JP2014047178A - Porous metal complex, method for manufacturing porous metal complex, storage material, and optically functional material - Google Patents

Abstract

【選択図】なしProvided are a novel porous metal complex, a method for producing a porous metal complex, an occlusion material, and an optical functional material.
A porous metal complex comprising one metal atom or ion selected from Group 2 to Group 13 and a ligand represented by Formula (1). (P: one group selected from the group consisting of (A) and (B), or a divalent group formed by linking two or more and five or less groups selected from the group consisting of (A) and (B). At least one P includes one group selected from (A) and one group selected from (B) (A) a divalent aromatic heterocyclic group (B) a divalent aromatic hydrocarbon Group Q: m-valent aromatic hydrocarbon group R: —CO ₂ ^— , —SO ₃ ^— , —OPO ₃ ^{2 —} , —OPO ₃ H ⁻ , —C≡N, pyridyl group, imidazolyl group, imidazolate group M: 3 to 6, n: 0, 1. At least one of n is 1.)

[Selection figure] None

Description

  The present invention relates to a porous metal complex, a method for producing a porous metal complex, an occlusion material, and an optical functional material.

  A porous metal complex is a general term for a group of compounds having an infinite skeleton structure formed by connecting organic ligands with metal atoms or ions thereof. In recent years, this porous metal complex has attracted attention as a new porous material (Non-patent Document 1).

  A porous metal complex is a structure in which a pore structure is formed by accumulation of metal complex molecules, and is also called an integrated metal complex (Non-patent Document 2). The porous metal complex is considered to be capable of designing more uniform micropores and controlling the pore diameter as compared with porous materials such as zeolite and activated carbon.

Society for Fundamental Complex Engineering, “New edition: Coordination Chemistry-Fundamentals and Latest Developments”, Kodansha, 2002 Susumu Kitagawa, “Integrated Metal Complexes—From Crystal Engineering to Frontier Orbital Engineering”, Kodansha, 2001

  So far, porous metal complexes using compounds such as benzenedicarboxylic acid (terephthalic acid) and benzenetricarboxylic acid (trimesic acid) as ligands are well known, and the gas storage properties of these porous metal complexes are well known. Are known. However, the gas storage properties of these porous metal complexes are not sufficient.

  This invention is made | formed in view of such a situation, Comprising: It aims at providing the novel porous metal complex which has sufficient gas occlusion characteristic, its manufacturing method, and an occlusion material using the same.

  In order to solve the above-described problems, one embodiment of the present invention is represented by one kind of metal atom selected from Groups 2 to 13 of the periodic table or an ion thereof and the following general formula (1): Or a ligand having a coordinating group having an unshared electron pair capable of forming a coordination bond with the ion, and a coordination bond between the metal atom or the ion and the coordinating group. A porous metal complex is provided.

（式中、Ｐは、下記（Ａ）及び（Ｂ）からなる群から選ばれる１つの基、または下記（Ａ）及び（Ｂ）からなる群から選ばれる２以上５以下の基が連結してなる２価の基、を表し、少なくとも１つのＰは、下記（Ａ）からなる群から選ばれる１つの基と下記（Ｂ）からなる群から選ばれる１つの基とを含む。Ｐが複数ある場合、複数のＰは互いに同一でも異なっていてもよい。
（Ａ）置換基を有していてもよい芳香族複素環化合物から、芳香環に結合する２つの水素原子を取り去って得られる２価の基
（Ｂ）置換基を有していてもよい芳香族炭化水素化合物から、芳香環に結合する２つの水素原子を取り去って得られる２価の基
Ｑは、置換基を有してもよいｍ価の芳香族炭化水素基を表す。
Ｒは、配位基であり、−ＣＯ_２ ⁻、−ＳＯ_３ ⁻、−ＯＰＯ_３ ^２−、−ＯＰＯ_３Ｈ⁻、−Ｃ≡Ｎ、ピリジル基、イミダゾリル基又はイミダゾレート基を表す。
ｍは３〜６の整数を表し、ｎは０または１である。複数存在するｎは互いに同一であっても異なっていてもよい。ただし、複数存在するｎの少なくとも１つは１である。）

(In the formula, P is a group selected from the group consisting of the following (A) and (B), or 2 or more and 5 or less groups selected from the group consisting of the following (A) and (B). And at least one P includes one group selected from the group consisting of the following (A) and one group selected from the group consisting of the following (B). In this case, the plurality of P may be the same as or different from each other.
(A) A divalent group obtained by removing two hydrogen atoms bonded to an aromatic ring from an aromatic heterocyclic compound which may have a substituent (B) An aromatic which may have a substituent A divalent group Q obtained by removing two hydrogen atoms bonded to an aromatic ring from an aromatic hydrocarbon compound represents an m-valent aromatic hydrocarbon group which may have a substituent.
R is a coordinating ^{_{group, -CO 2 -, -SO 3 -}} , -OPO 3 2-, -OPO 3 H -, represents -C≡N, pyridyl group, an imidazolyl group or imidazolate group.
m represents an integer of 3 to 6, and n is 0 or 1. A plurality of n may be the same as or different from each other. However, at least one of a plurality of n is 1. )

  In one aspect of the present invention, m in the general formula (1) is preferably 3.

  In one aspect of the present invention, Q in the general formula (1) is preferably a benzene ring which may have a substituent.

  In one aspect of the present invention, it is preferable that all n in the general formula (1) is 1.

  In one aspect of the present invention, it further includes an auxiliary ligand that cross-links the two metal atoms or ions thereof by coordinating with the two metal atoms or ions thereof contained in the porous metal complex. Is preferred.

  One embodiment of the present invention is a metal salt containing one type of metal atom selected from Groups 2 to 13 of the periodic table, represented by the following general formula (2), and arranged on the metal atom or an ion thereof. A step of obtaining a reaction solution obtained by dissolving or dispersing an aromatic compound having a group capable of forming a coordinate bond in a solvent containing one or more polar solvents, a step of reacting the reaction solution, A method for producing a porous metal complex comprising:

（式中、Ｐは、下記（Ａ）及び（Ｂ）からなる群から選ばれる１つの基、または下記（Ａ）及び（Ｂ）からなる群から選ばれる２以上５以下の基が連結してなる２価の基、を表し、少なくとも１つのＰは、下記（Ａ）からなる群から選ばれる１つの基と下記（Ｂ）からなる群から選ばれる１つの基とを含む。Ｐが複数ある場合、複数のＰは互いに同一でも異なっていてもよい。
（Ａ）置換基を有していてもよい芳香族複素環化合物から、芳香環に結合する２つの水素原子を取り去って得られる２価の基
（Ｂ）置換基を有していてもよい芳香族炭化水素化合物から、芳香環に結合する２つの水素原子を取り去って得られる２価の基
Ｑは、置換基を有してもよいｍ価の芳香族炭化水素基を表す。
Ｒ^１は、−ＣＯ_２Ｒ^２、−ＳＯ_３Ｒ^２、−ＯＰＯ_３Ｒ^２ _２、−Ｃ≡Ｎ、ピリジル基、イミダゾリル基又は下記式（ｘ−１）又は（ｘ−２）で表される基を表す（ここで、Ｒ^２は水素原子、アルカリ金属原子又は炭素数１〜４のアルキル基を表し、複数ある場合は互いに同一であっても異なっていてもよい。下記式（ｘ−１）又は（ｘ−２）中、Ｍａはアルカリ金属原子を表す）。

(In the formula, P is a group selected from the group consisting of the following (A) and (B), or 2 or more and 5 or less groups selected from the group consisting of the following (A) and (B). And at least one P includes one group selected from the group consisting of the following (A) and one group selected from the group consisting of the following (B). In this case, the plurality of P may be the same as or different from each other.
(A) A divalent group obtained by removing two hydrogen atoms bonded to an aromatic ring from an aromatic heterocyclic compound which may have a substituent (B) An aromatic which may have a substituent A divalent group Q obtained by removing two hydrogen atoms bonded to an aromatic ring from an aromatic hydrocarbon compound represents an m-valent aromatic hydrocarbon group which may have a substituent.
R ¹ is represented by —CO ₂ R ² , —SO ₃ R ² , —OPO ₃ R ² ₂ , —C≡N, a pyridyl group, an imidazolyl group, or the following formula (x-1) or (x-2). Wherein R ² represents a hydrogen atom, an alkali metal atom or an alkyl group having 1 to 4 carbon atoms, and when there are a plurality of groups, they may be the same or different. 1) or (x-2), Ma represents an alkali metal atom).

ｍは３〜６の整数を表し、ｎは０または１を表す。複数存在するｎは互いに同一であっても異なっていてもよい。ただし、複数存在するｎの少なくとも１つは１である。）

m represents an integer of 3 to 6, and n represents 0 or 1. A plurality of n may be the same as or different from each other. However, at least one of a plurality of n is 1. )

  In one embodiment of the present invention, in the step of reacting the reaction solution, it is preferable that the reaction solution is reacted by heating in a range of 60 ° C. to 250 ° C.

In one embodiment of the invention, ^{R 1} in the general formula (2) is _-CO 2 ^{R 2,} and ^{R 2} is preferably a hydrogen atom or an alkali metal atom.

In one aspect of the present invention, R ² is preferably a hydrogen atom.

  In one aspect of the present invention, after the step of reacting the reaction solution, the two metal atoms are coordinated to the two metal atoms or ions thereof contained in the porous metal complex in the reaction solution. Alternatively, it is preferable to further include a step of dissolving or dispersing an auxiliary ligand capable of crosslinking the ions and reacting with the two metal atoms or ions thereof.

  In one embodiment of the present invention, before the step of reacting the reaction solution, the two metals are coordinated in the reaction solution to two metal atoms or ions thereof contained in the porous metal complex. It is preferable to further include a step of dissolving or dispersing an auxiliary ligand capable of cross-linking atoms or ions thereof.

  One embodiment of the present invention provides an occlusion material including the above-described porous metal complex.

  One embodiment of the present invention provides an optical functional material including the above-described porous metal complex.

  According to the present invention, a novel porous metal complex having a sufficient gas storage capacity can be provided. Moreover, according to this invention, the manufacturing method of a porous metal complex can be provided. Moreover, according to this invention, the optical functional material which consists of a porous metal complex can be provided.

It is a figure which shows the result of the thermogravimetry of the porous metal complex (A) synthesize | combined in Example 1. FIG. 2 is a powder X-ray diffraction pattern of the porous metal complex (A) synthesized in Example 1. FIG. 2 is an adsorption / desorption isotherm of nitrogen at 77 K of the porous metal complex (A) synthesized in Example 1. FIG. 2 is an adsorption / desorption isotherm of carbon dioxide at 195 K of the porous metal complex (A) synthesized in Example 1. FIG. 2 is an adsorption and desorption isotherm of hydrogen at 77K of the porous metal complex (A) synthesized in Example 1. FIG. 1 is an ORTEP diagram obtained by single crystal X-ray crystal structure analysis of a porous metal complex (A) synthesized in Example 1. FIG. 2 is an absorption and emission spectrum of the porous metal complex (A) synthesized in Example 1. FIG. It is a figure which shows the result of the thermogravimetry of the porous metal complex (B) synthesize | combined in Example 2. FIG. 3 is a powder X-ray diffraction pattern of the porous metal complex (B) synthesized in Example 2. FIG. 2 is an adsorption and desorption isotherm of nitrogen at 77K of the porous metal complex (B) synthesized in Example 2. FIG. 4 is an ORTEP diagram obtained by single crystal X-ray crystal structure analysis of a porous metal complex (B) synthesized in Example 2. FIG.

  The porous metal complex of this embodiment is represented by the following general formula (1) and one kind of metal atom selected from Groups 2 to 13 of the periodic table, and the metal atom or ion thereof. And a ligand provided with a coordination group having an unshared electron pair capable of forming a coordination bond, and having a coordination bond between the metal atom or its ion and the coordination group.

（式中、Ｐは、下記（Ａ）及び（Ｂ）からなる群から選ばれる１つの基、または下記（Ａ）及び（Ｂ）からなる群から選ばれる２以上５以下の基が連結してなる２価の基、を表し、少なくとも１つのＰは、下記（Ａ）からなる群から選ばれる１つの基と下記（Ｂ）からなる群から選ばれる１つの基とを含む。Ｐが複数ある場合、複数のＰは互いに同一でも異なっていてもよい。
（Ａ）置換基を有していてもよい芳香族複素環化合物から、芳香環に結合する２つの水素原子を取り去って得られる２価の基
（Ｂ）置換基を有していてもよい芳香族炭化水素化合物から、芳香環に結合する２つの水素原子を取り去って得られる２価の基
Ｑは、置換基を有してもよいｍ価の芳香族炭化水素基を表す。
Ｒは、配位基であり、−ＣＯ_２ ⁻、−ＳＯ_３ ⁻、−ＯＰＯ_３ ^２−、−ＯＰＯ_３Ｈ⁻、−Ｃ≡Ｎ、ピリジル基、イミダゾリル基又はイミダゾレート基を表す。
ｍは３〜６の整数を表し、ｎは０または１である。複数存在するｎは互いに同一であっても異なっていてもよい。ただし、複数存在するｎの少なくとも１つは１である。）

(In the formula, P is a group selected from the group consisting of the following (A) and (B), or 2 or more and 5 or less groups selected from the group consisting of the following (A) and (B). And at least one P includes one group selected from the group consisting of the following (A) and one group selected from the group consisting of the following (B). In this case, the plurality of P may be the same as or different from each other.
(A) A divalent group obtained by removing two hydrogen atoms bonded to an aromatic ring from an aromatic heterocyclic compound which may have a substituent (B) An aromatic which may have a substituent A divalent group Q obtained by removing two hydrogen atoms bonded to an aromatic ring from an aromatic hydrocarbon compound represents an m-valent aromatic hydrocarbon group which may have a substituent.
R is a coordinating ^{_{group, -CO 2 -, -SO 3 -}} , -OPO 3 2-, -OPO 3 H -, represents -C≡N, pyridyl group, an imidazolyl group or imidazolate group.
m represents an integer of 3 to 6, and n is 0 or 1. A plurality of n may be the same as or different from each other. However, at least one of a plurality of n is 1. )

  Moreover, the manufacturing method of the porous metal complex of this embodiment is represented by the following general formula (2), a metal salt containing one type of metal atom selected from Group 2 to Group 13 of the periodic table, Obtaining a reaction solution obtained by dissolving or dispersing an aromatic compound having a group capable of forming a coordination bond with an atom or an ion thereof in a solvent containing one or more polar solvents; Reacting the reaction solution.

（式中、Ｐは、下記（Ａ）及び（Ｂ）からなる群から選ばれる１つの基、または下記（Ａ）及び（Ｂ）からなる群から選ばれる２以上５以下の基が連結してなる２価の基、を表し、少なくとも１つのＰは、下記（Ａ）からなる群から選ばれる１つの基と下記（Ｂ）からなる群から選ばれる１つの基とを含む。Ｐが複数ある場合、複数のＰは互いに同一でも異なっていてもよい。
（Ａ）置換基を有していてもよい芳香族複素環化合物から、芳香環に結合する２つの水素原子を取り去って得られる２価の基
（Ｂ）置換基を有していてもよい芳香族炭化水素化合物から、芳香環に結合する２つの水素原子を取り去って得られる２価の基
Ｑは、置換基を有してもよいｍ価の芳香族炭化水素基を表す。
Ｒ^１は、−ＣＯ_２Ｒ^２、−ＳＯ_３Ｒ^２、−ＯＰＯ_３Ｒ^２ _２、−Ｃ≡Ｎ、ピリジル基、イミダゾリル基又は下記式（ｘ−１）又は（ｘ−２）で表される基を表す（ここで、Ｒ^２は水素原子、アルカリ金属原子又は炭素数１〜４のアルキル基を表し、複数ある場合は互いに同一であっても異なっていてもよい。下記式（ｘ−１）又は（ｘ−２）中、Ｍａはアルカリ金属原子を表す）。

(In the formula, P is a group selected from the group consisting of the following (A) and (B), or 2 or more and 5 or less groups selected from the group consisting of the following (A) and (B). And at least one P includes one group selected from the group consisting of the following (A) and one group selected from the group consisting of the following (B). In this case, the plurality of P may be the same as or different from each other.
(A) A divalent group obtained by removing two hydrogen atoms bonded to an aromatic ring from an aromatic heterocyclic compound which may have a substituent (B) An aromatic which may have a substituent A divalent group Q obtained by removing two hydrogen atoms bonded to an aromatic ring from an aromatic hydrocarbon compound represents an m-valent aromatic hydrocarbon group which may have a substituent.
R ¹ is represented by —CO ₂ R ² , —SO ₃ R ² , —OPO ₃ R ² ₂ , —C≡N, a pyridyl group, an imidazolyl group, or the following formula (x-1) or (x-2). Wherein R ² represents a hydrogen atom, an alkali metal atom or an alkyl group having 1 to 4 carbon atoms, and when there are a plurality of groups, they may be the same or different. 1) or (x-2), Ma represents an alkali metal atom).

ｍは３〜６の整数を表し、ｎは０または１を表す。複数存在するｎは互いに同一であっても異なっていてもよい。ただし、複数存在するｎの少なくとも１つは１である。）

m represents an integer of 3 to 6, and n represents 0 or 1. A plurality of n may be the same as or different from each other. However, at least one of a plurality of n is 1. )

Moreover, the occlusion material of this embodiment contains the above-mentioned porous metal complex.
Moreover, the optical functional material of this embodiment contains the above-mentioned porous metal complex.
Hereinafter, it demonstrates in order.

<Porous metal complex>
(Aromatic compounds)
The ligand represented by the general formula (1) of the present embodiment and having a coordinating group will be described.

In general formula (1), P is one group selected from the group consisting of the following (A) and (B), or two or more and five or less groups selected from the group consisting of the following (A) and (B). Represents at least one divalent group, and at least one P includes one group selected from the group consisting of the following (A) and one group selected from the group consisting of the following (B). When there are a plurality of P, the plurality of P may be the same as or different from each other.
(A) A divalent group obtained by removing two hydrogen atoms bonded to an aromatic ring from an aromatic heterocyclic compound which may have a substituent (B) An aromatic which may have a substituent Divalent group obtained by removing two hydrogen atoms bonded to an aromatic ring from an aromatic hydrocarbon compound

  The “divalent group formed by linking two or more and five or less groups selected from the group consisting of (A) and (B)” means two or more selected from the group consisting of (A) and (B). As a result of connecting 5 or less groups in series at each binding site, it indicates a divalent group having one binding site on each of the aromatic rings at both ends.

  Here, examples of the aromatic heterocyclic ring in the divalent group represented by (A) include a pyrrole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a furan ring, a thiophene ring, a thiazole ring, an imidazole ring, and an oxazole ring. It is done. From the viewpoint of easy synthesis of the porous metal complex of the present embodiment, a pyrrole ring, a pyridine ring, a furan ring, and a thiophene ring are preferable, and a furan ring, a thiophene ring, and a pyrrole ring are more preferable.

  Further, preferred examples of the aromatic hydrocarbon ring in the divalent group represented by (B) include a benzene ring, a naphthalene ring, an azulene ring, and an anthracene ring.

  In the general formula (1), when there are a plurality of P, it is easy to form an ordered pore structure.

In the general formula (1), Q represents an m-valent aromatic hydrocarbon group which may have a substituent. Examples of the aromatic hydrocarbon ring constituting the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, an azulene ring, an anthracene ring, and an anthraquinone ring.
Since the synthesis of the porous metal complex of this embodiment is easy, the aromatic hydrocarbon ring constituting Q is preferably a benzene ring, naphthalene ring, azulene ring, anthracene ring, or anthraquinone ring, more preferably A benzene ring, a naphthalene ring, an anthracene ring, and an anthraquinone ring, more preferably a benzene ring and a naphthalene ring, and particularly preferably a benzene ring.

As the substituent that P and Q may have,
Halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; silyl group having an alkyl group having 1 to 4 carbon atoms; methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group , Sec-butyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, norbornyl group, nonyl group, cyclononyl group, decyl group, adamantyl group, dodecyl group, cyclododecyl group, pentadecyl group C1-C50 linear, branched or cyclic alkyl groups such as octadecyl group and docosyl group; methoxy group, ethoxy group, propyloxy group, butoxy group, pentyloxy group, cyclohexyloxy group, norbornyloxy group , Straight chain, branched or ring having 1 to 50 carbon atoms such as decyloxy group, dodecyloxy group An alkoxy group having an alkyl group of: phenyl group, 4-bromophenyl group, 2,6-dimethylphenyl group, 4-biphenyl group, 2-methylphenyl group, 3-ethenylphenyl group, pentafluorophenyl group, 4- Trifluoromethylphenyl group, 3,5-dibromophenyl group, 3,5-dimethoxyphenyl group, 3,5-dihydroxyphenyl group, 4-tert-butyl-2,6-methoxymethylphenyl group, 4-tert-butyl Examples include aryl groups having 6 to 60 carbon atoms such as phenyl group, 4-octylphenyl group, 4-dodecylphenyl group, 4-methylphenyl group, 1-naphthyl group, 2-naphthyl group, and 9-anthryl group. .

Since the synthesis of the porous metal complex of the present embodiment is easy, the substituent that P and Q may have is preferably a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Alkyl groups having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, tert-butyl group, cyclohexyl group, norbornyl group and adamantyl group; methoxy group and ethoxy group , A propyloxy group, a butoxy group, a pentyloxy group, etc., a linear or branched alkoxy group having 1 to 10 carbon atoms; phenyl group, 4-bromophenyl group, 2,6-dimethylphenyl group, 4-biphenyl group, 2 -Methylphenyl group, 3-ethenylphenyl group, pentafluorophenyl group, 4-trifluoromethylphenyl group, 3,5-dibromophenyl 3,5-dimethoxyphenyl group, 3,5-dihydroxyphenyl group, 4-tert-butyl-2,6-methoxymethylphenyl group, 4-tert-butylphenyl group, 4-octylphenyl group, 4-dodecylphenyl An aryl group having 6 to 30 carbon atoms such as a group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group,
More preferably, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, isopropyl group, tert-butyl group, cyclohexyl group, norbornyl group, adamantyl group, methoxy group, ethoxy group, phenyl group, 4-bromophenyl group, 2,6-dimethylphenyl group, 4-biphenyl group, 2-methylphenyl group, pentafluorophenyl group, 4-trifluoromethylphenyl group, 4-tert-butylphenyl group, 4-octylphenyl Group, 4-dodecylphenyl group, 2-naphthyl group, 9-anthryl group,
More preferred are fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, isopropyl group and tert-butyl group.

  The explanation and illustration of these substituents are the same in the “substituent” in the present specification.

In the general formula (1), R is a coordinating group having an unshared electron pair capable of forming a coordination bond to a metal atom or an ion thereof in the porous metal complex, and —CO ₂ ^— , —SO ^{_{3 -, -OPO 3 2-, -OPO}} 3 H -, represents -C≡N, pyridyl group, an imidazolyl group or imidazolate group.

Here, the “pyridyl group” is a group represented by —C ₅ H ₄ N, and the bonding position may be any of 2-position, 3-position, and 4-position.

The “imidazolyl group” is a group represented by —C ₃ H ₃ N ₂ , and the bonding position may be any of the 1-position, 2-position, and 4-position.

In addition, the “imidazolate group” is a group represented by —C ₃ H ₂ N ₂ , and is coordinated to a metal with a total of five atoms of three carbon atoms and two nitrogen atoms constituting the ring. It is a group.

R is preferably —CO ₂ ^— , —SO ₃ ^— , —OPO ₃ ^2— , —OPO ₃ H ^— , and more preferably —CO ₂ ^— , —SO ₃ ^— .

  In the general formula (1), m represents an integer of 3 to 6. M is preferably 3 or 4 and more preferably 3 because the porous metal complex of this embodiment is easily synthesized.

  In the general formula (1), n is 0 or 1. A plurality of n may be the same as or different from each other. However, at least one of a plurality of n is 1. It is preferable that all n is 1 because the porous metal complex of the present embodiment is easily synthesized.

  As the ligand represented by the general formula (1), ligands represented by the following formulas (1-a) to (1-t) are preferable.

  Next, the manufacturing method of the aromatic compound (aromatic compound represented by the said General formula (2)) used as the precursor of the ligand represented by the said General formula (1) is demonstrated.

  The aromatic compound represented by the general formula (2) may be produced by any known method, for example, by the following method.

The aromatic compound represented by the general formula (2) includes compounds represented by the following general formulas (3-a) and (3-b), and the following general formulas (4-a) to (4- It can be synthesized by a cross-coupling reaction with a compound represented by j). The compounds represented by the following general formulas (3-a) and (3-b) are compounds corresponding to Q in the above general formula (2), and the following general formulas (4-a) to (4-j) Is a compound corresponding to P and R ¹ in the above general formula (2).

In the general formulas (3-a) and (3-b), X is a halogen atom, a nitro group, or a group represented by —OSO ₂ Y (where Y is an optionally substituted carbon atom having 1 to 6 carbon atoms). Represents a linear, branched or cyclic alkyl group. Several X may mutually be same or different.

In the above general formulas (4-a) to (4-j), R ³ is —CO ₂ R ⁴ , —SO ₃ R ⁴ , —OPO ₃ R ⁴ ₂ , —C≡N, pyridyl group, imidazolyl group, or The group represented by Formula (x-1) or (x-2) is represented.

Wherein, R ⁴ corresponds to R ² in the general formula (2) represents a hydrogen atom, an alkali metal atom or an alkyl group having 1 to 4 carbon atoms. When there are a plurality of R ^{4 s} , they may be the same or different. In the formula (x-1) or (x-2), Ma represents an alkali metal atom.

In the above general formulas (4-a) to (4-j), M is -B (OY ¹ ) ₂ , -Si (Y ² ) ₃ , -Sn (Y ³ ) ₃ , -Z ¹ (Z ² ). represents _α .
Here, Y ¹ represents a hydrogen atom or an optionally substituted linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and two Y ¹ may be the same or different, two Y ¹ are taken together may form a ring.
Y ² represents an optionally substituted linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and three Y ² may be the same or different.
Y ³ represents an optionally substituted linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and three Y ³ may be the same or different.
Z ¹ represents an ion of lithium, sodium, potassium, magnesium, calcium, copper or zinc, and Z ² represents a chloride ion, bromide ion or iodide ion.
Α is an integer of 0 or more.

  In the cross-coupling reaction, the compounds represented by the general formulas (3-a) and (3-b) and the compounds represented by the general formulas (4-a) to (4-j) It is preferable to carry out by dissolving the compound in an appropriate solvent that does not decompose. Examples of the solvent include toluene, xylene, benzene, acetonitrile, tetrahydrofuran, N, N-dimethylformamide and a mixed solvent thereof.

  Examples of the catalyst used for the cross-coupling reaction include iron complexes, nickel complexes, ruthenium complexes, palladium complexes, platinum complexes and the like.

  The cross coupling reaction is preferably performed at 60 ° C. or higher and 150 ° C. or lower, more preferably 80 ° C. or higher and 120 ° C. or lower. The reaction time of the cross coupling reaction is preferably 5 minutes to 100 hours, more preferably 1 hour to 48 hours, and particularly preferably 5 hours to 24 hours. In addition, reaction temperature and reaction time can be adjusted with the combination of a catalyst and a solvent.

(Metal atom or its ion)
Next, the metal atom and its ion contained in the porous metal complex of this embodiment will be described.

The metal atom or its ion of the present embodiment is a metal atom or its ion selected from Groups 2 to 13 of the periodic table.
Specifically, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, titanium, zirconium , Hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, mercury, aluminum , Gallium, indium, thallium atoms or ions.

Since it is easy to form a complex with the ligand represented by the general formula (1), preferably, magnesium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, Erbium, thulium, ytterbium, lutetium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, copper, zinc, cadmium, aluminum, gallium, indium, thallium An atom or ion,
More preferably, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, chromium, iron, copper, zinc, cadmium, aluminum, gallium, An atom or ion of indium.

(Auxiliary ligand)
The porous metal complex in the present embodiment may be referred to as a ligand (hereinafter referred to as an auxiliary ligand) necessary for forming a porous metal complex in addition to the ligand represented by the general formula (1). There may be).

  The auxiliary ligand is coordinated to two metal atoms or ions thereof included in the porous metal complex of the present embodiment, for example, two metal atoms or ions included per molecule of the porous metal complex, respectively. Thus, it is a ligand that bridges the two metal atoms or ions thereof. The auxiliary ligand includes two or more atoms or groups capable of coordinating to a metal atom or an ion thereof, and coordinates and bridges to the two metal atoms or the ions thereof to form a lattice (skeleton) of the porous metal complex. Part of it.

  For example, the product obtained by reacting the ligand represented by the general formula (1) with the above metal atom or ion thereof has a plate-like (layered) crystal structure that spreads in the plane direction. In this case, a porous metal complex can be obtained by adding an auxiliary ligand and crosslinking the layers with the auxiliary ligand.

Here, as an auxiliary ligand, a nitrogen atom having a lone electron pair such as pyridazine, pyrimidine, pyrazine, 2,2′-bipyridyl, 3,3′-bipyridyl, 4,4′-bipyridyl, triethylenediamine is used. Two compounds, oxalic acid (ethanedioic acid), malonic acid (propanedioic acid), succinic acid (butanedioic acid), phthalic acid (benzene-1,2-dicarboxylic acid), isophthalic acid (benzene-1, And compounds having two carboxy groups such as 3-dicarboxylic acid) and terephthalic acid (benzene-1,4-dicarboxylic acid).
Since it is easy to handle, pyrazine, 4,4′-bipyridyl, triethylenediamine, oxalic acid and terephthalic acid are preferred, and pyrazine, 4,4′-bipyridyl and triethylenediamine are more preferred.

(Porous metal complex structure)
The porous metal complex in the present embodiment has a structure in which a plurality of pores are regularly formed in a crystal structure. Although the manufacturing method of the porous metal complex in the present embodiment will be described in detail later, whether or not the obtained metal complex is “porous” confirms whether or not one of the following two conditions is satisfied. It can be judged by doing.

(Condition 1)
First, porous metal complexes tend to exhibit crystallinity (that is, tend to have regular repeating units). Therefore, the porous metal complex of this embodiment gives a diffraction peak (2θ) by powder X-ray diffraction (XRD) measurement. That is, when a metal complex produced by the production method described later has porosity, it tends to give a diffraction peak by XRD measurement.

  The porous metal complex in this embodiment is preferably one in which a 2θ diffraction peak is observed at 0.1 ° or more and 12 ° or less. More preferably, the 2θ diffraction peak is observed from 0.1 ° to 10 °, more preferably from 0.1 ° to 8 °, and more preferably from 0.1 ° to 7 °. What is observed is particularly preferred.

(Condition 2)
In addition, when the metal complex produced by the production method described later exhibits porosity, the surface area of the substance becomes very wide. Therefore, the BET calculated from the measurement of nitrogen adsorption / desorption isotherm at 77K The specific surface area shows a very large value. Specifically, when the metal complex produced by the production method described later has porosity, it tends to be a value of 5 m ² g ⁻¹ or more by measuring the BET specific surface area.

The porous metal complex preferably has a BET specific surface area of 5 m ² g ⁻¹ or more and 20000 m ² g ⁻¹ or less. Furthermore, the BET specific surface area is more preferably 50 m ² g ⁻¹ or more and 20000 m ² g ⁻¹ or less, more preferably 100 m ² g ⁻¹ or more and 20000 m ² g ⁻¹ or less, and even more preferably 200 m ² g ⁻¹ or more. What is 20000 m < ² > g < ^-1 > or less is still more preferable.

  The porous metal complex as described above has sufficient gas storage characteristics.

<Method for producing porous metal complex>
The porous metal complex of the present embodiment comprises an aromatic compound represented by the general formula (2) and a metal salt containing one metal atom selected from Groups 2 to 13 of the periodic table. A step (first step) of preparing a solution or dispersion (hereinafter referred to as a reaction solution) containing seeds or two or more polar solvents, and a step of reacting the reaction solution (second step) are provided. It can be obtained by a manufacturing method.

  Here, even if the reaction solution is a dispersion, the reaction substrate dispersed with the progress of the reaction is consumed, and the target porous metal complex can be obtained. However, since the reaction is likely to proceed, the reaction solution is preferably a solution.

In the aromatic compound of the general formula (2) that is a raw material of the porous metal complex of the present embodiment, R ¹ is a group that becomes R in the general formula (1). That is, R ¹ is a group capable of forming a coordination bond to a metal atom or metal ion during a complex formation reaction.

Specifically, groups capable of forming a coordination bond to a metal atom or metal ion are —CO ₂ R ² , —SO ₃ R ^2, and —OPO ₃ R ² ₂ , and have an unshared electron pair. The group is —C≡N, a pyridyl group, or an imidazolyl group. Here, R ² represents a hydrogen atom, an alkali metal atom or an alkyl group having 1 to 4 carbon atoms, and when there are a plurality of R ^{2 s} , they may be the same as or different from each other.

R ¹ is preferably —CO ₂ R ² , —SO ₃ R ² and —OPO ₃ R ² ₂ , more preferably —CO ₂ R ² and —SO ₃ R ² .

In addition, R ¹ is preferably a porous metal complex that easily becomes an anion because it interacts with a metal ion that is a cation. For example, when R ¹ is —CO ₂ R ² , those that are likely to be —CO ₂ ^— are preferable, and from this viewpoint, R ² is more preferably a hydrogen atom or an alkali metal atom. In addition, it is more preferable that R ² is a hydrogen atom (R ¹ is a carboxy group) because an inorganic salt is not generated and the removal process is simplified.

  The metal salt used as a raw material for the porous metal complex of the present embodiment represents a salt having the metal atom as a normal cation. The valence of the cation is preferably 2 to 6, more preferably 2 to 4, and still more preferably 2 to 3 because it is necessary to have a plurality of the aforementioned aromatic compounds in order to form a porous metal complex.

The metal salt has an anion that makes the whole metal salt electrically neutral because the metal atom is usually a cation.
Such anions include fluoride ion, chloride ion, bromide ion, iodide ion, oxide ion, sulfide ion, hydroxide ion, hydride ion, sulfite ion, phosphate ion, cyanide ion. , Acetate ion, carbonate ion, sulfate ion, nitrate ion, bicarbonate ion, trifluoroacetate ion, thiocyanide ion, trifluoromethanesulfonate ion, tetrafluoroborate ion, hexafluorophosphate ion, tetraphenylborate ion, Examples thereof include alkoxides such as tetrakis (3,5-bis (trifluoromethyl) phenyl) borate ion, acetylacetonate, methoxide, ethoxide and isopropoxide.

  Since it has high solubility and can be suitably used in the production method of the present embodiment, preferably chloride ion, bromide ion, iodide ion, oxide ion, hydroxide ion, phosphate ion, cyanide ion, acetate ion, Alkoxides such as carbonate ion, sulfate ion, nitrate ion, hydrogen carbonate ion, trifluoroacetate ion, trifluoromethanesulfonate ion, acetylacetonate, methoxide, ethoxide, isopropoxide, more preferably chloride ion, bromide ion , Iodide ion, acetate ion, sulfate ion, nitrate ion.

  Moreover, when a plurality of anions are present, they may be the same or different.

  In addition to the above anions, the metal salt may have as a ligand a molecule that solvates to form a solvated salt.

Examples of the molecule include water, methanol, ethanol, isopropyl alcohol, ethylene glycol, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and acetone. , Chloroform, acetonitrile, benzonitrile, triethylamine, pyridine, pyrazine, diazabicyclo [2,2,2] octane, 4,4′-bipyridine, tetrahydrofuran, diethyl ether, dimethoxyethane, methyl ethyl ether, 1,4-dioxane, etc. Named,
Preferred are water, methanol, ethanol, isopropyl alcohol, ethylene glycol, N, N-dimethylformamide, and N, N-diethylformamide. When a plurality of the molecules are present, they may be the same or different.

  In the first step, the molar ratio of the aromatic compound represented by the general formula (2) and the metal salt containing one kind of metal atom or ion selected from Group 2 to Group 13 of the periodic table is: Since a yield becomes high, Preferably it is 0.5-3.0, More preferably, it is 0.8-2.5.

  In the first step, the concentration of the reaction solution of the aromatic compound represented by the general formula (2) in the reaction solution is high in solubility and the reaction solution becomes a solution, and the yield increases. Preferably, they are 1 mmol / L or more and 1000 mmol / L or less, More preferably, they are 10 mmol / L or more and 500 mmol / L or less.

  In the first step, the concentration of the reaction solution of the metal salt containing one kind of metal atom or ion selected from Group 2 to Group 13 of the periodic table in the reaction solution is high in solubility and the reaction solution is the same as the solution. It is preferably 1 mmol / L or more and 1000 mmol / L or less, and more preferably 10 mmol / L or more and 500 mmol / L or less.

  In the first step, the solvent constituting the reaction solution is N, N-dimethylformamide, N, N-diethylformamide, water, methanol, ethanol, isopropyl alcohol, dimethyl sulfoxide, N, N-dimethylacetamide, N -Polar solvents such as methyl-2-pyrrolidone.

  N, N-dimethylformamide, N, N-diethylformamide, water, methanol, and ethanol are preferred because the solubility of the metal salt and aromatic compound in the reaction is easy to ensure.

Note that, in the aromatic compound represented by the general formula (2), when R ¹ is an ester bond, the solvent constituting the reaction liquid described above, for hydrolyzing the ester bond R ¹ has Water shall be mixed.

  In the second step, the reaction temperature is a metal salt containing the aromatic compound represented by the general formula (2) and one metal atom selected from Groups 2 to 13 of the periodic table or ions thereof. Depending on the type, it may be adjusted as appropriate. The reaction temperature is usually from room temperature to 300 ° C., preferably 60 to 250 ° C. and more preferably reacted, more preferably 80 to 220 ° C. and more preferably reacted. More preferably, the reaction is performed by heating in the range of 100 ° C. or more and 200 ° C. or less. By heating and reacting at 60 ° C. or higher, the yield of the metal complex is further improved, and by heating and reacting at 250 ° C. or lower, decomposition of the solvent is further suppressed.

  In the second step, the reaction of the reaction solution can be performed in an air atmosphere. Although the reaction of the reaction solution can be carried out in an open system, it is preferable to use a sealed reaction vessel such as an autoclave because it can be reacted by heating to a temperature not lower than the boiling point of the solvent. When heated to a temperature equal to or higher than the boiling point of the solvent using a sealed reaction vessel, the inside of the vessel becomes a pressurized environment, and the reaction is performed under high temperature and high pressure.

  In the second step, the reaction vessel can be heated in an oil bath, an oven, or the like. It can also be performed by irradiating microwaves or ultrasonic waves.

  In the second step, the reaction time is preferably 1 minute or more and 1 week or less, more preferably 1 hour or more and 120 hours or less, and further preferably 2 hours or more and 72 hours or less. Regarding the reaction temperature and reaction time, the aromatic compound represented by the general formula (2) and the metal salt containing one kind of metal atom selected from Groups 2 to 13 of the periodic table or ions thereof are used. You can select by type. In addition, the produced porous metal complex tends to precipitate in the process of this embodiment, and is separated and separated by filtration, etc., and is isolated and purified by performing a washing operation and a drying operation as necessary. Can do.

  When the auxiliary ligand is used, the auxiliary ligand is used after the step of reacting the reaction solution containing the aromatic compound represented by the general formula (2) and the metal salt containing the above metal atom or its ion. The above-described metal atom or its ion may be reacted with the auxiliary ligand by dissolving or dispersing in the reaction solution.

  In addition, an auxiliary ligand is added to the reaction solution before the step of reacting the reaction solution containing the aromatic compound represented by the general formula (2) and the metal salt containing the metal atom or ion described above. The reaction solution may be reacted in the presence of an auxiliary ligand.

  The timing at which the auxiliary ligand is added can be appropriately selected according to the metal atom contained in the porous metal complex or its ion and the kind of the aromatic compound represented by the general formula (2).

  According to the method for producing a porous metal complex as described above, complex formation can be promoted by reacting in a liquid phase, and the intended porous metal complex can be easily produced.

<Occlusion material>
In order to use the porous metal complex of this embodiment as an occlusion material, it is desirable to perform a pretreatment for removing solvent molecules and the like present in the porous metal complex. The solvent molecules are derived from the reaction solution used in the above production.

  The pretreatment can be performed by heating the porous metal complex. The heating temperature is preferably 15 ° C. or higher and 250 ° C. or lower, more preferably 20 ° C. or higher and 230 ° C. or lower, considering the boiling point of the solvent molecules. Further, as the pretreatment described above, the porous metal complex may be washed with supercritical carbon dioxide. The pretreatment using supercritical carbon dioxide can remove solvent molecules more effectively than the heat treatment.

  As the occlusion material of this embodiment, a porous metal complex may be used alone, or an additive may be added. Here, the additive refers to silica, alumina, zeolite, activated carbon, a porous material such as a porous metal complex other than the present embodiment, a simple metal such as palladium or platinum, and the above-mentioned simple metal supported on activated carbon.

The component stored in the storage material of the present embodiment may be a liquid but is preferably a gas.
The porous metal complex of the present embodiment includes nitrogen, carbon dioxide, hydrogen, oxygen, carbon monoxide, hydrocarbon having 1 to 4 carbon atoms, helium, neon, argon, krypton, xenon, hydrogen sulfide, ammonia, and sulfur oxide. It exhibits gas storage capacity for gases such as nitrogen oxides and water vapor, and it has excellent gas storage capacity for nitrogen, carbon dioxide and hydrogen. Therefore, according to the occlusion material of the present embodiment, occlusion / storage of gases such as nitrogen, carbon dioxide, and hydrogen can be effectively realized.

<Optical functional materials>
The porous metal complex of this embodiment absorbs ultraviolet rays and emits light having a longer wavelength than ultraviolet rays. Therefore, the porous metal complex of this embodiment can be used as an optical functional material, and can be considered as a light emitting material, a solar cell material, an organic EL material, and a photochromic material.

<Others>
Further, since the porous metal complex of the present embodiment has a pore structure, in addition to gas storage materials, storage materials such as pharmaceuticals, molecular storage materials and separation materials of different sizes and diffusion rates, nanospaces Is expected to be used as a catalyst material. In addition, since the ligand skeleton is composed of a ligand having at least one heterocyclic group, and the conjugation spreads over the entire porous metal complex, the organic EL material, the transistor material, the solar cell material, the organic matter, and water It can also be used as a photodecomposition catalyst material.

  Moreover, the porous metal complex of this embodiment is suitable for uses such as a solid catalyst for catalyzing a redox reaction. Specifically, hydrogen peroxide decomposition catalyst, aromatic compound oxidation polymerization catalyst, exhaust gas / drainage purification catalyst, dye-sensitized solar cell oxidation-reduction catalyst layer, carbon dioxide reduction catalyst, reformed hydrogen production catalyst, Applications such as oxygen sensors can be mentioned.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all. Moreover, the analysis and evaluation in an Example were performed using the following.

(1) Thermogravimetry (TG)
Device: Rigaku Corporation differential thermal balance Thermo plus EVO II TG8120
Atmosphere: Nitrogen Temperature rising rate: 5 ° C. min ⁻¹

(2) Powder X-ray diffraction (XRD) measurement device: Bruker AXS Co., Ltd. D8 DISCOVER with GADDS
X-ray tube: Cu-Kα
X-ray output: 40kV-40mA
Exposure time: 600 seconds Resolution: 0.02 °
Angle measurement range: 4-40.2 °

(3) Adsorption / desorption isotherm measurement Device: BELSORP-max manufactured by Nippon Bell Co., Ltd.
Equilibrium time: Nitrogen 300 seconds (P / P ₀ : 0 to 1.0)
Carbon dioxide 300 seconds (P / P ₀ : 0 to 1.0)
Hydrogen 300 seconds (P / P ₀ : 0 to 1.0)

(4) Single crystal X-ray structural analysis device: CCD single crystal automatic X-ray structural analysis device manufactured by Rigaku Corporation Saturn 724+

<Synthesis Example 1>
(Synthesis of aromatic compound (a))
The aromatic compound (a) was synthesized according to the following reaction formula (10).

Under a nitrogen atmosphere, 1.63 g (3.00 mmol) of 1,3,5-tris (4-bromophenyl) benzene, 5.16 g (30.0 mmol) of 5-carboxythiophene-2-boronic acid, potassium carbonate 6. A mixture of 23 g (45.1 mmol) and 354 mg (0.31 mmol) tetrakis (triphenylphosphine) palladium and 120 mL N, N-dimethylformamide / water (3: 1 (volume ratio)) was prepared. Stir at 48 ° C. for 48 hours. After cooling the obtained solution to room temperature, insoluble matters were removed by filtration, and a liquid separation operation was performed using chloroform. Hydrochloric acid was added to the obtained aqueous layer until the pH reached 1, and a precipitate was obtained. The precipitate was collected by filtration, washed with water, ethanol and chloroform, and dried to obtain an aromatic compound (a) (760 mg, 1.1 mmol, 37%).
Further, in place of 1,3,5-tris (4-bromophenyl) benzene, 2.05 g (3.00 mmol) of 1,3,5-tris (4-iodophenyl) benzene was used for the fragrance by the same method. Group compound (a) was obtained (980 mg, 1.4 mmol, 48%).
¹ H NMR (DMSO-d ₆ , 500 MHz, δ / ppm): 7.64 (d, ³ J _HH = 4.0 Hz, 3H, ArH), 7.74 (d, ³ J _HH = 4.0 Hz, 3H, ArH), 7.85 (d, ³ J _HH = 8.5 Hz, 6H, ArH), 7.96 (d, ³ J _HH = 8.5 Hz, 6H, ArH), 7.98 (s, 3H, ArH), 13.0 (br s, 3H, CO ₂ H ).
¹³ C NMR (DMSO-d ₆ , 125 MHz, δ / ppm): 124.43 (CH), 124.75 (CH), 126.37 (CH), 128.02 (CH), 132.27 (C), 133.63 (C), 134.33 (CH ), 140.18 (C), 140.82 (C), 149.24 (C), 162.86 (C).
HRMS-ESI (m / z) : [MH] - calcd for C 39 H 23 O 6 S 3, 683.0662; found 683.0686.

<Example 1>
(Synthesis of porous metal complex (A))
Aromatic compound (a) 103 mg (150 μmol) was placed in a polytetrafluoroethylene crucible together with lanthanum nitrate (III) hexahydrate 70.5 mg (163 μmol) and N, N-dimethylformamide 7.5 mL. Sealed with a stainless steel jacket. The stainless steel jacket was heated and stirred in an oil bath adjusted to 120 ° C. for 48 hours, then cooled to room temperature, and the precipitate formed in the reaction solution was collected by filtration to obtain a powdery porous metal complex (A). It was.

(Thermogravimetric measurement of porous metal complex (A))
The obtained porous metal complex (A) was subjected to thermogravimetry (TG). FIG. 1 shows the results of thermogravimetry. As shown in the figure, when there is a weight change due to desorption of low molecular components when the temperature is raised to about 140 ° C., the weight change is hardly seen until the temperature exceeds about 400 ° C., and the porous metal complex (A ) Was found to be thermally stable.

(Powder X-ray diffraction measurement of porous metal complex (A))
The obtained porous metal complex (A) powder was subjected to X-ray diffraction (XRD). FIG. 2 is a powder X-ray diffraction pattern of the porous metal complex (A). In the obtained diffractogram, a diffraction peak was observed at 0.1 ° or more and 7 ° or less, and it was confirmed that the porous metal complex (A) was “porous”. Further, the obtained diffractogram was free from disturbance due to impurity peaks, and the regularity of the structure could be confirmed. It was found that the obtained porous metal complex (A) powder was of high purity.
2θ (°): 4.7, 5.6, 7.5, 9.1, 11.0, 11.5, 14.3

(Adsorption / desorption isotherm measurement of porous metal complex (A))
The obtained porous metal complex (A) was subjected to adsorption / desorption isotherm measurement. 3 is an adsorption / desorption isotherm of nitrogen at 77K, FIG. 4 is an adsorption / desorption isotherm of carbon dioxide at 195K, and FIG. 5 is an adsorption / desorption isotherm of hydrogen at 77K. In each figure, a solid line shows an adsorption isotherm, and a broken line shows a desorption isotherm.

Since the BET specific surface area of the porous metal complex (A) obtained from the nitrogen adsorption isotherm at 77K is 1086 m ² g ⁻¹ and is 200 m ² g ⁻¹ or more and 20000 m ² g ⁻¹ or less, it is porous. It was confirmed that the metal complex (A) was “porous”. Further, in the same nitrogen adsorption isotherm, the nitrogen storage amount when P / P ₀ was 0.2 was 309 mL (STP) g ⁻¹ .

  Further, it was found that the obtained porous metal complex (A) can adsorb and desorb carbon dioxide and hydrogen, and can be used for storing these gases.

(Single crystal structure analysis of porous metal complex (A))
13.7 mg (20 μmol) of the aromatic compound (a) is placed in a glass vial together with 24.4 mg (200 μmol) of benzoic acid and 1.0 mL (20 μmol) of a 20 mM lanthanum (III) nitrate / N, N-dimethylformamide solution. The vial was sealed with a stainless steel jacket. A stainless steel jacket was placed in an oven, heated to 120 ° C. over 10 hours, held at 120 ° C. for 48 hours, then cooled to room temperature over 10 hours, and single crystals produced in the reaction solution were recovered.

The single crystal of the obtained porous metal complex (A) was subjected to single crystal X-ray crystal structure analysis. FIG. 6 is an ORTEP diagram obtained by single crystal X-ray crystal structure analysis of the porous metal complex (A). As shown in the figure, it was found that the porous metal complex (A) contains a structure derived from the aromatic compound (a).
C ₄₂ H ₂₈ LaNO ₇ S ₃ , FW 893.74, monoclinic, Cc, a = 32.314 (17) Å, b = 23.992 (12) Å, c = 8.225 (4) Å, β = 101.060 (7) °, V = 6258 (6) Å ³ , Z = 4, ρ = 0.815 mm ^-1 , T = 223 (2) K, θ _max = 25.00 °, R _int = 0.0531, R ₁ (I> 2σ (I)) = 0.0868, wR ₂ (all data) = 0.2601, GOF = 1.049

(Optical properties of porous metal complex (A))
Ultraviolet-visible absorption and emission spectra of the porous metal complex (A) powder were measured. FIG. 7 is an ultraviolet absorption and emission spectrum of the porous metal complex (A). In the figure, the solid line indicates the absorption spectrum, and the broken line indicates the emission spectrum. As a result of the measurement, absorption with a maximum at 342 nm was observed. Further, when the emission spectrum was measured by exciting the porous metal complex (A) at 320 nm, light emission with a maximum at 457 nm was observed.

<Synthesis Example 2>
(Synthesis of aromatic compound (b))
The aromatic compound (b) was synthesized according to the following reaction formula (11).

Under a nitrogen atmosphere, 842 mg (1.50 mmol) of 1,3,5-tris (5-bromo-2-thienyl) benzene, 2.50 g (15.0 mmol) of 4-carboxyphenylboronic acid, 3.12 g of potassium carbonate ( 22.6 mmol) and 175 mg (0.15 mmol) of tetrakis (triphenylphosphine) palladium and 60 mL of N, N-dimethylformamide / water (3: 1 (volume ratio)), and the mixture is prepared at 100 ° C. Stir for 48 hours. After cooling the obtained solution to room temperature, insoluble matters were removed by filtration, and a liquid separation operation was performed using chloroform. Hydrochloric acid was added to the obtained aqueous layer until the pH reached 1, and a precipitate was obtained. The precipitate was collected by filtration, washed with water, ethanol and chloroform, and recrystallized from DMSO to obtain an aromatic compound (b) (712 mg, 1.04 mmol, 69%).
¹ H NMR (DMSO-d ₆ , 500 MHz, 80 ° C, δ / ppm): 7.71 (d, ³ J _HH = 4.0 Hz, 3H, ArH), 7.80 (d, ³ J _HH = 4.0 Hz, 3H, ArH ), 7.85 (d, ³ J _HH = 8.5 Hz, 6H, ArH), 7.93 (s, 3H, ArH), 8.01 (d, ³ J _HH = 8.5 Hz, 6H, ArH), -COOH not observed.
¹³ C NMR (DMSO-d ₆ , 150 MHz, 80 ° C, δ / ppm): 121.20 (CH), 124.86 (CH), 126.11 (CH), 126.15 (CH), 129.62 (C), 129.79 (CH), 134.90 (C), 137.04 (C), 142.00 (C), 142.42 (C), 166.37 (C).
HRMS-DART (m / z): M ⁺ calcd for C ₃₉ H ₂₄ O ₆ S ₃ , 684.0730; found 684.0715.

<Example 2>
(Synthesis of porous metal complex (B))
Aromatic compound (b) (27 mg, 40 μmol) was placed in a polytetrafluoroethylene crucible together with 25 mM lanthanum (III) nitrate / N, N-dimethylformamide solution (2.0 mL, 50 μmol), and the crucible was sealed with a stainless steel jacket. . A stainless steel jacket is put in an oven, heated to 120 ° C. over 10 hours, held at 120 ° C. for 48 hours, cooled to room temperature over 10 hours, and the precipitate formed in the reaction solution is collected by filtration. A porous metal complex (B) was obtained.

(Thermogravimetric measurement of porous metal complex (B))
The obtained porous metal complex (B) was subjected to thermogravimetry (TG). FIG. 8 shows the results of thermogravimetry. As shown in the figure, when there is a change in weight due to desorption of low molecular components when the temperature is raised to about 140 ° C., there is almost no change in weight until the temperature exceeds about 500 ° C., and the porous metal complex (B ) Was found to be thermally stable.

(Powder X-ray diffraction measurement of porous metal complex (B))
The obtained porous metal complex (B) was subjected to X-ray diffraction (XRD). FIG. 9 is a powder X-ray diffraction pattern of the porous metal complex (B). In the obtained diffractogram, a diffraction peak was observed at 0.1 ° to 7 °, and it was confirmed that the porous metal complex (B) was “porous”. Further, the obtained diffractogram showed no disorder due to the impurity peak and the regularity of the structure could be confirmed, and it was found that the obtained porous metal complex (B) powder was of high purity.
2θ (°): 4.8, 5.6, 7.6, 9.0, 10.8, 11.7, 14.0

(Adsorption / desorption isotherm measurement of porous metal complex (B))
The obtained porous metal complex (B) was subjected to adsorption / desorption isotherm measurement. FIG. 10 is an adsorption / desorption isotherm of nitrogen at 77K. In the figure, the solid line indicates the adsorption isotherm, and the broken line indicates the desorption isotherm.

BET specific surface area of the porous metal complex obtained from the nitrogen adsorption isotherm (B) at 77K, since it is 1213m ² g ^-1, or less 200 meters ² g ^-1 or more 20000 m ² g ^-1, porous It was confirmed that the metal complex (B) was “porous”. It was. Further, in the same nitrogen adsorption isotherm, the nitrogen occlusion amount when P / P ₀ was 0.2 was 345 mL (STP) g ⁻¹ .

(Single crystal structure analysis of porous metal complex (B))
Aromatic compound (b) 6.8 mg (10 μmol), acetic acid 4.2 mg (70 μmol), 20 mM lanthanum nitrate (III) / N, N-dimethylformamide solution 0.5 mL (10 μmol), N, N-dimethylformamide 0 Placed in a glass vial with 5 mL and sealed the vial with a stainless steel jacket. A stainless steel jacket was placed in an oven, heated to 120 ° C. over 10 hours, held at 120 ° C. for 120 hours, then cooled to room temperature over 10 hours, and single crystals produced in the reaction solution were recovered.

The single crystal of the obtained porous metal complex (B) was subjected to single crystal X-ray crystal structure analysis. FIG. 11 is an ORTEP diagram obtained by single crystal X-ray crystal structure analysis of the porous metal complex (B). As shown in the figure, the porous metal complex (B) was found to contain a structure derived from the aromatic compound (b).
C ₃₉ H ₂₃ LaO ₇ S ₃ , FW 838.66, monoclinic, Cc, a = 33.741 (9) Å, b = 23.667 (6) Å, c = 8.129 (2) Å, β = 103.816 (4) °, V = 6303 (3) Å ³ , Z = 4, ρ = 0.805 mm ^-1 , T = 223 (2) K, θ _max = 25.00 °, R _int = 0.0606, R ₁ (I> 2σ (I)) = 0.0953, wR ₂ (all data) = 0.3032, GOF = 1.113

<Comparative Example 1>
A porous metal complex using 2,5-thiophenedicarboxylic acid and indium (III) nitrate is reported in J. Am. Chem. Soc. 2008, 130, 12882-12883. According to this report, the nitrogen storage amount of this porous metal complex is 82 mL (STP) g ⁻¹ when P / P ₀ is 0.2.

  The results of the porous metal complex (A) synthesized in Example 1, the porous metal complex (B) synthesized in Example 2 and the nitrogen occlusion amount of the porous metal complex in the literature shown as Comparative Example 1 are shown in the following table. It is shown in 1.

As shown in Table 1, in the porous metal complexes of Examples 1 and 2 having ligands having a plurality of heterocyclic rings, the porous metal of Comparative Example 1 having a ligand having only one heterocyclic ring Compared with the complex, the nitrogen storage amount was large.
From these results, the usefulness of the present invention was confirmed.

  The novel porous metal complex provided by the present invention has a sufficient gas storage capacity. Therefore, according to the present invention, a high performance occlusion material can be provided. Moreover, the manufacturing method of a novel porous metal complex can be provided. Furthermore, the porous metal complex provided by the present invention can be used as an optical functional material.

Claims (13)

Non-covalently represented by the following general formula (1) and capable of forming a coordinate bond to the metal atom or its ion with one type of metal atom or its ion selected from Groups 2 to 13 of the periodic table A porous metal complex having a coordination bond between the metal atom or an ion thereof and the coordination group.

(In the formula, P is a group selected from the group consisting of the following (A) and (B), or 2 or more and 5 or less groups selected from the group consisting of the following (A) and (B). And at least one P includes one group selected from the group consisting of the following (A) and one group selected from the group consisting of the following (B). In this case, the plurality of P may be the same as or different from each other.
(A) A divalent group obtained by removing two hydrogen atoms bonded to an aromatic ring from an aromatic heterocyclic compound which may have a substituent (B) An aromatic which may have a substituent A divalent group Q obtained by removing two hydrogen atoms bonded to an aromatic ring from an aromatic hydrocarbon compound represents an m-valent aromatic hydrocarbon group which may have a substituent.
R is a coordinating ^{_{group, -CO 2 -, -SO 3 -}} , -OPO 3 2-, -OPO 3 H -, represents -C≡N, pyridyl group, an imidazolyl group or imidazolate group.
m represents an integer of 3 to 6, and n is 0 or 1. A plurality of n may be the same as or different from each other. However, at least one of a plurality of n is 1. )   The porous metal complex according to claim 1, wherein m in the general formula (1) is 3.   The porous metal complex according to claim 1 or 2, wherein Q in the general formula (1) is a benzene ring which may have a substituent.   The porous metal complex according to any one of claims 1 to 3, wherein all n's in the general formula (1) are 1.   Any one of Claim 1 to 4 which further contains the auxiliary ligand which bridge | crosslinks the said 2 metal atom or its ion by coordinating to the 2 metal atom or its ion contained in the said porous metal complex, respectively. 2. The porous metal complex according to item 1. Group represented by the following general formula (2) and a metal salt containing one type of metal atom selected from Group 2 to Group 13 of the periodic table and capable of forming a coordinate bond to the metal atom or its ion Of a porous metal complex comprising: a step of obtaining a reaction solution obtained by dissolving or dispersing an aromatic compound comprising 1 or 2 or more types of polar solvents; and a step of reacting the reaction solution. Production method.

(In the formula, P is a group selected from the group consisting of the following (A) and (B), or 2 or more and 5 or less groups selected from the group consisting of the following (A) and (B). And at least one P includes one group selected from the group consisting of the following (A) and one group selected from the group consisting of the following (B). In this case, the plurality of P may be the same as or different from each other.
(A) A divalent group obtained by removing two hydrogen atoms bonded to an aromatic ring from an aromatic heterocyclic compound which may have a substituent (B) An aromatic which may have a substituent A divalent group Q obtained by removing two hydrogen atoms bonded to an aromatic ring from an aromatic hydrocarbon compound represents an m-valent aromatic hydrocarbon group which may have a substituent.
R ¹ is represented by —CO ₂ R ² , —SO ₃ R ² , —OPO ₃ R ² ₂ , —C≡N, a pyridyl group, an imidazolyl group, or the following formula (x-1) or (x-2). Wherein R ² represents a hydrogen atom, an alkali metal atom or an alkyl group having 1 to 4 carbon atoms, and when there are a plurality of groups, they may be the same or different. 1) or (x-2), Ma represents an alkali metal atom).

m represents an integer of 3 to 6, and n represents 0 or 1. A plurality of n may be the same as or different from each other. However, at least one of a plurality of n is 1. )   The method for producing a porous metal complex according to claim 6, wherein in the step of reacting the reaction solution, the reaction solution is reacted by heating in a range of 60 ° C. or more and 250 ° C. or less. Formula (2) ^{R 1} in is _-CO 2 ^{R 2,} and, ^{R 2} is a hydrogen atom or an alkali metal atom, the production method of the porous metal complex according to claim 6 or 7. The method for producing a porous metal complex according to claim 8, wherein R ² is a hydrogen atom.   After the step of reacting the reaction solution, the reaction solution is coordinated to two metal atoms or ions thereof contained in the porous metal complex, thereby assisting in crosslinking the two metal atoms or ions thereof. The method for producing a porous metal complex according to any one of claims 6 to 9, further comprising a step of dissolving or dispersing a ligand to react with the two metal atoms or ions thereof.   Before the step of reacting the reaction solution, the two metal atoms or ions thereof can be cross-linked by coordinating to the two metal atoms or ions thereof contained in the porous metal complex in the reaction solution, respectively. The method for producing a porous metal complex according to any one of claims 6 to 10, further comprising a step of dissolving or dispersing the auxiliary ligand.   The occlusion material containing the porous metal complex of any one of Claim 1 to 5.   The optical functional material containing the porous metal complex of any one of Claim 1 to 5.

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