JP3418954B2 - Metal complex having large lattice structure and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is obtained from a rigid linear organic ligand having an affinity (interaction) with a guest compound, and a transition metal compound forming a complex with the ligand.
Possess holes with a rectangular host lattice structure that has the function of selectively and easily encapsulating relatively large compounds
The present invention relates to an insoluble transition metal complex compound and a method for producing the same.

[0002]

2. Description of the Related Art It is known that an organic ligand is assembled with a metal compound to spontaneously form a complex compound having a precise structure having various functions, and the complex compound having the precise structure is known. In particular, a method is known in which the precise structure is formed by a stable bond, specifically, a coordinate bond, instead of a weak bond such as a hydrogen bond. As such a method, for example, 4,4′-bipyridine, trans-1,2-bis (4-pyridylethylene) or bis (4-pyridylacetylene) is used as the organic ligand, and the organic ligand is used. There is known a highly shape-selective coordination bond compound (metal complex compound) in which a rigid structure is formed as a lattice skeleton having an inclusion function by self-assembly from Cd (NO ₃ ) ₂ which is a metal compound. These are also called coordination-bonded zeolites. However, in the conventional metal complex compound, the pores having a rectangular host lattice structure are relatively small, and when large pores are to be formed, a penetrating structure is formed when the lattice structure is formed, so It was practically impossible to form a metal complex compound having pores having an inclusion lattice structure. Moreover, the characteristics (inclusion ability) of the guest compound incorporation were not good.

Since the above-mentioned coordination-bonded zeolite has the characteristics of zeolite as its name suggests, selective reversible adsorption, catalysis and catalyst support, which have been used for conventional zeolites, and recently become a topic. A cluster inclusion material having a desired size of particle clusters or fine line clusters (for example, JP-A-10-1300).
13)), or as a template material for forming mesosized crystals. From the above-mentioned clusters and meso-sized crystals, materials having new characteristics can be expected from the materials and shapes thereof, and this is a field where many studies have been conducted. At that time, the usefulness of the coordination-bonded zeolite is that it has pores (internal pore size) of a desired size, and its production method is reproducible and the method is easy. .

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to improve the guest compound uptake property (inclusion ability) of the above-mentioned conventional metal complex compound having a lattice-structured hole, and to have a lattice-structured hole. It is an object of the present invention to provide a metal complex compound having pores having a precise rectangular host lattice structure capable of incorporating a large compound by eliminating the disadvantage of forming a penetrating structure when producing a metal complex compound. In order to solve the above problems, in the study of various coordination organic compounds, by using a rigid linear organic ligand having an affinity (interaction) with a guest compound, the formation of the through structure can be achieved. It was discovered that the metal complex compound was eliminated and that the guest compound had good uptake ability (inclusion ability) into the pores of the rectangular host lattice structure. Furthermore, it has been confirmed that the inclusion compound is highly oriented due to the affinity of the ligand for the guest.

[0005]

The first aspect of the present invention comprises a rigid linear organic ligand having an affinity (interaction) with a guest compound represented by the general formula (1) and a metal compound. An insoluble transition metal complex compound having only vacancies, which is composed of a rectangular host lattice structure composed of the sides of the length of the linear organic ligand having the selective inclusion function, which is obtained from M. L-A-M. L ... (1) (However, ML is a 4-pyridyl group, -C≡N, -C≡
A substituent having a coordinating atom that coordinates with a metal of a metal compound selected from the group consisting of C ⁻ and —N═C group,
A is phenylene, polyphenylene (up to 6 polyphenylenes), 3,7-naphthylene, 9,10-anthrylene, 2,7-pyrenylene, or halogen-substituted versions thereof, or 5,15-metalporphyrilylene. It is a linear divalent organic group which has a affinity (interaction) with a guest compound and is bonded at both ends to a substituent having the above-mentioned coordinating atom and which has an axis of symmetry in the bonding direction. ) Second aspect of the present invention
Is selected by self-assembling and precipitating a rigid linear organic molecule having an affinity (interaction) with the guest compound represented by the general formula (1) and a transition metal compound in the presence of the guest compound. method for producing an insoluble transition metal complex compound having only the linear organic ligands length rectangular host lattice structure or Ranaru holes made from the side of having a clathrate function. The present inventor uses, as an organic ligand, a rigid linear organic molecule having an affinity (interaction) with a guest compound,
This is a solution to the above problem.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail. A. The rigid linear organic molecule (ligand) having an affinity (interaction) with the guest compound used for preparing the metal complex compound of the present invention has an affinity (interaction) with the guest compound. A rigid linear bonding group having, for example, an aromatic group having a divalent symmetry axis when benzene is used as a guest (in the structural formula of the divalent group, both ends to which the group having the coordination atom is bonded) , Which means that there is an axis of symmetry linking to each other.), And an atom (coordinating atom) coordinately bonded to the metal compound, which is linearly bonded to both ends of the divalent linear bonding group.
A compound consisting of a substituent having Here, having an affinity (interaction) means a property (inclusion ability) for facilitating the incorporation of a guest compound into a hole having a rectangular host lattice structure of a metal complex compound, and a two-dimensional incorporation of the guest compound (inclusion ability). When forming a 2D) lattice and a three-dimensional (3D) lattice structure, they have a binding property (sufficient affinity with the guest compound) to a guest compound to the extent that a penetrating structure is not formed, and a mutual strong bond is formed. Means the property of being effective. Through-hole formation is a phenomenon in which a lattice structure that divides the host holes that enclose the guest compound is formed, and there is a technique of positively utilizing this to form a regular net structure. (Stuart R. Batten, Richard
Robson, Angew.Chem.Int.Ed.1998,37,1460-1494), which is an unfavorable phenomenon for forming a large lattice structure (large frame structure) as in the present invention. Another feature is that the formation of the penetrating structure is eliminated by using a rigid linear organic molecule having an affinity (interaction) with the guest compound.

1. As a ring-constituting atom having an atom that forms a coordinate bond with the transition metal, a heterocycle having an N atom, such as a pyridine ring, can be given. As another substituent that forms a coordinate bond with the transition metal, Mention may be made of C≡N, —C≡C, or —N═C groups. 2. Further, the rigid linear bonding group that bonds the heterocycle or the substituent to both ends must have affinity (interaction) with the guest compound to form a rigid linear organic molecule. In some cases, it is required that a transition metal and a basic lattice structure (which means a frame structure having a size predicted from the length of the rigid molecule) not be coordinated so as not to break. Preferred are phenylene and polyphenylene (up to 6 polyphenylenes) [in FIG. 4 (a), 1 ≦ n
≦ 6, R is hydrogen, or a substituent having an affinity for the guest] or a derivative thereof (a substituent that improves the affinity for the guest compound, for example, a halogen atom such as fluorine may be included), 3,7-naphthylene [Fig. 4
(B)], 9,10-anthrylene [FIG. 4 (c)],
2,7-pyrenylene [FIG. 4 (d)], or those having the substituents exemplified above for improving the affinity for these guest compounds, or 5,15-metalporphyrilylene [FIG. 4 (e)] And so on. 3. Therefore, phenylene, polyphenylene (up to 6 polyphenylenes), 3,7-naphthylene, 9,10-anthrylene, 2,7-pyrenylene can be used as rigid linear organic molecules having an affinity (interaction) with the guest compound. ,
Or a halogen-substituted product thereof, or a pyridyl group [5 (15)-(e)] on 5,15-metal porphyrilylene,
C≡N [dicyanobiphenyl (f)], -C≡C, or a compound in which -N = C group is substituted can be mentioned, and particularly preferable one is a 4-pyridyl group bonded to both terminals of phenylene or polyphenylene. [(A) 1 ≦ n ≦ 6 in FIG. 4, R has an affinity for hydrogen or guest. Substituents such as fluorine] can be mentioned.

By using such an organic ligand,
It has become possible to easily design a metal complex compound having pores composed of a precise rectangular host lattice structure, which can take in a larger compound more easily (with sufficient inclusion ability). These rigid linear organic compounds are
When synthesizing the metal complex compound, it is supplied on the metal complex solution as a solution of a suitable solvent for the compound (it may be a guest compound itself), for example, an aromatic solvent.

B. Examples of the transition metal compound that forms a complex by coordination with the rigid organic molecule include inorganic compounds such as halides and mineral acid salts, or organic compounds such as organic acid salts, alkoxides, amine salts, complex salts and organic complexes. Alternatively, various compounds such as organometallic compounds may be used. Preferred examples thereof include inorganic acids of transition metals and salts of organic acids. A solvent that dissolves the organic coordination compound is selected as the solvent.

C. The size of the pores of the complex compound formed is basically determined by the kind of the rigid linear organic molecule or the transition metal compound, but the kind of the solvent (methanol) of the rigid linear organic molecule. The processing temperature also affects the porosity of the product. Further, since the porosity is a factor related to the purpose of use and the purpose of use, the respective factors of the latter will be selected according to the purpose of use. The solvent for forming the metal complex may be any solvent that dissolves the raw material compound, but is preferable. Examples thereof include alcohols, ethers, nitriles, ketones, esters and the like.

[0011]

Example 1 1,4-bis (4-pyridyl) benzene was used as a rigid organic molecule having an affinity (interaction) with a guest compound, and this (9 mg) was dissolved in benzene (10 mL). The reaction was carried out at room temperature (25 ° C). A solution of 6 mg of Ni (NO ₃ ) ₂ in 5 mL of MeOH is added to the above solution. The target rectangular host lattice structure spreads two-dimensionally, and the metal complex compound having the pores developed by stacking the two-dimensional structures and developing three-dimensionally comes out. The crystal of the obtained lattice complex can be isolated (collected) by filtering.
The resulting compound has the formula [Ni (2) ₂ (H ₂ O) ₂ ] / 2 (NO ₃ ).
It is represented by C ₆ H ₆ · 2.5 (MeOH) (wherein 2 in the formula (2) is bispyridylphenyl). Data of the obtained complex compound: monoclinic system, Cc, a = 16.854Å, b = 1
5.626Å, c = 19.144Å, β = 114.785 (2) °, V = 4577.5 (10) Å
³ , Z = 4, Dc = 1.334gcm ^-3 , final R value (finalR-factors), R
₁ = 0.0657; wR ₂ = 0.2224. This structure belongs to the space group C2 / c. All data were measured at 195K using a Bruker SMART / CCD diffractometer. FIG. 1 illustrates a state in which precise square host lattice structures are arranged in a two-dimensional direction, and is a top view of a metal complex compound having holes of the precise square host lattice structure of the present invention. is there. Figure 2
Indicates a structure in which the two-dimensionally grown structure is laminated and three-dimensionally developed. FIG. 3 shows a state in which a guest compound, here, benzene or benzene and methanol is included in the inner hole of the three-dimensionally grown tube structure. There are no special chemical bonds between layers, but various interactions that act between the host skeleton or between the host and guest (eg, intermolecular affinity such as van der Waals forces) are maximized. Laminate naturally due to the positional relationship.
Therefore, the layers are not always stacked vertically, and generally stacked while causing a shift. The metal complex compound of the present invention includes a structure in which a square lattice structure is two-dimensionally developed, and a structure in which the structures are stacked and developed in a three-dimensional direction to form a tube structure, and a void for taking in a guest compound is formed. Is.

Example 2 Using 4,4'-bis (4-pyridyl) biphenyl as a rigid ligand molecule, 12.6 mg of this compound is dissolved in 15 mL of benzene. The reaction was carried out at room temperature (25 ° C). 6 mg of Ni (N) in 5 mL of MeOH on the solution.
A solution in which O ₃ ) ₂ is dissolved is added. The target rectangular host lattice structure spreads two-dimensionally, and the metal complex compound having the pores developed by stacking the two-dimensional structures and developing three-dimensionally comes out. Four out of five molecules of benzene as a guest compound interact with the ligand. The deposited metal complex has a lattice structure that forms a large rectangular tube structure (channel). The axial channel is filled with guest molecules as shown in FIG. The laminated interlayer (IL) distance was 4.5Å. The obtained compound is represented by the formula [Ni (3) ₂ (NO ₃ ) ₂ ] .5C ₆ H ₆ .1.5 (MeOH) (wherein 3 in the formula (3) is bispyridylbiphenyl). . Data for complex compounds obtained: monoclinic, P21 /
n, a = 13.570 (2) Å, b = 19.874 (3) Å, c = 49.646 (7) Å, β = 96.
815 (3) °, V = 13294 (3) Å ³ , Z = 8, Dc = 1.237gcm ^-3 , final R
Value, R ₁ = 0.1561; wR ₂ = 0.3795. It shows that the pore volume is larger than that in Example 1 and the inclusion volume is large.

Comparative Example 4,4 'instead of the rigid organic molecule used in the above examples
-When using bipyridine. Lattice complexes using 4,4'-bipyridine are described in the literature, for example J. Am. Chem. Soc., 11
As reported in 6, 1151 (1994), the compounds that can be incorporated into the holes are relatively small.

The metal complex compound having precise square host pores obtained in the present invention is superior to the compounds of Comparative Examples in that it has a high clathrate ability and can clathrate large compounds. I understand.

The complex compound of the present invention may be used as a separation material or a storage material because it may have functions such as selective inclusion, permeation, adsorption / desorption of a substance (gas or liquid).
Furthermore, by arranging specific molecules in a complex in a certain direction and including them, a novel magnetic material, optical material, or electronic material that exhibits unique magnetic, optical, and electrical properties can be developed.

[0016]

INDUSTRIAL APPLICABILITY As described above, the metal complex compound of the present invention has a guest structure having a lattice structure forming a large rectangular tube structure (channel) and improved guest compound uptake properties. In addition, such a metal complex compound can easily design a lattice structure that forms various tube structures (channels) by designing a rigid linear organic molecule having an affinity (interaction) with the guest compound. Excellent effect is brought about.

[Brief description of drawings]

FIG. 1 shows a two-dimensional array of precise square host lattice structures (top view).

FIG. 2 shows a structure in which the two-dimensionally grown structure of FIG. 1 is stacked and three-dimensionally developed.

FIG. 3 is an observation of one tube structure in which a guest compound is included and arranged in the inner pores of the three-dimensionally grown tube structure.

FIG. 4 illustrates a compound of general formula (1).

[Explanation of symbols]

M metal atom L. G ligand G1, G2 guest molecule T tube structure G. S
Lattice structure I. L layer

Continuation of front page (56) References Makoto Fujita et al. J. Am. Chem. So c. , 1994, Vol. 116, No. 3, p. 1151-1152 Charles Michael Drain et al. J. Chem. Soc. Chem. Commun, 1994, p. 2313-2315 Stuart R.L. Battene et al. , Angewandte Chemie, International Edition, 1998, Vol. 37, No. 17, p. 1460-1494 Makoto Fujita et al. Chemistry Letters, 1991, p. 1031-1032 Makoto Fujita et al. , Bull. Chem. Soc. Jpn. 1996, Vol. 69, No. 6, p. 1471-1482 Makoto Fujita et al. J. Am, Chem. So c. , 1995, Vol. 117, No. 27, p. 7287-7288 (58) Fields surveyed (Int.Cl. ⁷ , DB name) C07D 213/06 C07D 487/22 C07C 255/50 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A rigid linear organic ligand having an affinity (interaction) with the guest compound represented by the general formula (1),
A rectangular host lattice structure composed of the sides of the length of the linear organic ligand having a selective inclusion function obtained from a metal compound
Insoluble transition metal complex compound having only granulated or Ranaru vacancies. M. L-A-M. L ... (1) (However, ML is a 4-pyridyl group, -C≡N, -C≡
A substituent having a coordinating atom that coordinates with a metal of a metal compound selected from the group consisting of C ⁻ and —N═C group,
A is phenylene, polyphenylene (up to 6 polyphenylenes), 3,7-naphthylene, 9,10-anthrylene, 2,7-pyrenylene, or halogen-substituted versions thereof, or 5,15-metalporphyrilylene. It is a linear divalent organic group which has a affinity (interaction) with a guest compound and is bonded at both ends to a substituent having the above-mentioned coordinating atom and which has an axis of symmetry in the bonding direction. ), 2. A rigid linear organic ligand having an affinity (interaction) with the guest compound represented by the general formula (1),
A transition metal compound and a self-assembly in the presence of a guest compound,
A method for producing an insoluble transition metal complex compound having only vacancies, which has a rectangular host lattice structure composed of the sides of the length of the linear organic ligand which is deposited to have a selective inclusion function. M. L-A-M. L ... (1) (However, ML is a 4-pyridyl group, -C≡N, -C≡
A substituent having a coordinating atom that coordinates with a metal of a metal compound selected from the group consisting of C ⁻ and —N═C group,
A is phenylene, polyphenylene (up to 6 polyphenylenes), 3,7-naphthylene, 9,10-anthrylene, 2,7-pyrenylene, or halogen-substituted versions thereof, or 5,15-metalporphyrilylene. It is a linear divalent organic group which has a affinity (interaction) with a guest compound and is bonded at both ends to a substituent having the above-mentioned coordinating atom and which has an axis of symmetry in the bonding direction. )