JP5025970B2 - Hollow transition metal complex having fluorine-containing alkyl group inside hollow shell and method for producing the same - Google Patents

Description

  The present invention has a hollow shell formed from a transition metal atom and a bidentate organic ligand having a substituent having a fluorine-containing alkyl group moiety at the end, and the substituent of the bidentate organic ligand is The present invention relates to a hollow transition metal complex oriented inside a hollow shell and a method for producing the same.

  Strictly controlled nano-sized hollow structures can be classified into three regions: surface, inner surface, and isolated interior space. So far, the surface and internal space have been extensively studied, but there have been few reports on research using the inner surface in artificial systems.

  In recent years, studies using the inner surface of natural nanoscale structures such as globular proteins such as ferritin and globular virus CCMV have been conducted. Even if these structures are decomposed by an artificial stimulus, they are restored to their original structures by self-organization. The functional group is modified on the subunit so that it faces the inner surface of the spherical shell structure (spherical structure having a hollow shell), and the spherical shell structure is formed again by self-organization, so that the functional group is precisely applied to the spherical inner surface. (Non-patent Documents 1 and 2).

  The present inventors have also studied self-organization using a coordinate bond between an organic ligand and a transition metal ion. Since the coordinate bond has an appropriate binding force and the directionality is clearly defined, it is possible to spontaneously and quantitatively construct a molecular assembly whose structure is precisely controlled. In addition, since the coordination number and the bond angle can be controlled in accordance with the type of metal and the oxidation number, various coordination-bonding structures can be obtained (Non-Patent Documents 3 to 5).

For example, when planar four-coordinate Pd (II) ions are used, the direction of coordination bond can be defined as 90 degrees. In particular, a palladium ethylenediamine nitrate complex [(en) Pd (NO ₃ ) ₂ ] (M) whose cis position is protected with ethylenediamine (en) and a panel-shaped organic ligand (L) are used as ligands. Various hollow structures are self-assembled as the most stable state (Non-Patent Documents 6 to 11).

In addition, a self-assembly of a cubic octahedral spherical complex of M ₁₂ L ₂₄ composition composed of multiple components has been found (Non-patent Document 12). The resulting complex consists of 24 bent-type bidentate organic ligands of about 120 degrees centered on furan or benzene and 12 Pd (II) ions self-assembled into 8 equilateral triangles and 6 squares. It consists of a total of 14 surfaces. In this case, the number of vertices is 12, the number of sides is 24, which corresponds to the number of metal ions and ligands, respectively.

This structure is clarified by X-ray crystal structure analysis, and has a diameter of about 3.5 nm and an internal space volume of about 22 nm ³ , and a huge three-dimensional hollow structure is constructed. In addition, it is known that a spherical complex having a composition of M ₁₂ L ₂₄ is similarly constructed from a bidentate organic ligand in which the length of the ligand is changed, and a spherical complex having a diameter of 5 nm self-assembles. These complexes have a spherical structure in which the internal space is the widest, and this size is sufficient for inclusion of biomolecules such as proteins and nucleic acids.

In the spherical complex having the M ₁₂ L ₂₄ composition, by introducing a functional group at a predetermined position of the ligand, it is possible to arrange 24 functional groups at once on the nano surface of the spherical capsule through a self-assembly reaction. It is clear. For example, a complex in which porphyrin or fullerene is precisely arranged on the surface has been reported (Non-Patent Document 12), and application to physiological activity and optical properties utilizing a nano-surface with a spherical structure is expected.

In addition, by introducing a cationic trimethylammonium group, a cationic ball having a charge of 48 ⁺ is constructed on the surface, and a unique function of the nanosurface has been found, such as remarkably increasing the protein metamorphism (non-non-functionality). Patent Document 13).

R. M.M. Kramer, C.I. Li, D.D. C. Carter, M.M. O. Stone, R.M. R. Naik, J .; Am. Chem. Soc. , 2004, 126, 13283 T.A. Douglas, E .; Strable, D.M. Willits, A.D. Aitouchen, M.A. Libera, M .; Young, Adv. Mater. , 2002, 14, 415 P. J. et al. Stang, B.M. Olynuk, Acc. Chem. Res. 1997, 30, 507 M.M. Fujita, Chem. Soc. Rev. 1998, 27, 417 B. Olynuk, A .; Fechtencotter, P.M. J. et al. Stang, J. et al. Chem. Soc. Dalton Trans. 1998, 1707 M.M. Fujita, K .; Umemoto, M.M. Yoshizawa, N .; Fujita, T .; Kusukawa, K. et al. Biradha, Chem. Commun. , 2001, 509 M.M. Fujita, D .; Oguro, M .; Miyazawa, H .; Oka, K .; Yamaguchi, K .; Ogura, Nature, 1995, 378, 469 N. Takeda, K .; Umemoto, K.M. Yamaguchi, M .; Fujita, Nature, 1999, 398, 794 K. Umemoto, H.M. Tsukui, T .; Kusukawa, K. et al. Biradha, M .; Fujita, Angew. Chem. Int. Ed. , 2001, 40, 2620 M.M. Aoyagi, S .; Tashiro, M .; Tominaga, K .; Biradha, M .; Fujita, Chem. Commun. , 2002, 2036 T.A. Yamaguchi, S .; Tashiro, M .; Tominaga, M .; Kawano, T .; Ozeki, M .; Fujita, J .; Am. Chem. Soc. , 2004, 10818 M.M. Tominaga, K .; Suzuki, M .; Kawano, T .; Kusukawa, T .; Ozeki, S .; Sakamoto, K .; Yamaguchi, M .; Fujita, Angew. Chem. Int. Ed. , 2004, 43, 5621 Kenichiro Yakura, graduation thesis, University of Tokyo

  The present invention has been made as part of the present inventors' research and development, and includes n1 transition metal atoms (n1 represents an integer of 6 to 60) and 2 (n1) two atoms. A transition metal complex having a hollow shell formed from a bidentate organic ligand, wherein the bidentate organic ligand has a fluorine-containing alkyl group moiety at the end, and the substituent is hollow It is an object of the present invention to provide a hollow transition metal complex that is formed so as to be oriented inside the shell and a method for producing the same.

  The present inventors synthesized a compound in which a substituent having a fluorine-containing alkyl group moiety was introduced at the 2-position of 1,3-bis (4-pyridylethynyl) benzene, and this was synthesized as a bidentate organic ligand. Was used to form a self-organized hollow transition metal complex with a transition metal compound. And it discovered that the substituent which has a fluorine-containing alkyl-group part at the terminal can arrange | position the hollow transition metal complex arrange | positioned inside the hollow shell of a complex efficiently, and came to complete this invention.

Thus, according to the first aspect of the present invention, there is provided the hollow transition metal complex according to any one of the following (1) to (9).
(1) A hollow transition metal complex having a hollow shell, wherein the hollow shell has n1 transition metal atoms (n1 represents an integer of 6 to 60) and 2 (n1) two transition metal atoms. The bidentate organic ligand has a substituent having a fluorine-containing alkyl group moiety at the end, and the substituent is oriented inside the hollow shell. A hollow transition metal complex characterized by being formed as described above.

(2) A hollow transition metal complex having a hollow shell, wherein the hollow shell has n2 transition metal atoms (n2 is 6, 12, 24, 30 or 60) and 2 (n2 A bidentate organic ligand having a substituent having a fluorine-containing alkyl group moiety at the terminal, and the substituent is hollow. A hollow transition metal complex formed so as to be oriented inside a shell.

(3) From the transition metal compound (M) and the bidentate organic ligand (L) having a substituent having a fluorine-containing alkyl group moiety at the terminal, the self-alignment so that the substituent is oriented inside the hollow shell Formula: M _n1 L _{2 (n1)} formed systematically (n1 is an integer of 6 to 60, and M and L may be the same or different from each other. The hollow transition metal complex according to (1), which is represented by:

(4) From the transition metal compound (M) and the bidentate organic ligand (L) having a substituent having a fluorine-containing alkyl group at the terminal, the self-alignment is performed so that the substituent is oriented inside the hollow shell. Formula: M _n2 L _{2 (n2)} (n2 is 6, 12, 24, 30 or 60, and M and L are the same or different from each other. The hollow transition metal complex according to (2), which is represented by:

(5) The hollow transition metal complex according to any one of (1) to (4), wherein the fluorine-containing alkyl group moiety is a perfluoroalkyl group.
(6) The transition metal atom constituting the transition metal complex is a kind selected from the group consisting of Ti, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Cd, Os, Ir, and Pt. The hollow transition metal complex according to any one of (1) to (5), wherein
(7) The bidentate organic ligand is represented by the formula (I)

{Wherein, R ¹ and R ² each independently represents a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, a cyano group, or a nitro group.
m1 and m2 each independently represents an integer of 0 to 4. m1, m2 is 2 or more, ^{R 1} each other, even ^{R 2} together are each identical or may be different phases.
A represents the following formulas (a-1) to (a-4)

[R ³ represents a group having a fluorine-containing alkyl group at the terminal.
R ⁴ represents a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, a cyano group, or a nitro group.
m3 represents an integer of 0 to 3, and m4 represents an integer of 0 to 2. When m3 is 2 or more and m4 is 2, the plurality of R ⁴ may be the same or different.
Q is, -Nr1-, (r1 represents a hydrogen atom, an alkyl group, an aryl group or an acyl group.) - O -, - C (= O) -, - S-, or -SO ₂ - represents a. ] Is represented. } The hollow transition metal complex according to any one of (1) to (6), which is a compound represented by

(8) R ³ is a group represented by the formula: -D-Rf [D is a linking group represented by the formula:-(O-CH ₂ ) s-(s represents an integer of 1 to 20). ), formula :-( _CH 2) t-represented by a linking group (t is an integer of 1 to 20), or represents a linking group comprising a combination thereof, Rf represents a perfluoroalkyl group. The hollow transition metal complex according to (7), wherein
(9) The bidentate organic ligand is represented by the formula (I-1)

(In formula, D and Rf represent the same meaning as the above.) The hollow transition metal complex according to any one of (1) to (6),

According to a second aspect of the present invention, there is provided a method for producing the hollow transition metal complex of the present invention (10) below.
(10) The bidentate organic compound (M) and the bidentate organic ligand (L) having a substituent having a fluorine-containing alkyl group moiety at the end are bidentate organic to 1 mol of the transition metal compound (M). The method for producing a hollow transition metal complex according to any one of (1) to (9), wherein the ligand (L) is reacted at a ratio of 1 to 5 mol.

According to the first aspect of the present invention, the bidentate organic ligand has a hollow shell having a precisely controlled size, and a substituent having a fluorine-containing alkyl group moiety at the terminal is located inside the hollow shell. A hollow transition metal complex having a special structure oriented in the direction is provided.
According to the hollow transition metal complex of the present invention, the inside of the hollow shell of the complex can be made an environment rich in fluorine atoms, so that other molecules and ions containing fluorine can be selectively incorporated as guests. Become. In addition, by selecting and using the type of the fluorine-containing alkyl group of the substituent, it is possible to control the type and number of guests to be incorporated.

  According to the second aspect of the present invention, a hollow capable of efficiently producing a nanometer-scale hollow transition metal complex having a fluorine-containing alkyl group inside a spherical structure (the hollow transition metal complex of the present invention) without requiring a complicated step. A method for producing a transition metal complex is provided.

  Hereinafter, the present invention will be described in detail by dividing it into 1) a hollow transition metal complex and 2) a method for producing a hollow transition metal complex.

1) Hollow transition metal complex The hollow transition metal complex of the present invention is a hollow transition metal complex having a hollow shell, and the hollow shell comprises n1 transition metal atoms and 2 (n1) bidentate. The bidentate organic ligand has a substituent having a fluorine-containing alkyl group moiety at the end, and the substituent is oriented inside the hollow shell. It is formed as follows.
Here, n1 is an integer of 6-60.
In the hollow transition metal complex of the present invention, n1 is preferably n2 because self-assembly easily proceeds. n2 is 6, 12, 24, 30 or 60, preferably 6 or 12, particularly preferably 12.

  The hollow transition metal complex of the present invention is formed by self-assembly using a coordinate bond between a transition metal ion and a bidentate organic ligand having a substituent having a fluorine-containing alkyl group moiety at the terminal. is there. Since the coordinate bond has an appropriate binding force and the directionality is clearly defined, it is possible to spontaneously and quantitatively construct a molecular assembly whose structure is precisely controlled. In addition, since the coordination number and the bond angle can be controlled in accordance with the type of metal and the oxidation number, various coordination bond structures can be obtained.

The hollow transition metal complex of the present invention includes a transition metal compound (M) and a bidentate organic ligand (L) having a substituent whose terminal is a fluorine-containing alkyl group (hereinafter simply referred to as “bidentate organic coordination”). The substituent is formed in a self-organized manner so that the substituent is oriented inside the hollow shell, and the formula: M _n1 L _{2 (n1)} Are the same meanings.) And are preferably formed from the transition metal compound (M) and the bidentate organic ligand (L) so that the substituent is oriented in the hollow shell. More preferably, the compound represented by the formula: M _n2 L _{2 (n2)} (n2 represents the same meaning as described above) is used. Here, M and L may be the same or different from each other, but are preferably the same.

  The size of the hollow shell of the hollow transition metal complex of the present invention is not particularly limited, but the diameter is preferably 3 to 15 nm.

(1) Transition metal atom Although it does not restrict | limit especially as a transition metal atom which comprises the hollow transition metal complex of this invention, Ti, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Cd, Os, Ir And a platinum group atom such as Ru, Rh, Pd, Os, Ir, and Pt is preferable because Ru can be easily formed as a four-coordinated complex. , Pd, and Pt are more preferable, and Pd is particularly preferable.
The valence of the transition metal atom is usually 0 to 4, preferably 2. The coordination number is usually 4 to 6, preferably 4.

(2) Bidentate organic ligand (L)
The bidentate organic ligand (L) forming the hollow transition metal complex of the present invention has a substituent having a fluorine-containing alkyl group moiety at the terminal, and this substituent is oriented inside the hollow shell. As long as it can form a hollow transition metal complex with a transition metal atom in a self-organizing manner, the compound represented by the following formula (I) is preferable. The compound represented by the formula (I) has an acetylene group as a bridge portion adjacent to the pyridyl group, and has a structure having a wide space between the pyridyl groups at both ends while maintaining planarity.

In the formula, R ¹ and R ² each independently represent a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, a cyano group, or a nitro group.
m1 and m2 each independently represents an integer of 0 to 4. m1, m2 is 2 or more, ^{R 1} each other, even ^{R 2} together are each identical or may be different phases.
A represents one type of compounds represented by the following formulas (a-1) to (a-4).

In the formula, R ³ represents a group having a fluorine-containing alkyl group at the terminal, and is preferably a group represented by the formula: -D-Rf. Wherein, D is represents formula :-( _O-CH 2) s- represented by a linking group of the formula :-( _CH 2) t-represented by a linking group, or a linking group consisting of a combination . In the formula, s and t each independently represent an integer of 1 to 20.

  Rf represents a perfluoroalkyl group. Although there is no restriction | limiting in particular as carbon number of a perfluoroalkyl group, Usually, 1-20, Preferably it is 3-10. The perfluoroalkyl group may be a chain or a branch.

R ⁴ represents a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, a cyano group, or a nitro group.
m3 represents an integer of 0 to 3, and m4 represents an integer of 0 to 2. When m3 is 2 or more and m4 is 2, the plurality of R ⁴ may be the same or different.

Examples of the halogen atom for R ¹ , R ² and R ⁴ include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group of the alkyl group which may be substituted for R ¹ , R ² and R ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-pentyl group, C1-C20 alkyl groups, such as n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, are mentioned.
In addition, examples of the substituent of the alkyl group which may be substituted for R ¹ , R ² and R ⁴ include a halogen atom, an alkoxyl group, and a phenyl group which may have a substituent.

Examples of the alkoxyl group of the alkoxyl group which may be substituted for R ¹ , R ² and R ⁴ include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, t-butoxy group, pentyloxy group, hexyloxy C1-C20 alkoxyl groups, such as group, are mentioned. In addition, examples of the substituent of the alkoxyl group which may be substituted for R ¹ , R ² and R ⁴ include a halogen atom and a phenyl group which may have a substituent.

Q is, -Nr1- (r1 represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group.), - O -, - C (= O) -, - S-, or -SO ₂ - represents a .
Examples of the alkyl group of r1 include a methyl group and an ethyl group, examples of the aryl group include a phenyl group and a p-methylphenyl group, and examples of the acyl group include an acetyl group and a benzoyl group.

  The bidentate organic ligand (L) used in the present invention is particularly preferably a compound represented by the following formula (I-1).

In the formula, D and Rf represent the same meaning as described above.
The bidentate organic ligand (L) can be produced by applying a known synthesis method.
For example, among the compounds represented by the formula (I), a compound represented by the following formula (I-2) is prepared by a method known in the literature (K. Sonogashira, Y. Tohda, N. Hagihara, Tetrahedron Lett., 1975, 4467; JF Nguefack, V. Bolitt, D. Sinou, Tetrahedron Lett., 1996, 31, 5527).

In the formula, A, R ¹ and m1 represent the same meaning as described above.
(A-1) represents a compound represented by the formula: X-A-X.
X represents a halogen atom such as a chlorine atom, a bromine atom or an iodine atom.

That is, the compound represented by the formula (I-2) includes a base, a palladium catalyst such as Pd (PhCN) ₂ Cl ₂ / P (t-Bu) ₃ , Pd (PPh ₃ ) _{4 in} an appropriate solvent, and In the presence of a copper salt such as cuprous iodide, 4-ethynylpyridines (or a salt thereof) represented by formula (II) and a compound (A-1) represented by formula (III) are reacted. Can be obtained.

  The above reaction is an example in which two 4-ethynylpyridines (or salts thereof) are reacted at once to produce a compound having two identical pyridinylethynyl groups. Compounds having different substituted pyridylethynyl groups can be obtained by reacting the corresponding 4-ethynylpyridines (or salts thereof) stepwise under similar reaction conditions.

  Examples of the base used here include amines such as dimethylamine, diethylamine, diisopropylamine, triethylamine, and diisopropylethylamine.

Examples of the solvent to be used include ethers such as 1,4-dioxane, diisopropyl ether, tetrahydrofuran and 1,3-dimethoxyethane; amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide; nitriles such as acetonitrile; It is done.
The reaction temperature is usually in the temperature range from 0 ° C. to the boiling point of the solvent used, preferably 10 ° C. to 70 ° C., and the reaction time is usually from several minutes to several tens of hours depending on the reaction scale and the like.

  4-Ethynylpyridine (or a salt thereof) can be produced by a known method, but a commercially available product can also be used as it is.

Moreover, the compound represented by Formula (III) can be manufactured by a well-known method.
For example, the compound represented by the following formula (III-1) used for the production of the compound represented by the formula (I-1) can be produced by the following production method 1 or 2.
(Production method 1)

(In the formula, X and Rf represent the same meaning as described above, L represents a leaving group, and the group: -OD 'corresponds to D above.)
That is, the compound represented by formula (IV) is reacted with the compound represented by formula (V) in the presence of a base in an inert gas atmosphere, thereby being represented by formula (III-1). A compound can be obtained.

  As the base to be used, inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, sodium hydroxide, sodium hydride; triethylamine, pyridine, 1,8-diazabicyclo [5.4.0] -7- And amines such as undecene (DBU); metal alkoxides such as potassium t-butoxide and sodium methoxide; and the like.

  This reaction is preferably carried out in a solvent. The solvent to be used is not particularly limited as long as it is an inert solvent for the reaction. For example, ethers such as diethyl ether, tetrahydrofuran (THF) and 1,4-dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; Nitriles such as acetonitrile; Amides such as dimethylformamide (DMF); Sulfoxides such as dimethyl sulfoxide (DMSO); Aromatic amines such as pyridine;

This reaction proceeds smoothly in a temperature range from 0 ° C. to the boiling point of the solvent used. The reaction time is several minutes to 48 hours depending on the reaction scale and the like.
(Production method 2)

(In the formula, X, Rf, and D ′ have the same meaning as described above.)
That is, the compound represented by the formula (IV) is reacted with the compound represented by the formula (VI) in an inert gas atmosphere in the presence of a dehydrating agent, thereby being represented by the formula (III-1). A compound can be obtained.

The dehydrating agent to be used is not particularly limited, and examples thereof include 1,3-dicyclohexylcarbodiimide, diisopropyl azodicarboxylate (DIAD) and the like.
This reaction is preferably carried out in a solvent. The solvent to be used is not particularly limited as long as it is an inert solvent for the reaction, and examples thereof include those exemplified in Production Method 1.

  This reaction proceeds smoothly in a temperature range from 0 ° C. to the boiling point of the solvent used. The reaction time is several minutes to 48 hours depending on the reaction scale and the like.

In any reaction, after completion of the reaction, the desired product can be isolated by performing a usual post-treatment operation and, if desired, a known purification operation.
The structure of the resulting compound can be identified and confirmed by measuring elemental analysis, IR, NMR, MS spectrum and the like.

An example of the hollow transition metal complex of the present invention is shown in FIG. The hollow transition metal complex shown in FIG. 1 is composed of 12 transition metal compounds (M) and 24 bidentate organic ligands (L).
The hollow transition metal complex shown in FIG. 1 is constructed by self-assembling twelve metal ions and twenty-four bent bidentate organic ligands (L), and has a wide space inside. The bidentate organic ligand (L) has a substituent R having a fluorine-containing alkyl group moiety at the end, and the substituent R is precisely arranged inside the hollow shell.

2) Method for producing hollow transition metal complex The method for producing a hollow transition metal complex of the present invention comprises a transition metal compound (M) and a bidentate organic ligand (L) with respect to 1 mol of the transition metal compound (M). The bidentate organic ligand (L) is reacted in a proportion of 1 to 5 mol, preferably 2 to 3 mol.

  The transition metal compound (M) used in the present invention is not particularly limited as long as it can form a hollow transition metal complex with the bidentate organic ligand (L) in a self-organizing manner, but a divalent transition metal compound is preferable. .

  Examples of the transition metal atom constituting the transition metal compound (M) include transition metal atoms such as Ti, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Cd, Os, Ir, and Pt. . Among them, a platinum group atom such as Ru, Rh, Pd, Os, Ir, and Pt is preferable, Ru, Pd, and Pt are more preferable, and Pd is particularly preferable because a planar four-coordinate complex can be easily formed. .

  Specific examples of the transition metal compound (M) include transition metal halides, nitrates, hydrochlorides, sulfates, acetates, methanesulfonates, trifluoromethanesulfonates, p-toluenesulfonates, and the like. It is done. Among these, nitrates and trifluoromethanesulfonates of transition metals are preferred because the desired hollow transition metal complex can be obtained efficiently.

The use ratio of the transition metal compound (M) and the bidentate organic ligand (L) can be appropriately set according to the composition of the intended hollow transition metal complex. For example, when it is desired to obtain the transition metal complex having the composition of the formula: M ₁₂ L ₂₄ as described above, 2 to 3 mol of the bidentate organic ligand (L) per 1 mol of the transition metal compound (M). The reaction may be performed at the ratio of

The reaction between the transition metal compound (M) and the bidentate organic ligand (L) can be carried out in a suitable solvent.
Solvents used include nitriles such as acetonitrile; sulfoxides such as dimethyl sulfoxide (DMSO); amides such as N, N-dimethylformamide; diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane and the like. Ethers; halogenated hydrocarbons such as dichloromethane and chloroform; aliphatic hydrocarbons such as pentane and hexane; aromatic hydrocarbons such as benzene and toluene; alcohols such as methanol, ethanol and isopropyl alcohol; acetone; Ketones such as methyl ethyl ketone; cellosolves such as ethyl cellosolve; water and the like. These solvents can be used alone or in combination of two or more.

The reaction between the transition metal compound (M) and the bidentate organic ligand (L) proceeds smoothly in a temperature range from 0 ° C. to the boiling point of the solvent used.
The reaction time is several minutes to several days.
After completion of the reaction, the desired hollow transition can be obtained by performing the usual post-treatment operations in organic synthetic chemistry and, if desired, purification by known separation and purification means such as column purification with ion exchange resin, distillation, recrystallization, etc. Metal complexes can be isolated.

The counter ion of the obtained hollow transition metal complex is usually an anion of the transition metal compound (M) to be used, but the counter ion is used for the purpose of improving crystallinity or improving the stability of the hollow transition metal complex. May be replaced. Examples of such counter ions include PF ₆ ⁻ , ClO ₄ ⁻ , SbF ₄ ⁻ , AsF ₆ ⁻ , BF ₄ ⁻ , SiF ₆ ^{2− and the} like.

The structure of the obtained hollow transition metal complex is known as ¹ H-NMR, ¹³ C-NMR, IR spectrum, mass spectrum, visible light absorption spectrum, UV absorption spectrum, reflection spectrum, X-ray crystal structure analysis, elemental analysis, etc. This can be confirmed by means of analysis.

  As described above, the hollow transition metal complex of the present invention can be efficiently produced by an extremely simple operation. Therefore, mass synthesis on a gram scale is also possible.

  The hollow transition metal complex of the present invention has a constant size on the nanometer scale, and the substituent R having a fluorine-containing alkyl group at the terminal of the bidentate organic ligand (L) is inside the spherical structure of the complex. It has a special structure that is precisely controlled and precisely controlled.

  Thus, in the hollow transition metal complex of the present invention, the fluorine-containing alkyl groups of the bidentate organic ligand (L) are accumulated inside the hollow shell of the complex, and the shell interior is a special one rich in fluorine atoms. Has an environment. Therefore, the hollow transition metal complex of the present invention can selectively include a fluorine-containing compound inside the shell.

  The number of fluorine-containing compounds included in the inside of the shell of the hollow transition metal complex of the present invention depends on the size (volume) of the shell and the size of the fluorine-containing compound. In general, the larger the shell, the more fluorine-containing compounds can be included, and the larger the fluorine-containing compound, the smaller the number of fluorine-containing compounds included. On the other hand, the smaller the shell of the hollow transition metal complex and the shorter the distance between the fluorine atoms present in the shell, the more special fluorine-rich environment can be formed, and the fluorine-containing compound is selectively taken into the shell. Ability is thought to increase.

  In order to include the fluorine-containing compound inside the shell of the hollow transition metal complex of the present invention, the fluorine-containing compound is added to the solution of the hollow transition metal complex of the present invention and the whole volume is stirred.

  Here, as a fluorine-containing compound, fluorine-containing alkane, fluorine-containing alkene, etc. are mentioned, for example. The number of carbon atoms of the fluorine-containing compound is usually 3 to 20 although it depends on the size of the shell of the hollow transition metal complex of the present invention.

  Although there is no restriction | limiting in particular as a solvent to be used, The thing similar to having enumerated as a solvent used for reaction with the said transition metal compound (M) and a bidentate organic ligand (L) is mentioned. Further, even in a solvent in which the fluorine-containing compound does not dissolve, a uniform solution can be obtained by mixing the hollow transition metal complex of the present invention and the fluorine-containing compound in the solvent, and the fluorine-containing compound is hollow. It can be inferred that it was incorporated into the shell of the transition metal complex.

The temperature when mixing and stirring with the fluorine-containing compound is not particularly limited, but is usually 0 to 50 ° C, preferably 10 to 30 ° C.
The mixing / stirring time is usually 0.5 to 10 hours although it depends on the type of compound used.

The incorporation of the fluorine-containing compound into the inside of the shell of the hollow transition metal complex of the present invention measured ¹⁹ F-NMR spectrum, ¹⁹ F-NOESY spectrum, ¹⁹ F-COSY spectrum, ¹⁹ F-DOSY spectrum, etc. This can be confirmed by the change in the signal.

Next, the present invention will be described in more detail by way of examples. In addition, this invention is not limited at all by the Example.
(Equipment)
(1) Measurement of ¹ H-NMR spectrum
^{The 1} H-NMR spectrum was measured by Bruker DRX 500 (500 MHz) NMR spectrometer and JEOL JNM-AL 300 (300 MHz) NMR spectrometer. The measurement temperature is 27 ° C.
When CDCl ₃ or DMSO was used as a solvent, tetramethylsilane (TMS) was used as an internal standard.
Chemical shifts were expressed as δ values and the following abbreviations were used. s (single line), d (double line), t (triple line), br (broad).

(2) Measurement of ¹³ C-NMR spectrum and various two-dimensional NMR spectra
^{The 13} C-NMR spectrum and ¹⁹ F-NMR spectrum were measured using a Bruker DRX 500 ( ¹³ C: 125 MHz, ¹⁹ F: 470 MHz) NMR spectrometer. The measurement temperatures are all 27 ° C. At the time of ¹⁹ F-NMR measurement, a solution obtained by dissolving trifluoroacetic acid (TFA) in each solvent and sealed in a glass capillary was used as an external standard.

(3) Measurement of mass spectrum GC-MS was measured using Agilent 5973 inert.
Cold spray ionization mass spectrometry (CSI-MS) was measured by JEOL JMS-700C.

(Reagents)
Wakosil C-300 (Wako Pure Chemical Industries) was used for the separation of the product by column chromatography.
As the reaction solvent, a dehydrated solvent for organic synthesis (water content of 0.005% or less) commercially available from Wako Pure Chemical Industries, Ltd. and Kanto Chemical Co., Ltd. was used as it was.
Reagents were used as they were without any purification.

(Examples 1-4)
Hollow transition metal complexes (2a) to (2d) shown below were produced.

Example 1 Production of Hollow Transition Metal Complex (2a)

(1) Synthesis of 1,3-dibromo-2- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyloxy) benzene (4a) To a mixture of 2,6-dibromophenol (1.0 g, 4.0 mmol) and triphenylphosphine (1.0 g, 4.0 mmol) was added diisopropyl azodicarboxylate (DIAD, 0.78 mL, 4.0 mmol). And tetrahydrofuran (THF) (10 mL) were added, and the whole volume was stirred at room temperature for 30 minutes under an argon atmosphere, and then 3,3,4,4,5,5,6,6,7,7,8,8,8. -Tridecafluoro-1-octanol (0.88 mL, 4.0 mmol) was added, and the mixture was further stirred for 12 hours under the same conditions.
The reaction mixture was concentrated under reduced pressure, and the concentrate was purified by silica gel column chromatography (n-hexane) to obtain compound (4a) (1.8 g, 3.1 mmol) as a transparent oil (yield 77%). .

(Physical property data)
¹ H-NMR (500 MHz, CDCl ₃ , δ ppm); 7.52 (d, J = 8.0 Hz, 2H), 6.90 (t, J = 8.0 Hz, 1H), 4.31 (t, J = 7.3 Hz, 2H), 2.77 (m, 2H)

_{GC-MS calcd for C 14 H} 7 Br 2 F 13 O ([M +]); 598, found 598

(2) 1,3-bis (4-pyridylethynyl) -2- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyloxy) Synthesis of benzene (1a) Compound (4a) (1.5 g, 2.5 mmol) obtained above, 4-ethynylpyridine hydrochloride (0.98 g, 7.0 mmol), Pd (PhCN) ₂ Cl ₂ (58 mg, 0.15 mmol) and CuI (19 mg, 0.10 mmol) in dioxane (6 mL), tri-t-butylphosphine (0.77 mL, 0.31 mmol; 10% hexane solution) and diisopropylamine (1.8 mL, 13 mmol) And the whole was stirred at 50 ° C. for 22 hours under an argon atmosphere. Ethyl acetate (10 mL) was added to the reaction mixture and filtered, and water (150 mL) was added to the filtrate, washed with ethylenediamine (1 mL), and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The resulting concentrate was purified by silica gel column chromatography (chloroform: methanol = 100: 1 (v / v)) to give the ligand (1a) ( 1.1 g, 1.7 mmol) was obtained as a white solid (67% yield).

(Physical property data)
Melting point: 65-66 ° C
¹ H-NMR (500 MHz, CDCl ₃ , δ ppm); 8.64 (d, J = 6.0 Hz, 4H), 7.57 (d, J = 7.5 Hz, 2H), 7.37 (d, J = 6.5 Hz, 4H), 7.18 (t, J = 7.5 Hz, 1H), 4.61 (t, J = 6.5 Hz, 2H), 2.78 (m, 2H)

¹³ C-NMR (125 MHz, DMSO-d ₆ , δ ppm); 160.2 (C), 149.9 (C), 135.0 (CH), 129.8 (C), 125.1 (CH), 124.9 (CH), 116.0 (C), δ 91.3 (C), 88.7 (C), 78.9 (C), 66.2 (CH ₂ ), 31.1 (CH ₂ )

^{19 F-NMR (470Hz, DMSO} -d 6, δppm); - 82.0 (CF 3), - 113.8 (CF 2), - 123.2 (CF 2), - 124.2 (CF 2) , -124.6 (CF ₂ ), -127.3 (CF ₂ )

_{GC-MS calcd for C 28 H} 15 F 13 N 2 O ([M +]); 642, found 642
Elemental _{analysis: Calcd for C 28 H 15 F} 13 N 2 O: C, 52.35; H, 2.35; N, 4.36, Found: C, 52.40; H, 2.53; N, 4 .32

(3) Production of hollow transition metal complex (2a) Ligand (1a) (7.0 mg, 10.9 μmol) obtained above and Pd (NO ₃ ) ₂ (2.1 mg, 9.l μmol) The mixture was stirred in dimethyl sulfoxide (0.70 ml) at 70 ° C. for 3 hours.
When diethyl ether was added to the reaction mixture, a white solid was precipitated. Centrifugation was performed to remove the supernatant, and vacuum drying was performed to obtain the target product (4.6 mg) (yield 51%).

The physical property data of the obtained hollow transition metal complex (2a) are as follows.
¹ H-NMR (500 MHz, DMSO-d ₆ , δ ppm); 9.23 (br, 96H), 7.74 (br, 144H), 7.33 (br, 24H), 4.55 (br, 48H) , 2.88 (br, 48H)

¹⁹ F-NMR (470 Hz, DMSO-d ₆ , δ ppm); -82.9 (72F), -114.1 (48F), -123.5 (48F), -124.7 (48F), -125. 1 (48F), -128.0 (48F)

CSI-MS is a DMSO solution of the complex (2a) was added _CF 3 _SO 3 Na, a counter anion _CF 3 SO ₃ ^- was measured after replacing the.

_{CSI-MS (CF 3 SO 3} - _{salts, CH 3 CN: DMSO = 19} : 1): m / z; 2385.6 [M-8 (CF 3 SO 3 -)] 8+, 2103.9 [M-9 (CF ₃ SO ₃ ⁻ )] ⁹⁺ , 1878.7 [M-10 (CF ₃ SO ₃ ⁻ )] ¹⁰⁺ , 1694.3 [M-11 (CF ₃ SO ₃ ⁻ )] ¹¹⁺ , 1547.1 [M− 12 (CF ₃ SO ₃ ⁻ ) + (DMSO)] ¹²⁺ , 1540.6 [M-12 (CF ₃ SO ₃ ⁻ )] ¹²⁺ , 1416.7 [M-13 (CF ₃ SO ₃ ⁻ ) + (DMSO) ^{_{] 13+, 1410.7 [M-13}} (CF 3 SO 3 -)] 13+, 1310.342 [M-14 (CF 3 SO 3 -) +2 (DMSO)] 14+, 1304.8 [M-14 (CF ₃ SO ₃ ^-) + (DMSO _{^{] 14+, 1299.2 [M-14}} (CF 3 SO 3 -)] 14+

(Example 2) Production of hollow transition metal complex (2b)

(1) 1,3-dibromo-2- (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorode Synthesis of Siloxy) benzene (4b) To a mixture of 2,6-dibromophenol (400 mg, 1.6 mmol) and triphenylphosphine (420 mg, 1.6 mmol), DIAD (0.31 mL, 1.6 mmol) and THF ( 5 mL), and the reaction mixture was stirred at room temperature for 30 minutes under an argon atmosphere, and then 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro- 1-decanol (740 mg, 1.6 mmol, 5 mL of THF solution) was added, and the mixture was further stirred for 12 hours under the same conditions.
The reaction mixture was concentrated under reduced pressure, and the concentrate was purified by silica gel column chromatography (n-hexane) to give compound (4b) (768 mg, 1.1 mmol) as a clear oil (yield 70%).

(Physical property data)
GC-MS calcd for C ₁₆ H ₇ Br ₂ F ₁₇ O ([M ⁺ ]); 698, found 698

(2) 1,3-bis (4-pyridylethynyl) -2- (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, Synthesis of 10-heptadecafluorodecyloxy) benzene (1b) The obtained compound (4b) (700 mg, 1.0 mmol), 4-ethynylpyridine hydrochloride (390 g, 2.8 mmol), Pd (PhCN) ₂ Cl ₂ (23 mg, 0.060 mmol) and CuI (7.6 mg, 0.040 mmol) in dioxane (5 mL) and tri-t-butylphosphine (0.31 mL, 0.12 mmol; 10% hexane solution) and diisopropylamine. (0.72 mL, 5.2 mmol) was added.

  The reaction mixture was stirred at 50 ° C. for 17 hours under an argon atmosphere. Ethyl acetate (10 mL) was added to the reaction mixture, and the mixture was filtered. Water (150 mL) was added to the filtrate, and the mixture was washed with ethylenediamine (1 mL) and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The resulting concentrate was purified by silica gel column chromatography (chloroform: methanol = 100: 1 (v / v)) to give the ligand (1a) ( 180 mg, 0.24 mmol) was obtained as a white solid (yield 24%).

(Physical property data)
Melting point: 67-69 ° C
¹ H-NMR (500 MHz, CDCl ₃ , δ ppm); 8.64 (d, J = 6.0 Hz, 4H), 7.57 (d, J = 8.0 Hz, 2H), 7.37 (d, J = 6.5 Hz, 4H), 7.18 (t, J = 7.5 Hz, 1H), 4.61 (t, J = 6.5 Hz, 2H), 2.78 (m, 2H)

¹³ C-NMR (125 MHz, DMSO-d ₆ , δ ppm); 160.2 (C), 149.9 (CH), 135.0 (CH), 129.8 (C), δ 125.1 (CH), 124.9 (CH), 115.9 (C), 91.3 (C), 88.7 (C), 66.2 (CH ₂ ), 31.3 (CH ₂ )

^{19 F-NMR (470Hz, DMSO} -d 6, δppm); - 81.8 (CF 3), - 113.8 (CF 2), - 123.0 (CF 2), - 123.3 (CF 2) , -124.0 (CF ₂ ),-124.6 (CF ₂ ),-127.3 (CF ₂ )

Elemental _{analysis: Calcd for C 30 H 15 F} 15 N 2 O: C, 48.53; H, 2.04; N, 3.77, Found: C, 48.77; H, 2.30; N, 4 .06

(3) Production of Hollow Transition Metal Complex (2b) The obtained ligand (1b) (8.1 mg, 10.9 μmol) and Pd (NO ₃ ) ₂ (2.1 mg, 9.l μmol) were converted to dimethyl Stir in sulfoxide (0.70 ml) at 70 ° C. for 3 hours.
When diethyl ether was added to the reaction mixture, a white solid was precipitated. Centrifugation was performed to remove the supernatant, and vacuum drying was performed to obtain the target product (5.7 mg) (yield 56%).

The physical property data of the obtained hollow transition metal complex (2b) are as follows.
¹ H-NMR (500 MHz, DMSO-d ₆ , δ ppm); 9.20 (br, 96H), 7.72 (br, 144H), 7.35 (br, 24H), 4.51 (br, 48H) , 2.97 (br, 48H)

¹⁹ F-NMR (470 Hz, DMSO-d ₆ , δ ppm); -84.7 (72F), -114.4 (48F), -123.4 (48F), -124.3 (96F), -125. 2 (48F), -125.5 (48F), -129.3 (48F)

CSI-MS is a DMSO solution of the complex (2b) was added _CF 3 _SO 3 Na, a counter anion _CF 3 SO ₃ ^- was measured after replacing the.

_{CSI-MS (CF 3 SO 3} - _{salts, CH 3 CN): m /} z; 2829.4 [M-6 (CF 3 SO 3 -)] 6+, 2403.8 [M-7 (CF 3 SO 3 - )] ⁷⁺ , 2084.7 [M-8 (CF ₃ SO ₃ ⁻ )] ⁸⁺ , 1836.5 [M-9 (CF ₃ SO ₃ ⁻ )] ⁹⁺ , 1637.9 [M-10 (CF ₃ SO ₃₎ ⁻ )] ¹⁰⁺ , 1475.4 [M-11 (CF ₃ SO ₃ ⁻ )] ¹¹⁺ , 1340.0 [M-12 (CF ₃ SO ₃ ⁻ )] ¹²

(Example 3) Production of hollow transition metal complex (2c)

(1) 1,3-dibromo-2- (9-trifluoromethyl-3,3,4,4,5,5,6,6,7,7,8,8,9,10,10,10- Synthesis of tridecafluorodecyloxy) benzene (4c) 2,6-dibromophenol (600 mg, 2.4 mmol), cesium carbonate (1.6 g, 4.8 mmol), and 9-trifluoromethyl-3,3,4 4,5,5,6,6,7,7,8,8,9,10,10,10-hexadecafluoro-1-iodononane (4.1 g, 7.1 mmol) in acetonitrile (15 mL). The mixture was stirred at 80 ° C. for 17 hours under an argon atmosphere.
The reaction mixture was concentrated under reduced pressure, and the concentrate was purified by silica gel column chromatography (n-hexane) to obtain compound (4c) (420 mg, 0.56 mmol) as a clear oil (yield 24%).

(Physical property data)
¹ H-NMR (300 MHz, CDCl ₃ , δ ppm); 7.52 (d, J = 8.1 Hz, 2H), 6.90 (t, J = 8.1 Hz, 1H), 4.30 (t, J = 7.1 Hz, 2H), 2.77 (m, 2H)
_{GC-MS: calcd for C 17} H 7 Br 2 F 19 O ([M +]); 748, found 748

(2) 1,3-bis (4-pyridylethynyl) -2- (9-trifluoromethyl-
Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,9,10,10,10-tridecafluorodecyloxy) benzene (1c) Compound obtained above ( 4c) (410 mg, 0.55 mmol), 4-ethynylpyridine hydrochloride (210 g, 1.5 mmol), Pd (PhCN) ₂ Cl ₂ (18 mg, 0.034 mmol), and CuI (4.2 mg, 0.022 mmol) To a dioxane (1 mL) solution of tri-t-butylphosphine (0.14 mL, 0.066 mmol; 10% hexane solution) and diisopropylamine (0.40 mL, 2.8 mmol) were added. Stir at 17 ° C. for 17 hours. Ethyl acetate (5 mL) was added to the reaction mixture and filtered, and water (100 mL) was added to the filtrate, washed with ethylenediamine (1 mL), and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The resulting concentrate was purified by silica gel column chromatography (chloroform: methanol = 100: 1 (v / v)) to give the ligand (1a) ( 320 mg, 0.40 mmol) was obtained as a white solid (yield 86%).

(Physical property data)
Melting point: 73-75 ° C
_{GC-MS: calcd for C 31} H 15 F 19 N 2 O ([M +]); 792, found 792
¹ H-NMR (500 MHz, CDCl ₃ , δ ppm); 8.63 (d, J = 6.0 Hz, 4H), 7.57 (d, J = 8.0 Hz, 2H), 7.37 (d, J = 8.0 Hz, 4H), 7.18 (t, J = 7.5 Hz, 1H), 4.61 (t, J = 6.5 Hz, 2H), 2.76 (m, 2H)

IR (KBr, cm ⁻¹ ); 160.2 (C), 149.8 (CH), 135.0 (CH), 129.7 (C), 125.1 (CH), 124.8 (CH) 115.9 (C), 91.2 (C), 88.6 (C), 66.1 (CH ₂ ), 31.1 (CH ₂ )

¹⁹ F-NMR (470 Hz, DMSO-d ₆ , δ ppm); −72.9 (CF ₃ ), −113.8 (CF ₂ ), −116.4 (CF ₂ ), −122.1 (CF ₂ ) , -122.8 (CF ₂ ),-123.0 (CF ₂ ),-124.6 (CF ₂ ),-187.3 (CF)

(3) Production of Hollow Transition Metal Complex (2c) Ligand (1c) obtained above (8.6 mg, 10.9 μmol) and Pd (NO ₃ ) ₂ (2.1 mg, 9.l μmol) The mixture was stirred in dimethyl sulfoxide (0.70 ml) at 70 ° C. for 3 hours.
When diethyl ether was added to the reaction mixture, a white solid was precipitated. Centrifugation was performed to remove the supernatant, and vacuum drying was performed to obtain the target product (5.7 mg) (yield 56%).

The physical property data of the obtained hollow transition metal complex (2c) are as follows.
¹ H-NMR (500 MHz, DMSO-d ₆ , δ ppm); 9.19 (br, 96H), 7.72 (br, 144H), 7.34 (br, 24H), 4.51 (br, 48H) , 2.95 (br, 48H)

¹⁹ F-NMR (470 Hz, DMSO-d ₆ , δ ppm); -72.9 (144F), -113.8 (48F), -116.4 (48F), -122.1 (48F), -122. 8 (48F), -123.0 (48F), -124.6 (48F), -187.3 (24F)

CSI-MS is a DMSO solution of the complex (2c) was added to _CF 3 _SO 3 Na, a counter anion _CF 3 SO ₃ ^- was measured after replacing the.

_{CSI-MS (CF 3 SO 3} - _{salts, CH 3 CN): m /} z; 3630.4 [M-6 (CF 3 SO 3 -)] 6+, 3090.4 [M-7 (CF 3 SO 3 - )] ⁷⁺ , 2685.4 [M-8 (CF ₃ SO ₃ ⁻ )] ⁸⁺ , 2370.4 [M-9 (CF ₃ SO ₃ ⁻ )] ⁹⁺ , 218.4 [M-10 (CF ₃ SO ₃₎ ⁻ )] ¹⁰⁺ , 1926.5 [M-11 (CF ₃ SO ₃ ⁻ ) +2 (DMSO)] ¹¹⁺ , 1919.5 [M-11 (CF ₃ SO ₃ ⁻ ) + (DMSO)] ¹¹⁺ , 1912.3 [M-11 (CF ₃ SO ₃ ⁻ )] ¹¹⁺ , 1760.1 [M-12 (CF ₃ SO ₃ ⁻ ) +3 (DMSO)] ¹²⁺ , 1735.58 [M-12 (CF ₃ SO ₃ ⁻ ) +2 (DMSO)] ¹²⁺ , 1747.0 [ M-12 (CF ₃ SO ₃ ⁻ ) + (DMSO)] ¹²⁺ , 1740.5 [M-12 (CF ₃ SO ₃ ⁻ )] ¹²⁺

(Example 4) Production of hollow transition metal complex (2d)

(1) Synthesis of 1,3-dibromo-2- (3,3,4,4,5,5,6,6,6-nonafluorohexyloxy) benzene (4d) 2,6-dibromophenol (850 mg, 3.4 mmol) and triphenylphosphine (880 mg, 3.4 mmol) were added diisopropyl azodicarboxylate (0.66 mL, 3.4 mmol) and THF (10 mL), and the whole volume was added under an argon atmosphere at room temperature. For 30 minutes. Furthermore, 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexanol (1.1 mL, 6.8 mmol) was added and stirred for 12 hours under the same conditions.
The reaction mixture was concentrated under reduced pressure, and the concentrate was purified by silica gel column chromatography (n-hexane) to give compound (4b) (1.1 g, 2.2 mmol) as a clear oil (yield 67%). .

(Physical property data)
¹ H-NMR (500 MHz, DMSO-d ₆ , δ ppm); 7.52 (d, J = 8.2 Hz, 2H), 6.90 (t, J = 8.0 Hz, 1H), 4.31 (t , J = 7.0 Hz, 2H), 2.77 (m, 2H)

(2) Synthesis of 1,3-bis (4-pyridylethynyl) -2- (3,3,4,4,5,5,6,6,6-nonafluorohexyloxy) benzene (1d) Compound (4d) (1.3 g, 2.6 mmol), 4-ethynylpyridine hydrochloride (1.0 g, 7.4 mmol), Pd (PhCN) ₂ Cl ₂ (61 mg, 0.16 mmol), and CuI (20 mg, Trit-butylphosphine (0.82 mL, 0.33 mmol; 10% hexane solution) and diisopropylamine (1.9 mL, 14 mmol) were added to a dioxane (6 mL) solution of 0.11 mmol), and the whole volume was added under an argon atmosphere. And stirred at 50 ° C. for 17 hours. Ethyl acetate (10 mL) was added to the reaction mixture and filtered, and water (150 mL) was added to the filtrate, washed with ethylenediamine (1 mL), and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The resulting concentrate was purified by silica gel column chromatography (chloroform: methanol = 100: 1 (v / v)) to give the ligand (1a) ( 874 mg, 1.6 mmol) was obtained as a black solid (61% yield).

(Physical property data)
Melting point: 61-63 ° C
¹ H-NMR (500 MHz, CDCl ₃ , δ ppm); 8.64 (d, J = 6.0 Hz, 4H), 7.57 (d, J = 8.0 Hz, 2H), 7.37 (d, J = 6.0 Hz, 4H), 7.18 (t, J = 7.0 Hz, 1H), 4.61 (t, J = 6.5 Hz, 2H), 2.75 (m, 2H)

¹³ C-NMR (125 MHz, DMSO-d ₆ , δ ppm); 160.2 (C), 150.0 (CH), 135.0 (CH), 129.8 (C), 125.1 (CH), 124.9 (CH), 115.9 (C), 91.3 (C), 88.7 (C), 66.2 (CH ₂ ), 31.0 (CH ₂ )

¹⁹ F-NMR (470 Hz, DMSO-d ₆ , δ ppm); −82.2 (CF ₃ ), −114.2 (CF ₂ ), −125.5 (CF ₂ ), −127.3 (CF ₂ )

Elemental _{analysis: Calcd for C 26 H 15 F} 9 N 2 O: C, 57.57; H, 2.79; N, 5.16, Found: C, 57.77; H, 3.00; N, 4 .93

(3) Production of Hollow Transition Metal Complex (2d) The obtained ligand (1d) (5.9 mg, 10.9 μmol) and Pd (NO ₃ ) ₂ (2.1 mg, 9.l μmol) were converted to dimethyl Stir in sulfoxide (0.70 ml) at 70 ° C. for 3 hours.
When diethyl ether was added to the reaction mixture, a white solid was precipitated. Centrifugation was performed to remove the supernatant, and vacuum drying was performed to obtain the target product (5.7 mg) (yield 56%).

The physical property data of the obtained hollow transition metal complex (2d) are as follows.
¹ H-NMR (500 MHz, DMSO-d ₆ , δ ppm); 9.27 (br, 96H), 7.78 (br, 96H), 7.72 (br, 48H), 7.31 (br, 24H) 4.54 (br, 48H), 2.81 (br, 48H)

¹⁹ F-NMR (470 Hz, DMSO-d ₆ , δ ppm); -82.5 (72F), -114.4 (48F), -125.8 (48F), -127.6 (48F)

CSI-MS is a DMSO solution of the complex (2d) was added _CF 3 _SO 3 Na, a counter anion _CF 3 SO ₃ ^- was measured after replacing the.

_{CSI-MS (CF 3 SO 3} - _{salts, CH 3 CN): m /} z; 3261.4 [M-7 (CF 3 SO 3 -)] 7+, 2835.0 [M-8 (CF 3 SO 3 - )] ⁸⁺ , 2503.4 [M-9 (CF ₃ SO ₃ ⁻ )] ⁹⁺ , 2238.1 [M-10 (CF ₃ SO ₃ ⁻ )] ¹⁰⁺ , 2021.22 [M-11 (CF ₃ SO ₃₎ ⁻ )] ¹¹⁺ , 1840.2 [M-12 (CF ₃ SO ₃ ⁻ )] ¹²⁺

(Reference Example) The hollow transition metal complexes (2a) to (2d) obtained above have a space with a diameter of about 5 nm inside. This internal space is expected to behave as a fluorous phase having a diameter of about 5 nm due to the fluorophilic interaction of the 24 accumulated perfluoroalkyl chains. Therefore, using this space, we investigated the inclusion of fluorous small molecules by fluorophilic interactions.

The inclusion was observed by ¹⁹ F-NMR. This method focuses on ¹⁹ F nuclei contained in both the host and guest, and enables quantitative analysis with high sensitivity. Analysis was performed using the fact that the chemical shift value of the signal changes when the guest molecule is included.
Furthermore, not only analysis by a one-dimensional spectrum but also detailed analysis by various two-dimensional spectra were performed. In this study, ¹⁹ F-NMR spectra were assigned by ¹⁹ F-NOESY and ¹⁹ F-COSY spectra, and the identification of the site contributing to inclusion was examined. Furthermore, it was also confirmed by the ¹⁹ F-DOSY spectrum that the guest molecule was indeed included in the host molecule. The details of the experiment are as follows.

(1) Inclusion of perfluorooctane by hollow transition metal complex (2a) The inclusion of perfluorooctane (3, C ₈ F ₁₈ ) was examined using the hollow transition metal complex (2a). A DMSO-d ₆ solution (0.43 mM) of complex (2a) and perfluorooctane (3, liquid) were stirred at room temperature for 2 hours. When allowed to stand after completion of the stirring, the solution of the complex (2a) and the perfluorooctane (3) were separated into two phases of an organic layer (upper layer) and a fluorous layer (lower layer). Excess perfluorooctane (3) was removed by centrifugation, and ¹⁹ F-NMR measurement was performed.

The ¹⁹ F-NMR spectrum before and after the inclusion examination is shown in FIG. In the ¹⁹ F-NMR spectrum of only the complex (2a) shown in FIG. 2A, 6 signals derived from 6 types of ¹⁹ F nuclei were observed independently. When this is compared with the spectrum after the inclusion examination shown in FIG. 2 (b), a new signal (FIG. 2 (b): ○) derived from perfluorooctane (3) is generated. Dissolution of perfluorooctane (3) was confirmed. Further, a high magnetic field shift was observed in the signal derived from the complex (2a) (FIG. 2 (b): ●). In particular, the tip portion of the fluoroalkyl chain was introduced into the complex, i.e., the signals derived from the ^{19 F} nucleus is located in the portion close to the center of the spherical structure upfield shift is large ^{(F d-f: Δδ =} 0. ^{4-1.3ppm, F a-c: cf.Δδ} = 0.0-0.1ppm), the fluorophilic interaction of this part, in particular strongly involved in the dissolution of perfluorooctane (3) Was suggested.

Next, in order to confirm that the observed dissolution of perfluorooctane (3) involves the accumulation of fluoroalkyl chains in the internal space of complex (2a), perfluorooctane in DMSO-d ₆ ( 3) Dissolution by itself and dissolution of perfluorooctane (3) in a DMSO-d ₆ solution (8.9 mM) of the ligand (1a) were examined. Similarly to the complex (2a) solution, the DMSO-d ₆ and ligand (1a) solution and perfluorooctane (3) were stirred at room temperature for 2 hours, respectively, and then excess perfluorooctane (3) was added. It removed by centrifugation and measured by < ¹⁹ > F-NMR.

FIG. 3A shows a ¹⁹ F-NMR spectrum when perfluorooctane (3) and DMSO-d ₆ are mixed. In this spectrum, since the non-signal derived from trifluoroacetic acid, which is an external standard was not observed, perfluorooctane (3) alone was found not to dissolve in DMSO-d _6. The ¹⁹ F-NMR spectrum of ligand (1a) in FIG. 3 (b), the ¹⁹ F-NMR spectrum in the case of mixed ligands (1a) and perfluorooctane (3) in FIG. 3 (c) Shown respectively.

In this spectrum, a new signal derived from perfluorooctane (3) and a high magnetic field shift of the signal derived from ligand (1a) were not observed, and the same spectrum was obtained before and after mixing. This suggests that perfluorooctane (3) does not dissolve in DMSO-d ₆ even when ligand (1a) is present.
From the above results, it was revealed that the dissolution of perfluorooctane (3) in the DMSO-d ₆ solution of the complex (2a) was due to the effect of accumulating the fluoroalkyl chain on the inner surface of the complex (2a). .

Subsequently, ¹⁹ F-DOSY measurement was performed to show that dissolution of perfluorooctane (3) occurred by inclusion of the complex (2a) into the internal space. As shown in FIG. 4, it was found that all signals derived from the complex (2a) and perfluorooctane (3) have the same diffusion rate. This diffusion coefficient value D = 0.32 × 10 ⁻¹⁰ m ² s ⁻¹ (log D = −10.5) is about the same as the diffusion coefficient value of the complex (2a) alone measured by ¹ H-DOSY. there were. This revealed that the host molecule (complex (2a)) included the guest molecule (perfluorooctane (3)).

Furthermore, the correlation between the concentration of the complex (2a) and the inclusion behavior of perfluorooctane (3) was examined. Three complex (2a) solutions ([2a] = 0.18, 0.37, 0.54 mM) with different concentrations were mixed with 3 at room temperature, and then excess perfluorooctane (3) was centrifuged. And the ¹⁹ F-NMR measurement was performed. The measurement results are shown in FIG. The number of guest molecules included per host molecule was estimated from the integration ratio of each signal. As a result, in any case of [2a] = 0.18, 0.37, 0.54 mM, about 5.8 molecules of perfluorooctane ((3) is included per molecule of the complex (2a). In other words, the concentration of the guest molecule (3) present in the solution is proportional to the concentration of the host molecule (2a), which means that the guest molecule (3) is DMSO-d. _This is considered to be because it exists only in the fluorous space inside the host molecule (2a) existing in ₆ .

  As described above, it was found that the complex (2a) included about 5.8 molecules of perfluorooctane (3) in DMSO. The inclusion of perfluorooctane (3) was similarly examined for the complexes (2b) to (2d) having different fluoro chains. Complexes (2a) to (2d) have different internal effective volumes depending on the volume occupied by the fluoroalkyl chain contained therein. Moreover, it is considered that there is a difference in the strength of the fluorophilic interaction due to the difference in the number of fluorine atoms of the complex.

First, the inclusion of perfluorooctane (3) by the complex (2b) having a fluoroalkyl chain longer than the complex (2a) was examined. The ¹⁹ F-NMR spectrum before and after the inclusion examination is shown in FIG. When the number of inclusions per molecule of the complex (2b) was estimated from the signal integration ratio, it was found that about 2.5 molecules of perfluorooctane (3) were included. Complex (2b) has a longer fluoroalkyl chain than complex (2a), and the ratio of the volume occupied by the fluoroalkyl chain to the internal space of the complex is large. According to the molecular mechanics calculation, 19% of the internal space volume is occupied by the fluoroalkyl chain in the complex (2a), whereas 23% is occupied in the complex (2b). Therefore, the effective volume inside is small and the number of guests that can be included is considered to be small.

Subsequently, the inclusion of perfluorooctane (3) by a complex (2c) having a branched fluoroalkyl chain longer than that of the complex (2b) was examined. The ¹⁹ F-NMR spectrum before and after the inclusion examination is shown in FIG. When the number of inclusions per molecule of the complex (2c) was estimated from the signal integration ratio, it was found that about 2.0 molecules of perfluorooctane (3) was included. The number of guest inclusions of the complex (2c) is small compared to the complexes (2a) and (2b), as in the comparison of the complexes (2a) and (2b) described above. Discuss based on the difference. According to the molecular mechanics calculation, the ratio of the volume occupied by the fluoroalkyl chain to the internal space of the complex (2c) is 25%, and the guest inclusion number is less than that of the complexes (2a) and (2b). It can be said that this is a reasonable result.

Finally, the inclusion of perfluorooctane (3) by the complex (2d) having a shorter fluoroalkyl chain than the complex (2a) was examined. The ¹⁹ F-NMR spectrum before and after the inclusion examination is shown in FIG. In the case of the complex (2d), the spectrum obtained after stirring with the guest molecule (3) is the same as the spectrum before stirring, and the change in the chemical shift value of the signal derived from the complex (2d) or perfluorooctane No new signal derived from (3) was observed. This suggests that inclusion of perfluorooctane (3) did not occur in the case of complex (2d). Since the complex (2d) has a shorter fluoroalkyl chain than the complex (2a), the number of internal fluorine atoms is small. For this reason, it is considered that the inclusion of sufficient fluorophilic interaction for the inclusion of the guest did not occur and the inclusion did not occur. The occupied volume ratio of the fluoroalkyl chain by molecular mechanics calculation was 14%.
Table 1 summarizes the above results.

  Inclusion of perfluorooctane (3) by the hollow transition metal complexes (2a) to (2d) requires a fluorinated interaction with a long fluorine chain and requires an internal space in which guest molecules exist. It became clear. These two elements of interaction and effective volume can be precisely controlled by the length of the fluoroalkyl chain arranged on the inner surface, and can be freely designed at the stage of ligand synthesis. That is, by designing a relatively simple unit structure, the property of the fluorous space inside the complex can be easily and accurately changed.

It is a figure which shows the three-dimensional structure of the hollow transition metal complex of this invention comprised from 12 transition metal compounds (M) and 24 bidentate organic ligands (L). It is a ¹⁹ F-NMR spectrum before and after examination of inclusion of perfluorooctane (3) with a hollow transition metal complex (2a). It is a ¹⁹ F-NMR spectrum figure at the time of mixing a ligand (1a), perfluorooctane (3), and a ligand (1a) and perfluorooctane (3). When (a) is the ligand (1a), (b) is perfluorooctane (3), and (c) is a case where the ligand (1a) and perfluorooctane (3) are mixed. It is a ¹⁹ F-DOCY spectrum figure after the inclusion examination of perfluorooctane (3) by a hollow transition metal complex (2a). ¹⁹ F after removing excess perfluorooctane (3) after mixing solutions (0.18, 0.37, 054 mM) of different types of complexes (2a) with perfluorooctane (3). -NMR spectrum diagram. When (a) has a concentration of 0.18 mM, (b) has a concentration of 0.37 mM, and (c) has a concentration of 0.54 mM. It is a ¹⁹ F-NMR spectrum before and after examination of inclusion of perfluorooctane (3) by a hollow transition metal complex (2b). It is a ¹⁹ F-NMR spectrum figure before and behind inclusion examination of perfluorooctane (3) by a hollow transition metal complex (2c). (A) is a spectrum diagram from −60 ppm to −200 ppm of the complex (2c), and (b) is a spectrum from −60 ppm to −200 ppm after the complex (2c) and perfluorooctane (3) are mixed. (C) is a spectrum diagram of complex (2c) from −70 ppm to −85 ppm (left side) and from −110 ppm to −130 ppm (right side), and (d) is a complex (2c) and perfluorooctane. It is a spectrum figure of -70 ppm to -85 ppm (left side) and -110 ppm to -130 ppm after mixing (3) (right side). It is a ¹⁹ F-NMR spectrum before and after examination of inclusion of perfluorooctane (3) with a hollow transition metal complex (2d).

Claims (7)

A hollow transition metal complex having a hollow shell, wherein the hollow shell has n1 transition metal atoms (n1 represents an integer of 6 to 60) and 2 (n1) bidentate organic coordination. Formed from
The bidentate organic ligand is of the formula (I)

{Wherein, R ¹ and R ² each independently represents a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, a cyano group, or a nitro group.
m1 and m2 each independently represents an integer of 0 to 4. m1, m2 is 2 or more, ^{R 1} each other, even ^{R 2} together are each identical or may be different phases.
A represents the following formulas (a-1) to (a-4)

^{[R 3} has the formula: represents a group represented by -D-Rf, D represents an integer of formula :-( _O-CH 2) s- represented by the linking group (s 1 to 20) the formula :-( _CH 2) t-represented by a linking group (t is an integer of 1 to 20), or represents a linking group comprising a combination thereof, Rf represents a perfluoroalkyl group.
R ⁴ represents a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, a cyano group, or a nitro group.
m3 represents an integer of 0 to 3, and m4 represents an integer of 0 to 2. When m3 is 2 or more and m4 is 2, the plurality of R ⁴ may be the same or different.
Q is, -Nr1-, (r1 represents a hydrogen atom, an alkyl group, an aryl group or an acyl group.) - O -, - C (= O) -, - S-, or -SO ₂ - represents a. ] Is represented. }, And a compound represented by
A hollow transition metal complex, wherein R ³ is formed so as to be oriented inside a hollow shell. A hollow transition metal complex having a hollow shell, wherein the hollow shell has n2 (n2 is 6, 12, 24, 30 or 60) transition metal atoms and 2 (n2) Formed from a bidentate organic ligand,
The bidentate organic ligand is of the formula (I)

{Wherein, R ¹ and R ² each independently represents a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, a cyano group, or a nitro group.
m1 and m2 each independently represents an integer of 0 to 4. m1, m2 is 2 or more, ^{R 1} each other, even ^{R 2} together are each identical or may be different phases.
A represents the following formulas (a-1) to (a-4)

^{[R 3} has the formula: represents a group represented by -D-Rf, D represents an integer of formula :-( _O-CH 2) s- represented by the linking group (s 1 to 20) the formula :-( _CH 2) t-represented by a linking group (t is an integer of 1 to 20), or represents a linking group comprising a combination thereof, Rf is selected from the group consisting having 1 to 20 carbon atoms par Represents a fluoroalkyl group.
R ⁴ represents a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, a cyano group, or a nitro group.
m3 represents an integer of 0 to 3, and m4 represents an integer of 0 to 2. When m3 is 2 or more and m4 is 2, the plurality of R ⁴ may be the same or different.
Q is, -Nr1-, (r1 represents a hydrogen atom, an alkyl group, an aryl group or an acyl group.) - O -, - C (= O) -, - S-, or -SO ₂ - represents a. ] Is represented. }, And a compound represented by
A hollow transition metal complex, wherein R ³ is formed so as to be oriented inside a hollow shell.

From the transition metal compound (M) and the bidentate organic ligand (L), R ^{3 of the} bidentate organic ligand (L) is self-organized so as to be oriented inside the hollow shell. And M _n1 L _{2 (n1)} (where n1 is an integer of 6 to 60, and M and L may be the same or different from each other). Item 2. The hollow transition metal complex according to Item 1. From the transition metal compound (M) and the bidentate organic ligand (L), R ^{3 of the} bidentate organic ligand (L) is self-organized so as to be oriented inside the hollow shell. Formula: M _n2 L _{2 (n2)} (n2 is 6, 12, 24, 30 or 60, and M and L may be the same or different from each other). The hollow transition metal complex according to claim 2 represented. The transition metal atom constituting the transition metal complex is a kind selected from the group consisting of Ti, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Cd, Os, Ir, and Pt. The hollow transition metal complex according to any one of claims 1 to 4 . The bidentate organic ligand is represented by the formula (I-1)

(In the formula, D and Rf represent the same meaning as described above. )
The hollow transition metal complex according to claim 1 , wherein the hollow transition metal complex is a compound represented by the formula: The transition metal compound (M) and the bidentate organic ligand (L) are reacted at a ratio of 1 to 5 mol with respect to 1 mol of the transition metal compound (M). The method for producing a hollow transition metal complex according to any one of claims 1 to 6 .

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