester β), 3.80-3.92 (trans; m, 4Hx4 / 5; ester β), 3.79-3.85 (cis; m, 4Hx1 / 5; ester β), 4.05-4.14 (cis; m, 4Hx1 / 5; ester β), 5.00 (trans; d, J = 10.2 Hz, 2Hx4 / 5 ; O-CH ₂ -C = C), 5.06 (trans; d, J = 10.2 Hz, 2Hx4 / 5; O-CH ₂ -C = C), 5.10 (cis; dd, J = 6.0, 12 Hz, 2Hx1 / 5; O-CH ₂ -C = C), 5.20 (cis; dd, J = 6.0, 12 Hz, 2Hx1 / 5; O-CH ₂ -C = C), 5.22-5.29 (trans &cis; m, 4H; C1), 5.33 (cis; d, J = 4.2 Hz, 4Hx1 / 5; Porβ4), 5.39 (trans; d, J = 4.2 Hz, 4H 4/5; Porβ4), 5.43 (trans &cis; s, 2H; CH (imidazole ring)), 5.42-5.50 (trans &cis; m, 4H; ester α), 6.40 (cis; t, J = 6.0 Hz, 4Hx1 / 5; -CH = C), 6.45-6.47 ( trans; m, J = <1.2 Hz, 4Hx4 / 5; -CH = C), 8.89 (trans; d, J = 4.2 H z, 4Hx4 / 5; Porβ3), 8.91 (cis; d, J = 4.2 Hz, 4Hx1 / 5; Porβ3), 9.63 (trans; d, J = 4.2 Hz, 4Hx4 / 5; Porβ1), 9.67 (cis; d , J = 4.2 Hz, 4Hx1 / 5; Porβ1), 9.75 (trans; d, J = 4.2 Hz, 4Hx4 / 5; Porβ2), 9.75 (cis; d, J = 4.2 Hz, 4Hx1 / 5; Porβ2); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 14.3 (C7), 22.9 (C6), 29.6 (C4), 30.9 (C3), 31.4 (ester α), 32.2 (C5), 32.7 (NCH ₃ ), 36.3 (C1 ), 39.8 (C2), 43.2 (ester β), 58.9 (O- C -C = C; cis), 63.4 (O- C -C = C; trans), 96.0 (C), 116.7 (C; trans) , 116.8 (C; cis), 117.86 & 117.90 (imidazole), 121.61 & 121.65 (imidazole), 122.7 (C; cis), 122.8 (C; trans), 127.32 & 127.37 (Porβ4), 128.2 (Porβ1), 128.6 ( Porβ3; trans), 128.7 (Porβ3; cis), 129.6 (Porβ2), 129.8 (OC- C = C; cis), 130.8 (OC- C = C; trans), 145.9 (C; trans), 146.0 (C; cis), 148.3 (C; cis), 148.4 (C; trans), 148.9 (C; cis), 149.0 (C; trans), 149.60 (C; trans), 149.63 (C; cis), 149.9 (C; cis ), 150.0 (C; trans), 172.5 (C = O; trans), 172.9 (C = O; cis); UV-Vis (CHCl ₃ ): 617 (Abs .; 0.0799), 570 (0.2089), 435 ( 2. 2464), 416 (2.0287), (pyridine): 617 (0.0301), 570 (0.712), 436 (0.8064), 417 (0.7124), (MeOH / CHCl ₃ = 100/1): 615 (0.0045), 566 ( 0.0100), 431 (0.1135), 416 (0.1009) nm; Fluorescence (EX = 435 nm, CHCl ₃ ): 674, 620, (EX = 416 nm, CHCl ₃ ): 673, 620 nm; MALDI-TOF Mass C ₈₂ H ₈₄ N ₁₂ O ₈ Zn ₂ Calcd: 1492.51; Found: 1493.3 (M + H) ⁺ .

Metathesis 1'-trimethylsilyl-ethynyl (A-11b)
Using the same method as A-11a, this compound was added to a ruthenium carbene complex (Grubbs complex A-10) (2 mg, 5 μmol) in a chloroform (5 mL) solution of porphyrin A-9b (40 mg, 52 μmol). ) Was added. The resulting crude product was fractionated by silica gel chromatography (eluent: chloroform / acetone (9: 1)) to obtain A-11b in a yield of 36 mg and a yield of 93%.

(Note) For A-11b are with two olefinic sites, the olefin site trans / trans, trans / cis, but the possibility of three isomers of cis / cis is considered, two from ¹ H NMR As an isomer (isomer ratio 4/1). These cannot be separated by chromatography or the like, and it is unclear whether they are two kinds of mixtures or three kinds of mixtures. In NMR, the part where the signal was separated into 1 to 4 was assigned as trans, cis for convenience. In the macrocycles with more than 16-membered rings, the trnas body is energetically stable, so the main product is trans. The UV-visible absorption spectrum and fluorescence spectrum were measured using these mixtures. However, since there is no difference in the arrangement of the two porphyrins, it is considered that these electronic properties are hardly different between the mixtures.

¹ H NMR (600 MHz, CDCl ₃ ) δ 0.74 (trans &cis; s, 18H; TMS), 1.68 (trans &cis; s, 6H; NCH ₃ ), 2.00 (trans &cis; br, 2H; CH ( imidazole ring)), 3.60-3.73 (trans; m, 4Hx4 / 5; ester β), 3.80-3.89 (trans; m, 4Hx4 / 5; ester β), 3.75-3.82 (cis; m, 4Hx1 / 5; ester β), 4.02-4.10 (cis; m, 4Hx1 / 5; ester β), 5.00 (trans; d, J = 10.2 Hz, 4Hx4 / 5; O-CH ₂ -C = C), 5.07 (trans; d, J = 10.2 Hz, 4Hx4 / 5; O-CH ₂ -C = C), 5.10 (cis; dd, J = 6.0, 12 Hz, 4Hx1 / 5; O-CH ₂ -C = C), 5.20 (cis; dd, J = 6.0, 12 Hz, 4Hx1 / 5; O-CH ₂ -C = C), 5.37 (cis; d, J = 4.2 Hz, 4Hx1 / 5; Porβ4), 5.42 (trans &cis; s, 2H ; imidazole ring)), 5.44 (trans; d, J = 4.2 Hz, 4Hx4 / 5; Porβ4), 5.40-5.41 (trans &cis; m, 8H; ester α), 6.40 (cis; br.t, J = 6.0 Hz, 4Hx1 / 5; -CH = C), 6.45-6.47 (trans; dd, J = <2.0 Hz, 4Hx4 / 5; -CH = C), 8.89 (trans; d, J = 4.2 Hz, 4Hx4 / 5; Porβ3), 8.90 (cis; d, J = 4.2 Hz, 4Hx1 / 5; Porβ3), 9.62 (trans; d, J = 4.2 Hz, 4Hx4 / 5; Porβ1), 9.65 (cis; d, J = 4.2 Hz, 4Hx1 / 5; Porβ1), 9.928 (trans; d, J = 4.2 Hz, 4Hx4 / 5; Porβ2 ), 9.933 (cis; d, J = 4.2 Hz, 4Hx1 / 5; Porβ2); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 0.7 (TMS), 29.8 (TMS- C ≡C-), 31.4 (ester α ), 32.8 (NCH ₃ ), 43.2 (ester β), 59.0 (O- C -C = C; cis), 63.4 (O- C -C = C; trans), 98.8 (C), 99.8 (C; cis ), 99.9 (C; trans), 100.6 (C), 109.0 (C), 118.2 (imidazole), 121.9 (imidazole), 127.8 (Porβ4), 128.5 (Porβ3; cis), 128.6 (Porβ3; trans), 129.0 ( Porβ2), 129.8 (OC- C = C; cis), 130.8 (OC- C = C; trans), 132.0 (Porβ1), 145.4 (C), 147.5 (C; cis), 147.6 (C; trans), 149.8 (C; trans), 149.9 (C; cis), 150.3 (C; cis), 150.4 (C; trans), 152.1 (C; trans), 152.3 (C; cis), 172.3 (C = O; trans), 172.8 (C = O; cis); UV-Vis (CHCl ₃ ): 637 (Abs .; 0.0253), 579 (0.0153), 445 (01505), 425 (0.0930) nm; Fluorescence (EX = 425 nm, CHCl ₃ ): 698, 640 nm; MALDI-TOF Mass C ₇₈ H ₇₂ N ₁₂ O ₈ Si ₂ Zn ₂ Calcd: 1488.37; Found: 1489.1 (M + H) ⁺ .

Metathesis N-methyl-imidazolyl (A-11c)
Using the same method as A-11a, this compound was dissolved in a ruthenium carbene complex (Grubbs complex A-10) (3 mg, 8 μmol) in a chloroform (10 mL) solution of porphyrin A-9c (60 mg, 80 μmol). ) Was added. The obtained crude product was fractionated by silica gel chromatography (eluent: chloroform / acetone (9: 1)) to obtain A-11c in a yield of 36 mg and a yield of 93%.

(Note) For A-11c is with two olefinic sites, the olefin site trans / trans, trans / cis, but the possibility of three isomers of cis / cis is considered, two from ¹ H NMR As an isomer (isomer ratio 4/1). These cannot be separated by chromatography or the like, and it is unclear whether they are two kinds of mixtures or three kinds of mixtures. In NMR, the part where the signal was separated into 1 to 4 was assigned as trans, cis for convenience. In the macrocycles with more than 16-membered rings, the trnas body is energetically stable, so the main product is trans. The UV-visible absorption spectrum and fluorescence spectrum were measured using these mixtures. However, since there is no difference in the arrangement of the two porphyrins, it is considered that these electronic properties are hardly different between the mixtures.

¹ H NMR (600 MHz, CDCl ₃ ) δ 1.64 and 1.65 (s, 6H; NCH ₃ (coordination)), 2.18-2.20 (m, 2H; imidazole ring (coordination)), 3.28 (s, 6H; NCH ₃ ( free)), 3.65-3.77 (m, 4Hx4 / 5; ester β), 3.82-3.94 (m; 4Hx4 / 5; ester β), 3.80-3.90 (m; 4Hx1 / 5; ester β), 4.02-4.15 ( m; 4Hx1 / 5; ester β), 4.95-5.02 (m; 4Hx4 / 5; -CH = C), 5.04-5.08 (m; 4Hx4 / 5; -CH = C), 5.05-5.12 (m; 4Hx1 / 5; -CH = C), 5.18-5.22 (m; 4Hx1 / 5; -CH = C), 5.43 (d, J = 4.2 Hz, 4Hx1 / 5; Porβ4), 5.50 (d, J = 4.2 Hz, 4Hx4 / 5; Porβ4), 5.48-5.55 (m, 8H; ester α), 5.518 (br, 2H; imidazole ring (coordination)), 6.39-6.42 (m, 4Hx1 / 5; -CH = C), 6.47-6.49 (m, 4Hx4 / 5; -CH = C), 7.53 (s, 2H; imidazole ring (free)), 7.84 (s, 2H; imidazole ring (free)), 8.95-9.01 (m, 8H; Porβ2, 3 ), 9.61-9.69 (m, 4H; Porβ1); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 31.4 (ester α), 32.7 (NCH ₃ (coordination)), 34.6 (NCH ₃ (free)), 43.3 ( ester β), 58.9 (O- C -C = C; cis), 63.4 (O- C -C = C; trans), 98.8 (C), 99.5 (C), 117.7 (C), 118.5 (imidazole ring ( coordination)), 121.2 (imidazole ri ng (free)), 122.3 (imidazole ring (coordination)), 128.0 (β4), 128.6 (imidazole ring (free)), 128.7 (Porβ1), 129.6 (Porβ3), 129.8 (Porβ2), 130.8 (OC- C = C; cis), 131.5 (OC- C = C; trans), 145.1 (C), 147.6 (C), 147.7 (C), 150.0 (C), 150.2 (C), 150.8 (C), 172.3 (C = O; trans), 172.7 (C = O; cis); UV-Vis (CHCl ₃ ): 620 (ABS .; 0.0145), 564 (0.0210), 435 (0.1775), 412 (0.01553) nm; Fluorescence (EX = 412 nm, CHCl ₃ ): 681, 624 nm; MALDI-TOF Mass C ₇₆ H ₆₄ N ₁₆ O ₈ Zn ₂ Calcd: 1456.37; Found: 1457.8 (M + H) ⁺ .

Metathesis Ph (A-11d)
Using the same method as A-11a, this compound was added to a ruthenium carbene complex (Grubbs complex A-10) (2 mg, 5 μmol) in a chloroform (15 mL) solution of porphyrin A-9d (30 mg, 40 μmol). ) Was added. The obtained crude product was fractionated by silica gel chromatography (eluent: chloroform / acetone (9: 1)) to obtain A-11d in a yield of 28 mg and a yield of 95%.

(Note) For A-11c is with two olefinic sites, the olefin site trans / trans, trans / cis, but the possibility of three isomers of cis / cis is considered, two from ¹ H NMR As an isomer (isomer ratio 4/1). These cannot be separated by chromatography or the like, and it is unclear whether they are two kinds of mixtures or three kinds of mixtures. In NMR, the part where the signal was separated into 1 to 4 was assigned as trans, cis for convenience. In the macrocycles with more than 16-membered rings, the trnas body is energetically stable, so the main product is trans. The UV-visible absorption spectrum and fluorescence spectrum were measured using these mixtures. However, since there is no difference in the arrangement of the two porphyrins, it is considered that these electronic properties are hardly different between the mixtures.

¹ H NMR (600 MHz, CDCl ₃ ) δ 1.68 (trans &cis; s, 6H; NCH ₃ ), 2.10 (trans &cis; br, 2H; CH (imidazole ring)), 3.65-3.78 (trans; m, 4Hx4 / 5; ester β), 3.80-3.95 (trans; m, 4Hx4 / 5; ester β), 3.87-3.90 (cis; m, 4Hx1 / 5; ester β), 4.05-4.15 (cis; m, 4Hx1 / 5; ester β), 5.00 (trans; d, J = 10.2 Hz, 4Hx4 / 5; O-CH ₂ -C = C), 5.06 (trans; d, J = 10.2 Hz, 4Hx4 / 5; O-CH ₂ -C = C), 5.10 (cis; dd, J = 6.0, 12 Hz, 4Hx1 / 5; O-CH ₂ -C = C), 5.19 (cis; dd, J = 6.0, 12 Hz, 4Hx1 / 5; O-CH ₂ -C = C), 5.39 (cis; d, J = 4.2 Hz, 4Hx1 / 5; Porβ4), 5.47 (trans; d, J = 4.2 Hz, 4Hx4 / 5; Porβ4), 5.48 (trans &cis; br, CH (imidazole ring)), 5.42-5.58 (trans &cis; m, 8H; ester α), 6.40 (cis; t, J = 6.0 Hz, 4Hx1 / 5; -CH = C), 6.47 ( trans; br.s, 4Hx4 / 5; -CH = C), 7.77 (trans &cis; br.t, J = 7.8 Hz, 2H; Ph), 7.87 (trans &cis; br.t, J = 8.4 Hz , 2H; Ph), 7.95 (trans &cis; br.t, J = 7.8 Hz, 2H; Ph), 8.01-8.15 (trans &cis; br, 2H; Ph), 8.65-8.74 (trans &cis; br , 2H; Ph), 8.97 (trans; d, J = 4.2 Hz, 4Hx4 / 5; Porβ3), 8.99 (cis; d, J = 4.2 Hz, 4Hx1 / 5; Porβ3), 9.07 (trans &cis; d, J = 4.2 Hz, 4H; Porβ1), 9.58 (trans; d, J = 4.2 Hz, 4Hx4 / 5; Porβ2), 9.61 ( cis; d, J = 4.2 Hz, 4Hx1 / 5; Porβ2); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 31.4 (ester α), 32.7 (NCH ₃ ), 43.2 (ester β), 58.9 (O- C -C = C; cis), 63.4 (O- C -C = C; trans), 117.3 (C), 118.0 (imidazole), 121.5 (imidazole), 126.2 (Ph), 126.6 (Ph), 127.4 (Ph) , 127.5 (Porβ4), 128.0 (Porβ2), 128.7 (OC- C = C; trans), 128.8 (OC- C = C; cis), 129.8 (Porβ3), 132.8 (Porβ1), 134.6 (Ph), 134.7 ( Ph), 143.8 (C), 148.0 (C), 148.1 (C), 149.5 (C), 149.6 (C), 150.6 (C), 172.4 (C = O; trans), 172.9 (C = O; cis) ; UV-Vis (CHCl ₃ ): 617 (Abs .; 0.079), 565 (0.0124), 436 (0.0739), 413 (0.0722), nm; Fluorescence (EX = 413 nm, CHCl ₃ ): 676, 620 nm; MALDI-TOF Mass C ₈₀ H ₆₄ N ₁₂ O ₈ Zn ₂ Calcd: 1448.36; Found: 1449.47 (M + H) ⁺ .

<Example 2: Corresponding to Scheme 1>
5,15- (methoxycarbonylethyl) -10- (1'-trimethylsilylethynyl) -20- (1``-methyl-2 ''-imidazolyl) porphyrinatozinc (B-1)
To a solution of porphyrin A-6b (120 mg, 0.18 mmol) in chloroform (15 mL) was added a solution of zinc acetate in saturated methanol (5 mL). After stirring at room temperature for 1 hour, water was added to the reaction solution, and the mixture was extracted with chloroform. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain B-1 in a yield of 130 mg. ¹ H NMR (600 MHz, CDCl ₃ ) δ 0.74 (s, 9H; TMS), 1.65 (s, 3H; NCH ₃ ), 1.98 (br.s, 1H; imidazole ring), 3.64-3.81 (m, 4H; ester β), 3.89 (s, 6H; COO Me ), 5.42-5.53 (m, 7H; ester α & imidazole ring & Porβ4), 8.86 (d, J = 5 Hz, 2H; Porβ3), 9.66 (d, J = 5 Hz, 2H; Porβ1), 9.93 (d, J = 5 Hz, 2H; Porβ2); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 0.7 (TMS), 31.0 (ester α), 32.7 (NCH ₃ ) , 42.5 (ester β), 52.1 (COO Me ), 98.7 (meso), 99.8 (TMS-C≡ C- ), 100.4 (TMS- C ≡C-), 109.2 (meso), 118.4 (imidazole ring), 118.5 (meso), 121.9 (imidazole ring), 127.9 (Porβ4), 128.8 (Porβ1), 129.3 (Porβ3), 131.9 (Porβ2), 145.5 (Im NC = N), 147.7 (Porα), 150.0 (Porα), 150.5 ( Porα), 152.0 (Porα), 172.6 (C = O).

5,15-Bis (methoxycarbonylethyl) -10- (ethynyl) -20- (1'-methyl-2'-imidazolyl) porphyrinatozinc (B-2)
A 1 M THF solution of tetrabutylammonium fluoride (0.6 mL) was added to a solution of porphyrin B-1 (130 mg, 0.18 mmol) in chloroform (15 mL). After stirring at room temperature for 30 minutes, water was added to the reaction solution, and the mixture was extracted with chloroform. The organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure to obtain B-2 in a yield of 117 mg. ¹ H NMR (600 MHz, CDCl ₃ ) δ 1.66 (s, 3H; NCH ₃ ), 2.0 (d, J = 1.2 Hz, 1H; imidazole ring), 3.61-3.82 (m, 4H; ester β), 3.90 ( s, 6H; COO Me ), 5.42-5.45 (m, 4H; ester α), 5.45 (d, J = 4.2 Hz, 2H; Porβ4), 5.55 (d, J = 1.2 Hz, 1H; imidazole ring), 8.87 (d, J = 4.2 Hz, 2H; Porβ3), 9.67 (d, J = 4.2 Hz, 2H; Porβ1), 9.95 (d, J = 4.2 Hz, 2H; Porβ2); UV (CHCl ₃ ): 632 (Abs 0.0125), 576 (0.0087), 440 (0.1280), 422 (0.0874) nm; Fluorescence (EX = 440 nm, CHCl ₃ ): 694, 634, (EX = 422 nm, CHCl ₃ ): 691, 635 nm; MALDI-TOF Mass C ₃₄ H ₂₈ N ₆ O ₄ Zn Calcd: 648.15; Found: 649.12 (M + H) ⁺ .

1,4-Bis [10 {5 ', 15'-Bis (methoxycarbonylethyl) -20'-(1 ''-methyl-2 ''-imidazolyl) porphyrinyl}] ethan-1,3-diyne (B-4)
Copper chloride first (89 mg) was added to a solution of porphyrin B-2 (117 mg, 0.18 mmol) in pyridine (20 mL). The reaction solution was stirred while bubbling oxygen at room temperature for 1 hour, water was added, and the mixture was extracted with chloroform. The organic layer was washed with a saturated aqueous EDTA solution, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. An excess amount of p-toluenesulfonic acid monohydrate was added to a chloroform (10 mL) solution of the obtained crude product (porphyrin bis-form B-3) and stirred for 1 hour, and then a saturated aqueous sodium hydrogen carbonate solution was added. Extracted with chloroform. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The resulting crude product was fractionated by silica gel column chromatography (eluent: chloroform / methanol (9: 1)) to obtain B-4 in a yield of 84 mg (40%). MALDI-TOF Mass C ₆₈ H ₅₈ N ₁₂ O ₈ Calcd: 1170.45; Found: 1171.33 (M + H) ⁺ .

1,4-Bis [10 {5 ', 15'-Bis (allyloxycarbonylethyl) -20'-(1 ''-methyl-2 ''-imidazolyl) porphyrinyl}] ethan-1,3-diyne (B-5)
After substituting porphyrin B-4 (80 mg, 68 μmol) and allyl alcohol (93 μL, 1.4 mmol) in toluene (1 mL) with N ₂ , add tin catalyst A-7 (1 mg, 2 μmol). Refluxed at 120 ° C. for 4 hours. The completion of the reaction was confirmed by MALDI-TOF Mass, water was added to the reaction solution, and the mixture was extracted with chloroform. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was fractionated by silica gel chromatography (eluent: chloroform / methanol (10: 1)) to obtain pure B-5 in a yield of 64 mg (80%).

¹ H NMR (600 MHz, CDCl ₃ ) δ -2.82 (s, 4H; inner proton), 3.34 (br.s, 6H; NCH ₃ ), 3.42-3.48 (m, 8H; ester β), 4.68-4.71 ( m, 8H; O-CH ₂ -C = C), 4.94-5.08 (m, 8H; ester α), 5.23 (br.d, J = 7.2 Hz, 4H; -C = CH ₂ ), 5.34 (br. d, J = 16.2 Hz, 4H; -C = CH ₂ ), 5.90-5.98 (m, 4H; -CH = C), 7.52 (br, 2H; imidazole ring), 7.77 (br, 2H; imidazole ring), 8.72 (br, 4H; Porβ), 9.31 (br, 8H; β), 9.89 (br, 4H; Porβ); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 30.5 (ester α), 34.6 (NCH ₃ ), 41.8 (ester β), 65.6 (O- C -C = C), 118.6 (OCC = C ), 121.6 (imdazole ring), 128.5 (Porβ), 128.9 (imidazole ring), 131.4 (Porβ), 132.1 (OC- C = C), 144.5-148.2 (br, 4 carbons (Porα)), 148.3 (Im NC = N), 172.2 (C = O); UV (CHCl ₃ ): 709 (Abs .; 0.0537), 608 (0.0500 ), 474 (0.1542), 445 (0.2224), 433 (0.2186), 415 (0.2085) nm; Fluorescence (EX = 474 nm, CHCl ₃ ): 789, 715 nm; MALDI-TOF Mass C ₇₆ H ₆₆ N ₁₂ O ₈ Calcd: 1274.51; Found: 1275.01 (M + H) ⁺ .

Zn form of B-5 (B-6)
A solution of zinc acetate in saturated methanol (1 mL) was added to a solution of porphyrin B-5 (64 mg, 50 μmol) in chloroform (3 mL). After stirring at room temperature for 1 hour, water was added to the reaction solution, and the mixture was extracted with chloroform. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain B-6 in an equivalent amount of 70 mg. UV (CHCl ₃ ): 731 (Abs .; 0.0161), 669 (0.0063), 582 (0.0036), 501 (0.0296), 462 (0.0188), 429 (0.0171) nm; Fluorescence (EX = 501 nm, CHCl ₃ ) : 817, 740 nm; MALDI-TOF Mass C ₇₆ H ₆₂ N ₁₂ O ₈ Zn ₂ Calcd: 1398.34; Found: 1399.21 (M + H) ⁺ .

B-7
A solution of zinc porphyrin B-6 (70 mg, 50 μmol) in chloroform (2 mL) was substituted with N _{2, and} then a ruthenium carbene complex (1 mg, 10 μmol) was added. After stirring at room temperature for 3 hours, water was added to the reaction solution, and the mixture was extracted with chloroform. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was fractionated by silica gel chromatography (eluent: chloroform / methanol (9: 1)) to obtain immobilized B-7 in a yield of 54 mg. As a result of analyzing the obtained B-7 by size exclusion column chromatography (JAIGEL-2.5HA), the chromatogram shown in FIG. 2 was obtained. As a result of comparison with polystyrene standards, it was found that a multimer with a distribution maximum around 20,000 molecular weight was generated. The results of MALDI-TOF mass spectrometry analysis of B-7 are shown in FIG. Since this compound undergoes a carbon-carbon bond cleavage reaction at the bisacetylene site during mass spectrometry, a peak is observed in the molecular weight corresponding to a multiple of the porphyrin unit, and the peak reaches 6000 or more. The peak around the molecular weight 6742 corresponds to the porphyrin decamer. On the other hand, since no fragment peaks of 2000 or more were observed at all in B-6 before immobilization, it is apparent that the stability was increased by immobilization. In addition, when the ultraviolet-visible absorption spectrum of B-7 in pyridine was measured, it was found that the tissue structure was maintained.

  Figures 4, 5 and 6 respectively show the UV-vis absorption spectrum (UV-vis spectrum) of the polymer B-7 after immobilization in chloroform and the UV-vis absorption spectrum of the polymer B-7 after immobilization in pyridine. It is an ultraviolet-visible absorption spectrum (UV-vis spectrum) in pyridine of B-6 before immobilization. Unimmobilized zinc porphyrin B-6 is completely dissociated into monomers in pyridine, and the large absorption peak at 453 nm in FIG. 6 is a peak characteristic of this monomer. On the other hand, in the immobilized multimer B-7, this peak is not large even in pyridine (FIG. 5), and it can be seen that it is similar to the spectrum in chloroform (FIG. 4). This indicates that the immobilized multimer exists while maintaining the multimeric structure even in a polar solvent, and it has become possible to provide a sample that can withstand functional evaluation in a polar environment.

GPC (CHCl ₃ , flow rate: 1.25 mL / h, detected 459.82 nm) 9.936 min; UV (CHCl ₃ ): 731 (Abs .; 0.0163), 581 (0.0081), 500 (0.0364), 460 (0.0328), 427 (0.0368); (pyridine): 727 (0.0078), 665 (0.0066), 579 (0.0055), 492 (0.0212), 456 (0.0280), 433 (0.0272) nm; Fluorescence (EX = 501 nm, CHCl ₃ ): 817, 740 nm; MALDI-TOF Mass Calcd .: 1346 (monomer), 2692 (dimer), 4038 (trimer), 5384 (tetramer), 6730 (pentamer); Found: 1346, 2692, 4039, 5388, 6742.

<Example 3: Corresponding to Scheme 2>
H2-Pre-gable C-1
5- (N-methylimidazol-2-yl) -10, 15-bis (methoxycarbonylethyl) -20- (3-formylphenyl) -porphyrin
0.9 g (8.18 mmol) N-methylimidazole-2-carbaldehyde, meso- (methoxycarbonylethyl) dipyrromethane A-4 4.0 g (17.23 mmol), isophthalaldehyde 1.15 g (8.61 mmol) in a 2 L four-necked flask Then, 1.7 L of chloroform was added. After bubbling nitrogen for 5 minutes, 5.97 mL (77.5 mmol) of trifluoroacetic acid was slowly added. After stirring for 5 hours under shading, 11.78 mL (77.5 mmol) of triethylamine and 4.76 g (19.38 mmol) of p-chloranil were added and stirred overnight. After the reaction solution was concentrated, it was purified by column chromatography (silica gel, developing solvent chloroform → chloroform / acetone 1/2). Recrystallization from chloroform / hexane gave 140 mg (2.4%) of purple powder C-1.

¹ H NMR (CDCl ₃ , 600 MHz) δ 10.34, 10.33 (each s, 2H, CHO, split due to atropisomers), 9.51, 9.47, 8.83 and 8.80 (each d, J = 4.86 and 5.40, 8H), 8.72, 8.63 (each s, 1H, phenyl-H ₂ ), 8.49, 8.39 (each d, J = 7.2 Hz, 1H, phenyl-H ₆ ), 8.37 (d, J = 7.2 Hz, 1H, phenyl-H ₃ ), 7.97 (m, 1H, phenyl-H ₅ ), 7.69 (s, 1H, imidazole-H ₄ ), 7.50 (s, 1H, imidazole-H ₅ ), 5.34 (t, J = 8.4 Hz, 4H, α-CH ₂ ), 3.75 (each s, 6H, COOMe), 3.51 (t, J = 8.4 Hz, 4H, β-CH ₂ ), 3.43, 3.42 (each s, 3H, N-Me), -2.74 (s, 2H MALDI MS (dithranol): m / z = 667.64 (cald. 666.26), UV-vis (CHCl ₃ ; λ _max , nm (relative intensity)): 418.0 (1.00), 515.0 (0.063), 549.5 (0.023), 592.0 (0.020), 648.5 (0.010) .Fluorescence, λ _ex = 418.0 nm, (CHCl ₃ , λmax, nm (relative intensity)): 652.8 (1.00), 718.4 (0.41).

H2-COOMeGable C-2
Pre-gable porphyrin C-1 30 mg (45 μmol), meso- (methoxycarbonylethyl) dipyrromethane 52.2 mg (2.3 × 10 ⁻⁴ mol) and chloroform 23 mL were added to a 100 mL eggplant-shaped flask, and nitrogen was bubbled for 5 minutes. TFA 27.7 μL (3.6 × 10 ⁻⁴ mol) was added, and the mixture was stirred for 11 hours under light shielding. Then, N-methylimidazole-2-carbaldehyde dissolved in 0.5 mL of chloroform was added, and the mixture was further stirred for 6 hours. 2,3-dicyano-5,6-dichlorobenzoquinone 40.8 mg (18.0 × 10 ^-5 mol) was added and stirred overnight, and the reaction solution was washed twice with a saturated aqueous sodium bicarbonate solution and once with water. The organic layer was dehydrated over anhydrous sodium sulfate, dried, dissolved in chloroform and filtered through celite. Purification by GPC chromatography (Column: TOSOH G2500HHR, Eluent: Chloroform / Methanol = 10/1) gave 53 mg (22%) of the target compound C-2.

¹ H NMR (CDCl ₃ , 600 MHz) δ 9.62 and 9.39 (each m, 4H × 2, pyrrole-H _β ), 9.46 (br, 4H, pyrrole-H _β ), 9.21, 9.03 and 8.88 (each s, 1H , phenyl-H ₂ ), 8.78 (br, 4H, pyrrole-H _β ), 8.69, 8.57 (d, J = 7.2 Hz 1H, phenyl-H _{4 (6)} ), 8.19 (m, 1H, phenyl-H ₅ ), 7.69 (m, 2H, imidazole-H ₄ ), 7.49 and 7.47 (each s, 2H, imidazole-H ₅ ), 5.33 (m, 8H, α-CH ₂ ), 3.747 (s, 12H, COOMe), 3.50 (m, 8H, β-CH ₂ ), 3.40 and 3.33 (each s, 6H, N-methyl), -2.72 (s, 4H, inner-NH). MALDI MS (dithranol): m / z = 1200.29 ( cald. 1199.48) .UV-vis (CHCl ₃ ; λ _max , nm (relative intensity)): 413.5 (1.000), 429.0 (0.940), 515.5 (0.096), 550.0 (0.035), 590.5 (0.026), 649.0 (0.018 Fluorescence, λ _ex = 413.0 nm, (CHCl ₃ , λmax, nm (relative intensity)): 653.5 (1.00), 717.6 (0.48).

H2-AllylGable C-3
21.2 mg (17.7 μmol) of H2-COOMeGable porphyrin C-2 was dissolved in 12 mL of a 1: 1 mixture of toluene / allyl alcohol, and Sn catalyst A-7 (synthesized according to the method of Otera et al. Was used. Junzo Otera, Nobuhisa Dan-oh, Hitosi Nozaki, J. Org. Chem. 1991, 56, 5307-5311) 9 mg (17.7 μmol) was added and refluxed for 12 hours. The organic layer was washed with water and purified by silica gel chromatography (developing solution chloroform / methanol = 10/1) to obtain 18.3 mg (79%) of a purple solid C-3.

¹ H NMR (CDCl ₃ , 600 MHz) δ 9.64 and 9.50 (br.s, 4H, pyrrole-H _β ), 9.40 (m, 4H, pyrrole-H _β ), 9.18, 9.03 and 8.92 (each s, 1H, phenyl-H ₂ , split due to atropisomerization), 8.81 (br. s, pyrrole-H _β ), 8.68 (br, 1H, phenyl-H _{4 (6)} ), 8.58 (d, J = 7.2 Hz, 1H, phenyl -H _{4 (6)} ), 8.18 (m, 1H, phenyl-H ₅ ), 7.68 (br. S, 2H, imidazole-H ₄ ), 7.49 and 7.47 (each s, 2H, imidazole-H ₅ ), 5.90 (m, 4H, -CH = C), 5.37 (m, 4H, α-CH ₂ ), 5.30 (d, J = 13.8 Hz, H _trans in ethylene), 5.19 (d, J = 10.8 Hz, H _cis in ethylene), 4.69 (s, 8H, OCH ₂ ), 3.55 (m, 8H, β-CH ₂ ), 3.42 and 3.37 (each s, 6H, N-methyl), -2.67 (s, 4H, inner-NH) MALDI MS (dithranol): m / z = 1304.51 [M + 1] ⁺ , (cald. 1303.47)
UV-vis (CHCl ₃ ; λ _max , nm (relative intensity)): 414.5 (1.000), 428.5 (0.885), 516.0 (0.103), 551.0 (0.045), 591.0 (0.034), 649.0 (0.021). Fluorescence, λ _ex = 414.0 nm, (CHCl ₃ , λmax, nm (relative intensity)): 654 (1.00), 718.8 (0.36)

Zn-Allylgable C-4
22.7 mg (1.74 × 10 ⁻⁵ mol) of H2-AllylGable porphyrin C-3 was dissolved in 8 mL of chloroform. To this, 38 mg (1.74 × 10 ⁻⁴ mol) of zinc acetate dihydrate dissolved in 1 mL of methanol was added and stirred at room temperature for 12 hours. The organic layer was washed with water and dried to quantitatively obtain 24.5 mg of the target zinc complex C-4.

MALDI MS (dithranol): m / z = 1431.75 [M + 1] ⁺ , (cald. 1430.21)
UV-vis (CHCl ₃ ; λ _max , nm (relative intensity)): 411.0 (1.000), 447.0 (0.913), 567.0 (0.138), 618.0 (0.072). Fluorescence, λ _ex = 411.0 nm, (CHCl ₃ , λmax , nm (relative intensity)): 622.5 (1.00), 669.0 (0.29)

Zn-Allylgable C-5 (Reorganization)
Zn-AllylGable porphyrin C-4 24.5 mg (1.74 × 10 ⁻⁵ mol) was dissolved in a mixed solvent of chloroform 45 mL / methanol 45 mL and stirred for 5 minutes. Thereafter, the solvent was slowly distilled off with an evaporator to obtain 24.5 mg of a mixture mainly containing cyclic Zn-AllylGable porphyrin C-5a and C-5b. FIG. 7 shows the results of GPC analysis of a mixture mainly containing C-4 before reorganization and C-5 after reorganization.

Cyclic-Zngable C-6a, C-6b
Zn-Allylgable C-5 7.4 mg (5.18 μmol), 10 mL chloroform, Grubbs's catalyst A-10 (Fluka 09587 Benzylidene-bis (tricyclohexyiphosphine) -dichlororuthenium was purchased and used in a 20 mL flask) 4.3 mg (5.1 mmol) and stirred for 12 hours under a nitrogen atmosphere, and then the reaction solvent was distilled off under reduced pressure. Purified by column chromatography (developing solvent: chloroform / methanol = 10/1), GPC chromatography (Column: TOSOH G3000HHR, Eluent: Chloroform / Methanol = 10/1), and ring-shaped porphyrin pentamer C-6a, 6 Each of the monomer C-6b was purified.

  FIG. 8 shows the results of GPC chromatography analysis of the mixture mainly containing C-6a and C-6b before purification and the isolated C-6a and C-6b after purification.

  9 and 10 are ultraviolet-visible absorption spectra of cyclic pentamer C-6a and hexamer C-6b in chloroform and pyridine, respectively. It can be seen that the immobilized cyclic pentamer C-6a and hexamer C-6b stably maintain a cyclic structure even in a polar solvent such as pyridine.

  11 and 12 are mass spectrometry spectra of the immobilized cyclic multimers C-6a and C-6b, respectively. The cyclic multimer formed by the coordination bond was dissociated in the mass spectrometer and did not give a signal corresponding to the molecular weight of the multimer. On the other hand, in the immobilized cyclic multimers C-6a and C-6b, porphyrin 10-mer (molecular weight 6870.5) and 12-mer (molecular weight 8245.5) are clearly observed, and a dramatic improvement in stability is seen. It was.

5-mer C-6a
1.0 mg (14%)
MALDI MS (dithranol): m / z = 6871.66 (cald. 6870.54).
UV-vis (CHCl ₃ ; λ _max , nm (relative intensity)): 410.5 (1.000), 445.5 (1.017), 567.5 (0.144), 618.5 (0.072), (pyridine, λ _max , nm (relative intensity)): 411.5 (1.000), 446.0 (1.033), 568.5 (0.141), 619.0 (0.076) .Fluorescence (λ _ex = 410.0 nm, CHCl ₃ , λmax, nm (relative intensity)): 622.0 (1.00), 673.8 (0.44)
6-mer C-6b
0.7 mg (9.8%)
MALDI MS (dithranol): m / z = 8245.51 (cald. 8244.65).
UV-vis (CHCl ₃ ; λ _max , nm (relative intensity)): 410.5 (1.000), 447.0 (0.973), 567.5 (0.1473), 618.5 (0.077), (pyridine, λ _max , nm (relative intensity)): 412.0 (1.000), 447.5 (1.029), 568.5 (0.141), 619.0 (0.079) .Fluorescence (λ _ex = 411.0 nm, CHCl ₃ , λmax, nm (relative intensity)): 622.0 (1.00), 665 (shoulder) ( 0.34). (Λ _ex = 412.0 nm, pyridine, λmax, nm (relative intensity)): 623 (1.00), 673.2 (0.35)

<Example 4: Example using combination of porphyrin metal complex and phenylene as divalent linking group>
1. Synthesis of raw material porphyrin 1

A 1000 mL three-necked flask was charged with dipyrromethane (2.36 g, 9.66 mmol), imidazole aldehyde (532 mg, 4.83 mmol), protected benzaldehyde (1.38 g, 6.28 mmol), and chloroform (1 L), and purged with nitrogen. . Trifluoroacetic acid (hereinafter TFA: 1.12 mL, 0.0145 mol) was added thereto and stirred at room temperature for 4 hours. Chloranil (3.7 g, 0.015 mol) was added and stirred overnight at room temperature. The reaction solution was neutralized with triethanolamine (TEA: 2.36 mL, 0.0169 mol), and the solvent was concentrated. This concentrated solution was passed through a celite column (φ4.5 × 10 cm) to remove insoluble components. Elution with 20% Acetone / CHCl ₃ excluding black tar-like components on silica gel column (1, 2nd φ4.5 × 20 cm, 3rd φ3.3 × 20 cm; CHCl ₃ → 20% Acetone / CHCl ₃ ) The second red fraction was concentrated to dryness and vacuum dried to obtain a purple solid. It was confirmed by TLC, MALDI-MS, and ¹ H NMR spectra that the desired product was obtained. Yield 379.4 mg (10%, 0.49 mmol)

¹ H NMR (270 MHz, CDCl ₃ ): δ9.509, 9.455, 8.861, 8.732 (d, 2H; d, 2H; d, 2H; d, 2H, β-pyrrole), 8.304 (d, 1H, PhH-2 ), 8.158 (dd, 1H, PhH-6), 7.997 (d, 1H, PhH-4), 7.777 (q, 1H, PhH-5), 7.676 (d, 1H, ImH-4), 7.448 (d, 1H, ImH-5), 5.999-6.143 (m, 2H, -CH = CH ₂ ), 5.677 (d, 1H, acetalCH), 5.408, 5.253 (dq, 2H; dq, 2H, -CH = CH ₂ ), 5.078 (t, 4H, H-α), 4.061 (m, 4H, -O-CH ₂ -CH =), 3.794 (dq, 4H, acetalCH ₂ ), 3.644 (t, 4H, H-γ), 3.398 ( d, 3H, ImN-CH ₃ ), 2.775 (m, 4H, H-β), 1.353 (d, 4H, acetalCH ₃ ), 0.810 (d, 4H, acetalCH ₃ ), -2.790 (s, 2H, NH) . Mass spectrometry (MALDI-TOF) Measured value 776.19 for [M + H] ⁺ , calculated value 776.41

2. Deprotection of raw material porphyrin 1

Porphyrin 1 (146 mg, 0.188 mmol), TFA (5 mL), acetic acid (10 mL) and 5% H ₂ SO ₄ aqueous solution (2.5 mL) were placed in a 100 mL flask and stirred at 70-80 ° C. for 30 minutes. The resulting porphyrin was neutralized with aqueous NaHCO ₃ and extracted with CHCl ₃ . The CHCl ₃ layer was washed three times with water and passed through a silica gel short column (10-20% acetone / CHCl ₃ ). The purple band was collected and the solvent was distilled off to obtain a purple solid. NMR confirmed that the desired product was obtained. Yield: 117 mg (90%, 0.170 mmol).

¹ H NMR (600 MHz, CDCl ₃ ): 10.3 (d, 1H, CHO), 9.54, 9.49, 8.80, 8.74 (d, 2H; d, 2H; d, 2H; d, 2H, β-pyrrole), 8.67 (d, 1H, Ph H-2), 8.42 (dd, 1H, Ph H-6), 8.34 (m, 1H, Ph H-4), 7.90-7.95 (m, 1H, Ph H-5), 7.69 (s, 1H, Im H-4), 7.47 (s, 1H, Im H-5), 6.04 to 6.10 (m, 2H, -CH =), 5.41, 5.25 (d, 2H; d, 2H, = CH ₂ ), 5.09 (t, 4H, H-α), 4.07 (m, 4H, -OCH _2- ), 3.64 (t, 4H, H-χ), 3.39 (d, 3H, NMe), 2.78 (t, 4H, H-β), -2.68 (s, 2H, NH). Mass spectrometry (MALDI-TOF) Measured value 690.31, calculated value 690.33 for [M + H] ⁺

3. Synthesis of Saddle porpyrin3

Porphyrin 2 (79 mg, 0.114 mmol), dipyrromethane (40 mg, 0.172 mmol) and chloroform (23 mL) were placed in a 50 mL flask, and the system was replaced with nitrogen. TFA (44 μl, 0.57 mmol) was added dropwise thereto, and the mixture was stirred for 22 hours under nitrogen in the dark. TEA (83 μl, 0.593 mmol) and chloranil (85 mg, 0.342 mmol) were added and stirred for 5 hours. The crude product after the reaction was purified with a silica gel column (3 times). The eluate was concentrated and reprecipitated with hexane. Yield: 20 mg (20%). Mass spectrometry (MALDI-TOF) Measured value 1802.81 and calculated value 1802.84 for [M + H] ⁺ .

4). Introduction of Zn ²⁺ into Saddle porpyrin 3

Zinc acetate (60 mg, 0.277 mmol) and methanol (1 mL) were placed in a 20 mL eggplant-shaped flask, and a chloroform solution (8 mL) of porphyrin 3 (10 mg, 5.54 μmol) was added thereto. After stirring at room temperature for 3 hours, the chloroform solution was washed with water. The resulting insoluble solid was filtered to separate the insoluble solid. The insoluble solid was dissolved in pyridine and added to the chloroform layer, concentrated and dried in vacuo. 10.5 mg (95%). Mass Spectrometry (MALDI-TOF) Measured value for 1991.58 for [M + H] ⁺ , calculated value for 1988.58.

5. Reorganization

A 300 mL eggplant-shaped flask was charged with 10.5 mg of porphyrin, 250 mL of chloroform, and 30 mL of methanol and allowed to stand for 2 days (chloroform / methanol = 9/1, porphyrin 0.02 mM). After standing, reprecipitation was performed with hexane. As a result of GPC analysis of the obtained sample, a very converged peak was obtained (see FIG. 13). From the NMR measurement results, it was found that it was a mixture of two isomers of Symmetric and Asymmetric having the same ring size (see FIG. 14).

6). Ring 5 metathesis reaction

Porphyrin 5 (1 mg, 5.01 × 10 ^-4 mmol) and chloroform (2.5 mL) were placed in a 20 mL eggplant flask and the system was replaced with nitrogen. Grubb's catalyst (about 0.2 mg) was added here, and stirring was continued for 2 hours. A time-of-flight paper mass spectrometer confirmed that the reaction had progressed completely. After stirring, it was washed with water, and the organic layer was concentrated and vacuum-dried. It was confirmed that the structure was retained by GPC and absorption spectrum (see FIG. 15). Mass spectrometry (MALDI-TOF) [M + H] ⁺ Measured value 5796.34, calculated value 5797.55.

  Fig. 13 shows the results of analysis of porphyrin 5 obtained after reorganization using analytical GPC (JAIGEL-3HA column / chloroform). The sharp peak does not change before and after reorganization. Slightly higher molecular weight components disappeared after reorganization.

  600 MHz NMR (deuterated chloroform) of porphyrin 5 obtained after reorganization. Assuming that it is a mixture of two isomers of the same ring size (see FIG. 14), all peaks could be assigned.

  Fig. 15 shows the results of mass analysis (MALDI-TOF) of Macroring 6 in which the structure of the metathesis reaction is immobilized by a covalent bond. From this figure, it can be seen that compound 6 is a single molecule with a ring-shaped structure in which three molecules of Saddle porpyrin 4 are organized, and that the ring structure of macro ring 5 is maintained after metathesis.

  From the GPC (JAIGEL-3HA column / chloroform) analysis results before and after the metathesis reaction (see FIG. 16), it can be seen that the organized structure is retained before and after the metathesis, and it can be estimated that the macroring structure is also before the metathesis.

<Example 5: Example using a combination of a porphyrin metal complex and ferrocene as a divalent linking group according to Scheme 4 below>

1,1'-ferrocenedialdehyde
It was synthesized and used according to the report of GGA Balavoine et al. GGA Balavoine; G. Doisneau; T. Fillebeen-Khan. J. organomet. Chem. 1991, 412, 381-382
It was synthesized and used according to meso- (n-heptyl) dipyrromethane literature (Y. Tomohiro, A. Satake, Y. Kobuke, J. Org. Chem. 2001, 66, 8442-8446).

5- (1'-formylferrocenyl) -15- (1-methylimidazol-2-yl) -10,20-bis (2-metoxycarbonylethyl) porphyrin (1)
In 1 L of chloroform, meso- (methoxycarbonylethyl) dipyrromethane (930 mg, 4.0 mmol), 1-methyl-2-formylimidazole (220 mg, 2.0 mmol), 1,1′-ferrocenedialdehyde (726 mg, 3.0 mmol) ), And the reaction solution was purged with nitrogen, and trifluoroacetic acid (0.60 mL, 8.0 mmol) was added and stirred at room temperature for 3.5 hours. After adding triethylamine (1.11 mL, 8.0 mmol), 2,3,5,6-tetrachloro-1,4, -benzoquinone (1.48 g, 6.0 mmol) was added and stirred at room temperature for 5 hours. After concentrating the reaction solution to 300 mL with a rotary evaporator, fractionating by silica gel column chromatography (eluent: chloroform / acetone (10: 1)) twice and alumina column chromatography (eluent: chloroform). Yield 78 mg, 5.0% yield.

¹ H-NMR (CDCl ₃ , 600 MHz): δ 9.92 (2H, s, pyrrole-βH), 9.91 (1H, s, CHO), 9.41 (d, 4H, J = 4.76 Hz, pyrrole-βH), 8.78 ( s, 2H, pyrrole-βH), 7.67 (d, 1H, J = 1.47 Hz, imidazole-H ₄ ), 7.45 (d, 1H, J = 1.47 Hz, imidazole-H ₅ ), 5.55, 4.95, 4.83, and 4.42 (t, 2H, J = 1.22 Hz, Cp), 5.25 (t, 4H, J = 8.42 Hz, α-CH ₂ ), 3.77 (s, 6H, -OCH ₃ ), 3.49 (t, 4H, J = _{. 8.24 Hz, β-CH 2} ), 3.38 (s, 6H, N-CH 3), -2.40 (s, 2H, inner-NH) 13 C-NMR (CDCl 3, 150MHz): δ 193.7 (C, CHO ), 173.0 (C, C = O), 137-153 (br.CH, pyrrole-α), 148.2 (C, imidazole-C ₂ ), 123-133 (br.CH, pyrrole-β), 128.6 (CH , imidazole-C ₄ ), 121.6 (CH, imidazole-C ₅ ), 117.6, 116.2, 105.0 (C, meso), 91.7, 79.8 (C, Cp), 78.4, 76.7, 71.6, 70.4 (CH, Cp), 51.9 (CH ₃ , -OCH ₃ ), 41.6 (CH ₂ ), 34.5 (CH ₃ , N-CH ₃ ), 30.5 (CH ₂ ). MS (MALDI-TOF, dithranol): Found m / z 775.29 [M + H] ⁺ , calculated for C ₄₃ H ₃₈ FeN ₆ O ₅ 774.23. UV-vis (λ _abs, CHCl ₃ ): 424, 521, 576, 670.5 nm

5,15-bis [1 '-[15 ”-(1-methylimidazol-2-yl) -10”, 20 ”-bis (2-metoxycarbonylethyl) porphyrin-5” -yl] ferrocenyl] -l0,20-bis (n-heptyl) porphyrin (2)
To 500 mL of chloroform, meso- (n-heptyl) dipyromethane (110 mg, 0.45 mmol) and porphyrin (2) (350 mg, 0.45 mmol) were added, and the reaction solution was purged with nitrogen, and then trifluoroacetic acid (0.17 mL, 2.3 mmol) and stirred at room temperature for 3 hours. The reaction solution was concentrated to 100 mL with a rotary evaporator over 1 hour, stirred for 1 hour at room temperature, and then added with triethylamine (0.32 mL, 2.3 mmol). 2,3,5,6-Tetrachloro-1,4, -benzoquinone (388 mg, 1.6 mmol) was added and stirred at room temperature for 30 minutes. Separation with silica gel column chromatography (eluent: chloroform / acetone (1: 1)) and silica gel column chromatography (eluent: chloroform / acetone (5: 1)) twice to yield 205 mg, 45% The yield was obtained.

¹ H-NMR (CDCl ₃ , 600MHz): δ 9.90, 9.69, 9.17, 8.69, 8.43 (s, 4H, 4H, 4H, 8H, 4H, respectively, pyrrole-βH), 7.72 (s, 2H, imidazole-H ₄ ), 7.45 (s, 2H, imidazole-H ₅ ), 5.55 (s, 8H, Cp), 4.83 and 4.81 (s, partially overlapped each other, 4H, Cp), 4.71 (s, 8H, α-CH ₂ ), 3.74 (br, 4H, alkyl-α-CH ₂ ), 3.65 (s, 12H, -OCH ₃ ), 3.33 (s, 6H, N-CH ₃ ), 3.09 (s, 8H, β-CH ₂ ) , 1.78 (s, 4H, alkyl-β-CH ₂ ), 1.13-1.33 (m, 16H, alkyl), 0.86 (t, 6H, J = 4.76 Hz, alkyl-CH ₃ ), -2.38, -2.66 (s , 2H, 4H, respectively, inner -NH) 13 C-NMR (CDCl 3, 150MHz):.. δ 172.9 (C, C = O), 148.5 (C, imidazole-C 2), 138-153 (br CH , pyrrole-α), 128.5 (CH, imidazole-C ₄ ), 124-134 (br.CH, pyrrole-β), 121.5 (CH, imidazole-C ₅ ), 119.3, 118.3, 117.1, 114.5, 104.2 (C , meso), 91.6, 91,3 (C, Cp), 79.6, 78.8, 71.8 (CH, Cp), 51.7 (CH ₃ , -OCH ₃ ), 41.2, 37.8, (CH ₂ ), 34.8 (CH ₃ , N-CH ₃ ), 34.3, 31.9, 30.1, 30.0, 29.1, 22.6 (CH ₂ ), 14.1 (CH ₃ ). MS (MALDI-TOF, dithranol): Found m / z 1995.78 [M + H] ⁺ , calculated for C ₁₁₈ H ₁₁₄ Fe ₂ N ₁₆ O ₈ 19 94.77.UV-vis (λ _abs, CHCl ₃ ): 421, 613.5, 701.5nm

5,15-bis [1 '-[15 "-(1-methylimidazol-2-yl) -10", 20 "-bis (2-metoxycarbonylethyl) porphyrinatozinc (II) -5" -yl] ferrocenyl] -l0, 20-bis (n-heptyl) porphyrinatozinc (II) (3).
To a solution of porphyrin (2) (110 mg, 55 μmol) in chloroform (275 mL) was added a saturated methanol solution of zinc acetate (20 mL), and the mixture was stirred at room temperature for 15 minutes. Extracted. The organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure. By fractionating with silica gel column chromatography (eluent: chloroform), the yield was 106 mg and the yield was 95%. MS (MALDI-TOF, dithranol): Found m / z 2181.51 [M + H] ⁺ , calculated for C ₁₁₈ H ₁₀₈ Fe ₂ N ₁₆ O ₈ Zn ₃ 2180.51. UV-vis (λ _abs, CHCl ₃ ): 420, 440.5, 538, 652.5nm

[The invention's effect]
As described above, the porphyrin multimer represented by the general formulas (1) and (2) of the present invention is immobilized by a covalent bond in addition to a coordination bond, so that a large amount even in a polar solvent. Body structure can be maintained. This makes it possible to provide a sample that can withstand the functional evaluation of porphyrin multimers in a polar environment.

  In addition, the method for producing a porphyrin multimer of the present invention is economical because the porphyrin multimer can be extended with relatively few synthesis steps. Moreover, according to the method for producing a porphyrin multimer of the present invention, it is considered possible to synthesize a multimer having hundreds of porphyrin units, which has been difficult in the past.

FIG. 1 is an ultraviolet-visible absorption spectrum of Compound A-11a. In the figure, solid line: in chloroform, thick line: methanol / chloroform (100/1), dotted line: in pyridine. FIG. 2 shows GPC chromatography of the compound B-7 (column JAIGEL-2.5HA manufactured by Nippon Analytical Industry, eluent: chloroform, flow rate: 1.2 mL / min). In the figure, the broad peak (maximum peak 9.6 minutes) is the result of Compound B-7. Sharp peaks at retention times of 8.6 minutes (molecular weight 44000), 9.6 minutes (molecular weight 21000), 11.2 minutes (molecular weight 7000), 12.0 minutes (molecular weight 3790), 12.6 minutes (molecular weight 2090), 13.5 minutes (molecular weight 920) are polystyrene. The standard substances analyzed under the same conditions were superimposed and displayed. FIG. 3 shows a MALDI-TOF mass spectrometry spectrum (matrix: dithranol) of Compound B-7. In the figure, molecular weight peaks 1346, 2698, 4039, 5388, and 6742 correspond to fragment peaks in which the carbon-carbon triple bond of polyacetylene is cleaved under the measurement conditions. Each porphyrin unit is 2, 4, 6, 8, 10 pieces. FIG. 4 shows an ultraviolet-visible absorption spectrum of multimer B-7 (solvent: in chloroform). FIG. 5 shows an ultraviolet-visible absorption spectrum of multimer B-7 (solvent: in pyridine). FIG. 6 is an ultraviolet-visible absorption spectrum of zinc porphyrin B-6 (solvent: in pyridine). FIG. 7 shows GPC chromatography before and after reorganization of multimeric C-5 (column JAIGEL-3HA manufactured by Nippon Analytical Industry, eluent: chloroform, flow rate: 1.2 mL / min).

In the figure, the bold line is the sample before reorganization. The solid line is the sample after reorganization. After reorganization, the chromatographic linewidth is narrowed.
FIG. 8 shows GPC chromatography of the multimeric C-6a and C-6b isolated and purified after the metathesis reaction (column: JAIGEL-3HA manufactured by Nippon Analytical Industry, eluent: chloroform, flow rate 1.2 mL / min). In the figure, bold line: C-6a (6 mer), solid line: C-6b (5 mer), dotted line: sample before isolation and purification. FIG. 9 shows an ultraviolet-visible absorption spectrum of compound C-6a. In the figure, bold line: in chloroform, solid line: in pyridine. FIG. 10 is an ultraviolet-visible absorption spectrum of compound C-6b. In the figure, bold line: in chloroform, solid line: in pyridine. FIG. 11 is a MALDI-TOF mass spectrometry spectrum (matrix: dithranol) of compound C-6a. FIG. 12 shows a MALDI-TOF mass spectrometry spectrum (matrix: dithranol) of compound C-6b. FIG. 13 shows GPC for analysis of porphyrin 5 obtained after reorganization (JAIGEL-3HA column / chloroform). FIG. 14 shows 600 MHz NMR (deuterated chloroform) of porphyrin 5 obtained after reorganization. FIG. 15 is a mass analysis (MALDI-TOF) of Macroring 6 in which a structure by a metathesis reaction is immobilized by a covalent bond. FIG. 16 shows GPC (JAIGEL-3HA column / chloroform) before and after the metathesis reaction.

Claims (24)

A linear porphyrin multimer comprising a coordination heteroaromatic ring-substituted porphyrin metal complex immobilized by a covalent bond represented by the following general formula (1) as a structural unit.

{Where,
R is an alkyl group or

(Wherein a, b and d each independently represents H, an alkyl group or an aryl group),
X represents —O—, —S—,> NR ₁₀₁ (wherein R ₁₀₁ represents H or an alkyl group), CH ₂ or a single bond;
Y represents = O, = S or 2H;
m represents an integer of 0 to 4,
X ₁ represents a divalent linking group,
Z represents a 5- or 6-membered nitrogen-containing coordinated heteroaromatic ring group,
M represents a metal ion selected from typical metals and transition metals;
Q ₁ represents a single bond or a linear divalent linking group,
p ₁ represents an integer of 2 or more. } A linear polyphyllin multimeric derivative represented by the following general formula (1-1).

{Where,
R, X, Y, m, X ₁ , Z, M, Q ₁ and p ₁ are as defined in claim 1;
e and f simultaneously represent H or a hydroxyl group, or e and f are bonded to each other to form an epoxy ring together with C—C to which they are bonded. } A cyclic porphyrin multimer comprising a coordination heteroaromatic ring-substituted porphyrin metal complex immobilized by a covalent bond represented by the following general formula (2) as a constituent unit.

{Where,
a represents H, an alkyl group or an aryl group;
X represents —O—, —S—,> NR ₁₀₁ (wherein R ₁₀₁ represents H or an alkyl group), CH ₂ or a single bond;
Y represents = O, = S or 2H;
m represents an integer of 0 to 4,
X ₁ represents a divalent linking group,
Z represents a 5- or 6-membered nitrogen-containing coordinated heteroaromatic ring group,
M represents a metal ion selected from typical metals and transition metals;
Q ₂ represents a bent divalent group,
p ₂ represents an integer of 3 or more. } The cyclic porphyrin multimer derivative represented by the following general formula (2-1).

{Where,
X, Y, m, X ₁ , Z, M, Q ₂ and p ₂ are as defined in claim 3;
e and f simultaneously represent H or a hydroxyl group, or e and f are bonded to each other to form an epoxy ring together with C—C to which they are bonded. } A linear porphyrin multimer having a coordination heteroaromatic ring-substituted porphyrin metal complex formed by a coordination bond represented by the following general formula (3) as a structural unit.

{Where,
a, b and d each independently represent H, an alkyl group or an aryl group;
X represents —O—, —S—,> NR ₁₀₁ (wherein R ₁₀₁ represents H or an alkyl group), CH ₂ or a single bond;
Y represents = O, = S or 2H;
m represents an integer of 0 to 4,
X ₁ represents a divalent linking group,
Z represents a 5- or 6-membered nitrogen-containing coordinated heteroaromatic ring group,
M represents a metal ion selected from typical metals and transition metals;
Q ₁ represents a single bond or a linear divalent linking group,
p ₁ represents an integer of 2 or more. } A cyclic porphyrin multimer comprising a coordination heteroaromatic ring-substituted porphyrin metal complex formed by a coordination bond represented by the following general formula (4) as a constituent unit.

{Where,
a, b and d each independently represent H, an alkyl group or an aryl group;
X represents —O—, —S—,> NR ₁₀₁ (wherein R ₁₀₁ represents H or an alkyl group), CH ₂ or a single bond;
Y represents = O, = S or 2H;
m represents an integer of 0 to 4,
X ₁ represents a divalent linking group,
Z represents a 5- or 6-membered nitrogen-containing coordinated heteroaromatic ring group,
M represents a metal ion selected from typical metals and transition metals;
Q ₂ represents a bent divalent group,
p ₂ represents an integer of 3 or more. } A bis-coordinate heteroaromatic substituted porphyrin monomer having a cross-linked portion represented by the following general formula (5).

{Where,
a, b and d each independently represent H, an alkyl group or an aryl group;
X represents —O—, —S—,> NR ₁₀₁ (wherein R ₁₀₁ represents H or an alkyl group), CH ₂ or a single bond;
Y represents = O, = S or 2H;
m represents an integer of 0 to 4,
X ₁ represents a divalent linking group,
Z ₂ represents H, a 5- or 6-membered nitrogen-containing coordinating heteroaromatic ring group, an alkyl group or an aryl group,
M represents a metal ion selected from typical metals and transition metals;
Q represents a single bond or a divalent linking group. } A coordinating heteroaromatic substituted porphyrin dimer immobilized by a covalent bond represented by the following general formula (6).

{Where,
a represents H, an alkyl group or an aryl group;
X represents —O—, —S—,> NR ₁₀₁ (wherein R ₁₀₁ represents H or an alkyl group), CH ₂ or a single bond;
Y represents = O, = S or 2H;
m represents an integer of 0 to 4,
X ₁ represents a divalent linking group,
Z represents a 5- or 6-membered nitrogen-containing coordinated heteroaromatic ring group,
M represents a metal ion selected from typical metals and transition metals;
R ¹ is H, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,

(In the formula, D represents a divalent group containing at least one of an arylene group and an alkylene group, E represents a trivalent group containing at least one of an arylene group and an alkylene group, and R ³ represents H or Represents an acetyl group). } Porphyrin dimer derivative represented by the following general formula (6-1).

{Where,
X, Y, m, X ₁ , Z, M and R ¹ are as defined in claim 8;
e and f simultaneously represent H or a hydroxyl group, or e and f are bonded to each other to form an epoxy ring together with C—C to which they are bonded. A coordination heteroaromatic substituted porphyrin dimer formed by a coordination bond represented by the following general formula (7).

{Where,
a, b and d each independently represent H, an alkyl group or an aryl group;
X represents —O—, —S—,> NR ₁₀₁ (wherein R ₁₀₁ represents H or an alkyl group), CH ₂ or a single bond;
Y represents = O, = S or 2H;
m represents an integer of 0 to 4,
X ₁ represents a divalent linking group,
Z represents a 5- or 6-membered nitrogen-containing coordinated heteroaromatic ring group,
M represents a metal ion selected from typical metals and transition metals;
R ¹ is H, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,

(In the formula, D represents a divalent group containing at least one of an arylene group and an alkylene group, E represents a trivalent group containing at least one of an arylene group and an alkylene group, and R ³ represents H or Represents an acetyl group). }   A linear porphyrin multimer of the general formula (3) described in claim 5 is subjected to a ring-closing metathesis reaction in the presence of a Grubbs complex, so that the linear form of the general formula (1) described in the claim 1 is used. A method for producing a porphyrin multimer.   By hydrogenating the linear porphyrin multimer of general formula (1) described in claim 1 in the presence of a metal catalyst, general formula (1-1) described in claim 2 (wherein , E = f = H).   By oxidizing the linear porphyrin multimer of general formula (1) described in claim 1 in the presence of a catalyst, the general formula (1-1) described in claim 2 (wherein e = F = hydroxyl)).   The linear porphyrin multimer of general formula (1) described in claim 1 is oxidized in the presence of a catalyst, if necessary, so that general formula (1-1) ( Wherein e and f are bonded to each other to form an epoxy ring together with C—C to which they are bonded.).   The cyclic porphyrin multimer of the general formula (4) described in claim 6 is subjected to a ring-closing metathesis reaction in the presence of a Grubbs complex, whereby the cyclic porphyrin multimer of the general formula (2) described in claim 3 is obtained. How to manufacture.   By hydrogenating the cyclic porphyrin multimer of the general formula (2) described in claim 3 in the presence of a metal catalyst, the general formula (2-1) (wherein e = F = H).   By oxidizing the cyclic porphyrin multimer of general formula (2) described in claim 3 in the presence of a catalyst, general formula (2-1) described in claim 4 (wherein e = f = Hydroxyl) derivative.   The cyclic porphyrin multimer of the general formula (2) described in claim 3 is oxidized in the presence of a catalyst, if necessary, so that the general formula (2-1) (in the formula) , E and f are bonded together to form an epoxy ring together with C—C to which they are bonded.).   The bis-coordinating heteroaromatic substituted porphyrin monomer of general formula (5) described in claim 7 is self-assembled by coordination bonds in a non-polar solvent, and the general described in claim 5 A method for producing a linear porphyrin multimer of the formula (3) or a cyclic porphyrin multimer of the general formula (4) according to claim 6. However, in the general formula (5), when Q is a single bond or a linear divalent group, a linear porphyrin multimer of the general formula (3) is obtained, whereas in the general formula (5), Q However, in the case of bent bivalent, a cyclic porphyrin multimer of the general formula (4) is obtained.   The porphyrin dimer formed by the coordinate bond of the general formula (7) described in claim 10 is subjected to a ring-closing metathesis reaction in the presence of a Grubbs complex, thereby generating a general formula (6 ) To produce a dimer immobilized by a covalent bond.   The porphyrin dimer of the general formula (6) described in claim 8 is hydrogenated in the presence of a metal catalyst to thereby generate the general formula (6-1) described in claim 9 (wherein e = F = H).   By oxidizing the porphyrin dimer of the general formula (6) described in claim 8 in the presence of a catalyst, the general formula (6-1) described in claim 9 (wherein e = f = Hydroxyl) derivative.   The porphyrin dimer of the general formula (6) described in claim 8 is oxidized in the presence of a catalyst as necessary, thereby the general formula (6-1) (in the formula) , E and f are bonded to each other to form an epoxy ring together with C—C to which they are bonded.). The coordinated heteroaromatic substituted porphyrin metal complex monomer represented by the following general formula (8) is self-assembled by a coordinate bond in a nonpolar solvent, and the general formula described in claim 10 (7) Method for producing porphyrin dimer :

{Where,
R is an alkyl group or

(Wherein a, b and d each independently represents H, an alkyl group or an aryl group),
X represents —O—, —S—,> NR ₁₀₁ (wherein R ₁₀₁ represents H or an alkyl group), CH ₂ or a single bond;
Y represents = O, = S or 2H;
m represents an integer of 0 to 4,
X ₁ represents a divalent linking group,
Z ₂ represents a 5- or 6-membered nitrogen-coordinating heteroaromatic ring,
M ₂ represents an ion of a metal selected from typical metals and transition metals,
R ¹ is H, a monovalent group derived from a linear divalent linking group or a bent divalent linking group,

(In the formula, D represents a divalent group containing at least one of an arylene group and an alkylene group, E represents a trivalent group containing at least one of an arylene group and an alkylene group, and R ³ represents H or Represents an acetyl group). }

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