Novel compound, microporous network complex, method for producing sample for crystal structure analysis, and method for determining molecular structure

Abstract

Provided are a novel compound suitable for a microporous network complex, a microporous network complex, a method for producing a sample for crystal structure analysis, and a method for determining a molecular structure. This compound is a 4,6-diamino-5-pyrimidinecarbonitrile derivative represented by, for example, general formula (1A). (In general formula (1A), regarding X1 moieties, any one of the X1 moieties is a nitrogen atom and the others are each CH, or any two of the X1 moieties are nitrogen atoms and the others are each CH; and Y1 represents one divalent group selected from the group consisting of optionally substituted arylene groups, optionally substituted heteroarylene groups, a single bond, optionally substituted alkylene groups, optionally substituted cycloalkylene groups, optionally substituted alkenylene groups, optionally substituted alkynylene groups, and -C(=O)- or represents a divalent group that is a combination of two or more groups of the same or different kinds which are selected from the above-mentioned group.)

Description

Novel compounds, porous network complexes, methods for preparing samples for crystal structure analysis, and methods for determining molecular structure

[0001] The present disclosure relates to a porous network complex. The present disclosure also relates to a novel compound useful for the porous network complex, etc. The present disclosure further relates to a method for preparing a sample for crystal structure analysis and a method for determining a molecular structure using the porous network complex.

[0002] Porous coordination networks (PCNs) consisting of metal ions and organic ligands have infinite structures, and various PCNs have been proposed. For example, 2,4,6-tris(4-pyridyl)triazine and ZnBr ２ PCNs that combine these have been proposed (Non-Patent Documents 1 and 2). Furthermore, a crystalline sponge method has been proposed in which non-crystalline molecules are trapped in crystalline pores using PCNs and X-ray structural analysis is performed (Patent Document 1). The crystalline sponge method allows the molecular structure to be visualized by encapsulating molecules in the pores of PCNs. The present inventors have recently reported PCNs that combine a tridentate ligand with a 4-pyridinyl group as a ligand and a connector molecule (Patent Document 2), and PCNs that combine a tridentate ligand with a 3-pyridinyl group as a ligand and a connector molecule (Patent Document 3).

[0003] International Publication No. 2016 / 140355 Japanese Patent Application Laid-Open No. 2020-147521 Japanese Patent Application Laid-Open No. 2022-114118

[0004] Masaki Kawano et al., Angew. Chem. Int. Ed. 2008, 47, 1269-1271Makoto Fujita et al. NATURE CHEMISTRY, VOL 3, 2011

[0005] Compared with zeolites and activated carbons, PCNs have a significantly larger surface area, and their structure can be customized to create coordinate structures. Therefore, they have attracted attention in the fields of catalyst support, adsorption, and separation and purification. Through extensive research, the inventors have found that in order to incorporate guest molecules into PCNs, compatibility between the molecular size of the guest molecule and the size of the PCN, as well as the shape of the guest molecule and the pore structure of the PCN, is important. In other words, it is not enough to simply adjust the pore size; it is necessary to select a PCN that corresponds to the chemical structure of the guest molecule. Providing a variety of PCNs with different pore shapes would significantly increase the number of compounds that can be structurally analyzed, making them extremely useful for structural analysis of compounds.

[0006] The present disclosure has been made in view of the above background, and aims to provide novel compounds suitable for porous network complexes, porous network complexes, methods for preparing samples for crystal structure analysis, and methods for determining molecular structures.

[0007] As a result of extensive research, the present inventors have found that the problems of the present disclosure can be solved in the following aspects, leading to the completion of the present disclosure: [1]: A 4,6-diamino-5-pyrimidinecarbonitrile derivative represented by any one of the following general formulas (1A) to (1C): (In general formula (1A), X １ is any X １ One of the groups is a nitrogen atom and the other is CH, or any X １ Two of them are nitrogen atoms, and the others are CH. １ represents a divalent group selected from the group consisting of optionally substituted arylene, optionally substituted heteroarylene, a single bond, optionally substituted alkylene, optionally substituted cycloalkylene, optionally substituted alkenylene, optionally substituted alkynylene, and -C(=O)-, or a divalent group formed by combining two or more of the same or different groups selected from the above group. (In general formula (1B), X ２ are each independently a nitrogen atom or CH, and X ３is NH, N-alkyl, N-aryl, and at least X ２ Either of the nitrogen atom or X ３ is NH. Y １ is the same as in general formula (1A). (In general formula (1C), R １ are each independently selected from a methyl group, a carboxy group, a hydroxy group, an amino group, an aldehyde group, and CH; R １ At least one of Y is a methyl group, a carboxy group, a hydroxy group, an amino group, or an aldehyde group. １ is the same as general formula (1A).) [2]: A 1,3,4,6,7,9-hexaazaphenalenyl derivative represented by any of the following general formulas (2A) to (2I) (excluding 2,5,8-tri(4-pyridyl)-1,3,4,6,7,9-hexaazaphenalene, 2,5,8-tri(3-pyridyl)-1,3,4,6,7,9-hexaazaphenalene, and 2,5,8-tri(4-carboxyphenyl)-1,3,4,6,7,9-hexaazaphenalene). (In general formula (2A), X １ Each of the aromatic rings independently represents an arbitrary X １ One of the groups is a nitrogen atom and the other is CH, or any X １ Two of them are nitrogen atoms, and the others are CH. １ are each independently a divalent group selected from the group consisting of optionally substituted arylene, optionally substituted heteroarylene, a single bond, optionally substituted alkylene, optionally substituted cycloalkylene, optionally substituted alkenylene, optionally substituted alkynylene, and —C(═O)—, or a divalent group formed by combining two or more of the same or different groups selected from the above group; M ＋ represents a counter cation.) (In general formula (2B), X ２ are each independently a nitrogen atom or CH for each aromatic ring, and X ３ are NH, N-alkyl, or N-aryl, and at least X are independently ２ Either of the nitrogen atom or X３ is NH. Y １ is the same as in general formula (2A), and M ＋ represents a counter cation.) (In general formula (2C), R １ are each independently selected from a methyl group, a carboxy group, a hydroxy group, an amino group, an aldehyde group, and CH for each aromatic ring; R １ At least one of Y is a methyl group, a carboxy group, a hydroxy group, an amino group, or an aldehyde group. １ is the same as in general formula (2A), and M ＋ represents a counter cation.) (In general formula (2D), X １ , Y １ and M ＋ is the same as in general formula (2A), and X ２ and X ３ is the same as in general formula (2B). (In general formula (2E), １ , Y １ and M ＋ is the same as in general formula (2A), and R １ is the same as in general formula (2C). (In general formula (2F), Y １ and M ＋ is the same as in general formula (2A), and X ２ and X ３ is the same as in general formula (2B), and R １ is the same as in general formula (2C). (In general formula (2G), １ , Y １ and M ＋ is the same as in general formula (2A), and R １ is the same as in general formula (2C). (In general formula (2H), Y １ and M ＋ is the same as in general formula (2A), and X ２ and X ３ is the same as in general formula (2B), and R １ is the same as in general formula (2C). (In general formula (2I), X １ , Y １and M ＋ is the same as in general formula (2A), and X ２ and X ３ is the same as general formula (2B).) [3]: A porous network complex comprising a tridentate ligand and a connector having a transition metal, wherein the tridentate ligand is the 1,3,4,6,7,9-hexaazaphenalenyl derivative according to claim 2, and at least a portion of the transition metal is coordinated to the tridentate ligand. [4]: ​​A method for producing a sample for crystal structure analysis, comprising: preparing a sample in which a compound to be analyzed is dissolved in a solvent; immersing a single crystal of the porous network complex according to [3] in the sample; incorporating the compound to be analyzed into the pores of the porous network complex; and removing the porous network complex with the compound to be analyzed incorporated from the solvent. [5]: A method for determining the molecular structure of a compound to be analyzed, comprising performing crystal structure analysis using the sample for crystal structure analysis obtained by the method according to [4].

[0008] The present disclosure has the excellent effect of providing a novel compound suitable for a porous network complex, a porous network complex, a method for preparing a sample for crystal structure analysis, and a method for determining a molecular structure.

[0009] FIG. 1 shows the structure around the connector of the PCN crystal of Example 5. Structural diagram of the PCN crystal of Example 5 from the a-axis with maximum opening. FIG. 2 shows the structure around the connector of the PCN crystal of Example 6. Structural diagram of the PCN crystal of Example 6 from the c-axis direction with maximum opening. FIG. 3 shows the structure around the connector of the PCN crystal of Example 7. Structural diagram of the PCN crystal of Example 7 from the a-axis direction with maximum opening. FIG. 4 shows the structure around the connector of the PCN crystal of Example 8. Structural diagram of the PCN crystal of Example 8 from the a-axis direction with maximum opening. FIG. 5 shows the structural formula of artemisinin. Example 11: Diagram showing the electron density of artemisinin in PCN crystal. Example 11: Diagram showing the temperature factor of artemisinin in PCN crystal. Example 11: Diagram showing the interaction between PCN crystals and guest molecules, etc. Example 12: Diagram showing the electron density of quinine in PCN crystal. Example 12: Diagram showing the temperature factor of quinine in PCN crystal. Example 12: Diagram showing the interaction between PCN crystals and guest molecules, etc. Example 13: A diagram showing the electron density of quinidine in PCN crystals. Example 13: A diagram showing the temperature factor of quinidine in PCN crystals. Example 13: A diagram showing the interaction between PCN crystals and guest molecules, etc. Example 14: A diagram showing the electron density of caffeine in PCN crystals. Example 14: A diagram showing the temperature factor of caffeine in PCN crystals. Example 14: A diagram showing the interaction between PCN crystals and guest molecules, etc. Example 15: A diagram showing the electron density of omeprazole in PCN crystals. Example 15: A diagram showing the temperature factor of omeprazole in PCN crystals. Example 15: A diagram showing the interaction between PCN crystals and guest molecules, etc. Example 16: A diagram showing the electron density of nicotine in PCN crystals. Example 16: A diagram showing the temperature factor of nicotine in PCN crystals. Example 16: A diagram showing the interaction between PCN crystals and guest molecules, etc. Example 17: A diagram showing the electron density of cytisine in PCN crystals. Example 17: A diagram showing the temperature factor of cytisine in PCN crystals. Example 17: A diagram showing the interaction between a PCN crystal and guest molecules, etc. Example 18: A diagram showing the electron density of voriconazole in a PCN crystal. Example 18: A diagram showing the temperature factor of voriconazole in a PCN crystal. Example 18: A diagram showing the interaction between a PCN crystal and guest molecules, etc. Example 19: A diagram showing the electron density of cyclopenthiazide in a PCN crystal. Example 19: A diagram showing the temperature factor of cyclopenthiazide in a PCN crystal.Example 19: A diagram showing the interaction between a PCN crystal and a guest molecule, etc. Example 20: A diagram showing the electron density of abacavir in a PCN crystal. Example 20: A diagram showing the temperature factor of abacavir in a PCN crystal. Example 20: A diagram showing the interaction between a PCN crystal and a guest molecule, etc. Example 21: A diagram showing the electron density of compound A in a PCN crystal. Example 21: A diagram showing the temperature factor of compound A in a PCN crystal. Example 21: A diagram showing the interaction between a PCN crystal and a guest molecule, etc. Example 23: A diagram showing the interaction between a PCN crystal and a guest molecule, etc.

[0010] An example of an embodiment to which the present disclosure is applied will be described below. Note that other embodiments are also included within the scope of the present disclosure as long as they conform to the spirit of the present disclosure.

[0011] <1> 4,6-Diamino-5-pyrimidinecarbonitrile Derivatives The 4,6-diamino-5-pyrimidinecarbonitrile derivatives of the present disclosure (hereinafter also referred to as the present pyrimidine derivatives) are represented by the following general formulas (1A) to (1C). In general formula (1A), X １ is any X １ One of the groups is a nitrogen atom and the other is CH, or any X １ Two of them are nitrogen atoms, and the others are CH. １ represents a divalent group selected from the group consisting of optionally substituted arylene, optionally substituted heteroarylene, a single bond, optionally substituted alkylene, optionally substituted cycloalkylene, optionally substituted alkenylene, optionally substituted alkynylene, and -C(=O)-, or a divalent group formed by combining two or more of the same or different groups selected from the above group. In general formula (1B), X ２ are each independently a nitrogen atom or CH, and X ３ is NH, N-alkyl, N-aryl, and at least X ２ Either of the nitrogen atom or X ３ is NH. Y １ is the same as in general formula (1A). In general formula (1C), R １are each independently selected from a methyl group, a carboxy group, a hydroxy group, an amino group, an aldehyde group, and CH; R １ At least one of Y is a methyl group, a carboxy group, a hydroxy group, an amino group, or an aldehyde group. １ is the same as in general formula (1A).

[0012] In the general formula (1A), any X １ When one of X is a nitrogen atom and the other is CH, the group is a 2-pyridinyl group, a 3-pyridinyl group, or a 4-pyridinyl group. １ When two of are nitrogen atoms and the other is CH, the group is any of a 2,3-pyrimidinyl group, a 2,4-pyrimidinyl group, a 2,5-pyrimidinyl group, a 2,6-pyrimidinyl group, a 3,5-pyrimidinyl group, and a 3,4-pyrimidinyl group.

[0013] The general formula (1B) contains at least X ２ is a nitrogen atom, or X ３ has NH. X ２ and X ３ may have NH. The alkyl group of the N-alkyl is preferably an alkyl group having 1 to 6 carbon atoms, and a methyl group is particularly preferred. Preferred examples of the N-aryl include a phenyl group and a naphthyl group which may have a substituent. X ２ A preferred example of the five-membered ring having the formula (1B-1) below can be given.

[0014] R in general formula (1C) １ A preferred example of the aromatic ring having the following general formula (1C-1) can be given.

[0015] Below, Y １ The arylene which may have a substituent is preferably an arylene having 6 to 14 carbon atoms, more preferably an arylene having 6 to 10 carbon atoms, and particularly preferably an arylene having 6 carbon atoms. Suitable examples include phenylene, naphthylene, and anthracenylene which may have a substituent.

[0016] The heteroarylene which may have a substituent is preferably a monocyclic or bicyclic heteroarylene having 6 to 14 carbon atoms, more preferably a monocyclic or bicyclic heteroarylene having 6 to 10 carbon atoms. Examples of the heteroatom include a nitrogen atom, an oxygen atom, and a sulfur atom. Preferred examples include triazinylene, pyridinylene, pyrimidinylene, quinolinylene, isoquinolinylene, pyrazinylene, quinoxalinylene, and the like which may have a substituent, and among these, triazinylene, pyridinylene, and pyrimidinylene are more preferred.

[0017] The alkylene, which may have a substituent, may be either linear or branched. The alkylene preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 8 carbon atoms. Suitable examples include an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group, each of which may have a substituent. A methylene group is also suitable.

[0018] The cycloalkylene which may have a substituent preferably has 3 to 12 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 5 to 8 carbon atoms. Suitable examples include cyclopropylene, cyclopentylene, cyclohexylene, cyclooctylene, and cyclododecanylene, each of which may have a substituent.

[0019] The alkenylene which may have a substituent is preferably a straight-chain alkenylene having 2 to 6 carbon atoms, and more preferably a straight-chain alkenylene having 2 to 4 carbon atoms. Suitable examples include ethylenylene, n-propynylene, n-butenylene, n-pentenylene, and n-hexenylene, which may have a substituent.

[0020] The alkynylene which may have a substituent is preferably a straight-chain alkynylene having 2 to 6 carbon atoms, more preferably a straight-chain alkynylene having 2 to 4 carbon atoms. Preferred examples include n-propynylene, n-butynylene, n-pentynylene, and n-hexynylene which may have a substituent. Ethynylene is also preferred.

[0021] From the viewpoint of easily forming the present PCN, the above Y１ Among these, a single bond, an arylene which may have a substituent, and a heteroarylene which may have a substituent are preferred.

[0022] The substituents in general formulas (1A) to (1C) may be any as long as they do not deviate from the spirit of the present disclosure. Suitable examples include halogen atoms, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, silyloxy groups, heterocyclic oxy groups, and acyloxy groups. These substituents may be further substituted, and examples of the further substituents include groups selected from the above-mentioned substituent group.

[0023] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group includes a cycloalkyl group. The alkyl group includes linear, branched, and cyclic substituted and unsubstituted alkyl groups. The alkyl group preferably has 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group, a 2-ethylhexyl group, a cyclohexyl group, and a cyclopentyl group. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a phenylpropyl group, a 4-phenylbutyl group, a phenylpentyl group, a phenylhexyl group, a phenylheptyl group, a phenyloctyl group, a phenylnonyl group, a naphthylmethyl group, a naphthylethyl group, an anthrathymethyl group, and a phenyl-cyclopentylmethyl group. Examples of the alkenyl group include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group. Examples of the alkynyl group include a propynyl group, a butynyl group, a 2-chlorobutynyl group, a pentynyl group, and a hexynyl group. Examples of the aryl group include a phenyl group, a fluorophenyl group, a chlorophenyl group, and a tolyl group. Examples of the heterocyclic group include an imidazolyl group, a pyrazolyl group, a triazolyl group, a piperazinyl group, a pyridinyl group, a pyrrolyl group, a thiazolyl group, an oxazolyl group, a benzoxazolyl group, an indolyl group, a benzothiazolyl group, a benzimidazolyl group, a benzotriazolyl group, a morpholinyl group, a piperidinyl group, and a pyrrolidinyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and an isopropoxy group. Examples of the aryloxy group include a phenoxy group and a naphthyloxy group. Examples of the silyloxy group include a trimethylsilyloxy group and a diphenylmethylsilyloxy group. Examples of the heterocyclic oxy group include a 1-phenyltetrazole-5-oxy group and a 2-tetrahydropyranyloxy group, and examples of the acyloxy group include an acetyloxy group, a pivaloyloxy group, a stearoyloxy group, a benzoyloxy group, and a p-methoxyphenylcarbonyloxy group.

[0024] Suitable examples of the compounds represented by general formulas (1A) to (1C) include compounds selected from the compounds represented by the following chemical formula (1-s).

[0025] An example of a method for producing the pyrimidine derivative of the present invention will be described below. However, the methods for producing the compounds of general formulae (1A) to (1C) of the present disclosure are not limited to the following methods. The method for producing the compound of general formula (1A) will be specifically described below, but compounds of general formulae (1B) and (1C) can also be synthesized by the same method.

[0026] First, synthesis is carried out according to the following general formula (11). X in general formula (11) １ and Y １ The description of general formula (1A) is incorporated herein by reference. The amidino compound in general formula (11) also includes a non-protonated neutral compound. X in general formula (11) － is a monovalent anion. Examples of monovalent anions include halide ions and acetate anions.

[0027] The starting material (a) having a nitrile group in general formula (11) is reacted with thionyl chloride in methanol, for example, at 0 to 10°C for 1 to 10 hours to activate the nitrile group, and then the compound having an amidino group represented by (b) of general formula (11) is obtained by reacting the starting material (a) having a nitrile group in methanol, for example, at 10 to 30°C for 1 to 20 hours. Alternatively, the compound can be synthesized according to, for example, the literature, Eur. J. Org. Chem. 2014, 3614-3621.

[0028] Subsequently, compound (b) and tricyanide methanide are placed in a pressure-resistant vessel in a mixing ratio of 1:1, and reacted, for example, at 100 to 200°C for 10 to 96 hours to synthesize a 4,6-diamino-5-pyrimidinecarbonitrile derivative of general formula (1) shown in general formula (12). M ＋ is a monovalent metal cation. Although the synthesis is performed by a solid-phase reaction using a pressure vessel in the above example, it may also be performed by a solution reaction. １ and Y １ The description of general formula (1) is incorporated herein by reference.

[0029] <2> 1,3,4,6,7,9-Hexaazaphenalenyl Derivative The 1,3,4,6,7,9-hexaazaphenalenyl derivative of the present disclosure (hereinafter also referred to as the present phenalenyl derivative) is any one of the following general formulae (2A) to (2I) (excluding 2,5,8-tri(4-pyridyl)-1,3,4,6,7,9-hexaazaphenalene, 2,5,8-tri(3-pyridyl)-1,3,4,6,7,9-hexaazaphenalene, and 2,5,8-tri(4-carboxyphenyl)-1,3,4,6,7,9-hexaazaphenalene). In general formula (2A), X １ Each of the aromatic rings independently represents an arbitrary X １ One of the groups is a nitrogen atom and the other is CH, or any X １ Two of them are nitrogen atoms, and the others are CH. １ are each independently a divalent group selected from the group consisting of optionally substituted arylene, optionally substituted heteroarylene, a single bond, optionally substituted alkylene, optionally substituted cycloalkylene, optionally substituted alkenylene, optionally substituted alkynylene, and —C(═O)—, or a divalent group formed by combining two or more of the same or different groups selected from the above group; M ＋ represents the counter cation. In general formula (2B), X ２ are each independently a nitrogen atom or CH for each aromatic ring, and X ３ are NH, N-alkyl, or N-aryl, and at least X are independently ２ Either of the nitrogen atom or X ３ is NH. Y １ is the same as in general formula (2A), and M ＋ represents the counter cation. In general formula (2C), R １ are each independently selected from a methyl group, a carboxy group, a hydroxy group, an amino group, an aldehyde group, and CH for each aromatic ring; R １At least one of Y is a methyl group, a carboxy group, a hydroxy group, an amino group, or an aldehyde group. １ is the same as in general formula (2A), and M ＋ represents the counter cation. (In general formula (2D), X １ , Y １ and M ＋ is the same as in general formula (2A), and X ２ and X ３ is the same as in general formula (2B). (In general formula (2E), X １ , Y １ and M ＋ is the same as in general formula (2A), and R １ is the same as in general formula (2C). (In general formula (2F), Y １ and M ＋ is the same as in general formula (2A), and X ２ and X ３ is the same as in general formula (2B), and R １ is the same as in general formula (2C). (In general formula (2G), １ , Y １ and M ＋ is the same as in general formula (2A), and R １ is the same as in general formula (2C). (In general formula (2H), Y １ and M ＋ is the same as in general formula (2A), and X ２ and X ３ is the same as in general formula (2B), and R １ is the same as in general formula (2C). (In general formula (2I), X １ , Y １ and M ＋ is the same as in general formula (2A), and X ２ and X ３ is the same as general formula (2B).

[0030] M ＋The type of cation is not particularly limited, and may be either an organic cation or an inorganic cation. Suitable examples of organic cations include organic cations in which a positive charge exists on the nitrogen atom, phosphorus atom, or sulfur atom. Suitable examples of inorganic cations include alkali metal ions and alkaline earth metal ions. Examples of organic cations include ammonium cation, pyridinium cation, imidazolium cation, diaryliodonium cation, polyalkylphosphonium cation, polyarylphosphonium cation, and polyarylsulfonium cation. Specific examples include tetramethylammonium, tetraethylammonium, tetrabutylammonium, diphenyliodonium cation, 4-methoxyphenyl-4-(2-methylpropyl)phenyliodonium cation, 4-chlorophenyl-4-phenyliodonium cation, 4-(2-methylpropyl)phenyl-p-tolyliodonium cation, 4-hexyloxyphenyl-2,4,6-trimethoxyphenyliodonium cation, 4-hexyloxyphenyl-2,4,6-diethoxyphenyliodonium cation, 4-octyloxyphenyl-2,4,6-trimethoxyphenyliodonium cation, bis(2-methylpropyl) ... Examples of inorganic cations include (4-tert-butylphenyl)iodonium cation, tetrabutylphosphonium ion, butyltriphenylphosphonium ion, tetraphenylphosphonium ion, triphenylsulfonium cation, bis(4-chlorophenyl)phenylsulfonium cation, bis(4-chlorophenyl)-4-methylphenylsulfonium cation, tris(4-chlorophenyl)sulfonium cation, tris(2,4-dichlorophenyl)sulfonium cation, bis(2,4-dichlorophenyl)phenylsulfonium cation, and bis(2,4-dichlorophenyl)4-methoxyphenylsulfonium cation. Specific examples of inorganic cations include alkali metal ions such as lithium ion, sodium ion, and potassium ion, and alkaline earth metal ions such as calcium ion, magnesium ion, and calcium ion.

[0031] This phenalenyl derivative is suitable for use in the porous network complex described below. In general formulas (2A) and (2B), at least one nitrogen atom in each of the three outer aromatic rings functions as a tridentate ligand. In general formula (2C), a methyl group, a carboxy group, an aldehyde group, a hydroxy group, and an amino group in each of the three outer aromatic rings functions as a tridentate ligand. The tridentate ligands may be the same or different. They may be designed according to the desired pore size. The three Y in (2A) to (2I) １ may be independently the same or different. From the viewpoint of symmetry, three Y １ are preferably the same.

[0032] An example of a method for producing the phenalenyl derivative of general formula (2A) will be described below. However, the method for producing the phenalenyl derivative of general formula (2A) of the present disclosure is not limited to the following method. In addition, general formulae (2B) to (2I) can be similarly synthesized by combining compounds obtained by modifying the compound (b) of general formula (11) and the compound (c) of general formula (12) to have the desired structure.

[0033] First, compounds (b) of general formula (11) and (c) of general formula (12) are obtained by the synthesis methods of the above general formulas (11) and (12). Next, compound (b) obtained by general formula (11) and compound (c) obtained by general formula (12) are prepared and thoroughly mixed at a ratio of 2 to 4:1. The mixture is then heated in a pressure-resistant vessel, for example, at 150 to 300°C for 1 to 50 hours to synthesize a phenalenyl derivative, thereby obtaining a compound of general formula (2A) (general formula (15)). For example, amidinopyridine hydrochloride and a 4,6-diamino-5-pyrimidinecarbonitrile derivative are prepared as compounds obtained by general formula (12), and these are thoroughly mixed in a ratio of 2 to 4:1 using a mortar or the like. The mixture is then heated in a pressure-resistant vessel, for example, at 150 to 300°C for 1 to 50 hours to synthesize a phenalenyl derivative. Here, MZ is M ＋ is a salt for generating a counter cation of

[0034] The resulting solid is treated with an acid and a base. For example, it is dissolved in 2 M hydrochloric acid to form a saturated solution, and then a 5 M aqueous solution of potassium hydroxide is added to the solution. This solution is then added dropwise to a saturated aqueous solution of a salt that can serve as a counter cation, thereby obtaining the present phenalenyl derivative of general formula (2A).

[0035] <3> Porous Network Complex The porous network complex of the present disclosure (hereinafter also referred to as the present PCN) is a complex comprising a connector having a tridentate ligand and a transition metal. The present PCN uses the present phenalenyl derivative as the tridentate ligand. In the present PCN, at least a portion of the transition metal of the connector is coordinated to the tridentate ligand of the present phenalenyl derivative. The present PCN has, for example, a layered network structure having openings, and the openings overlap in the layering direction of the network, thereby forming pores that communicate in the layering direction. The network structure is preferably a two-dimensional network or a three-dimensional network structure.

[0036] Here, the term "two-dimensional network" refers to a network structure formed by coordinate bonds between a tridentate ligand and a transition metal, having openings, and extending in two dimensions from a macroscopic perspective. The term "three-dimensional network" refers to a network structure formed by coordinate bonds between a tridentate ligand and a transition metal, having openings, and extending in three dimensions from a macroscopic perspective.

[0037] The tridentate ligand is the present phenalenyl derivative, and the pores of the network are regularly formed by combining multiple connectors, which are connecting structures of coordinate bonds between the tridentate ligand, which uses three substituents of the present phenalenyl derivative as coordination sites, and the transition metal, between the layers and / or within the layers. The size of the pore openings can be easily adjusted depending on the tridentate ligand compound.

[0038] The interlayer connector is a connector that connects adjacent networks in the stacking direction of the networks, and the intralayer connector is a connector that forms a network. An example of an intralayer connector is a connector having an -N-Metal-N- bond in which a transition metal is sandwiched within the network.

[0039] Examples of transition metals include Co, Ni, Cu, Rh, Ag, Ir, Pt, Au, Zn, Cd, and Fe. Among these, any one of Co, Cu, Zn, Cd, and Fe is preferred. Although multiple types of transition metals can be used, it is preferable to use a single transition metal from the viewpoint of ease of structural analysis.

[0040] This PCN can be suitably used as a sample for crystal structure analysis. The pore opening diameter of this PCN is not limited, but when used as a sample for crystal structure analysis, the pore opening diameter can be adjusted depending on the compound to be analyzed. The pore opening diameter is primarily determined by the type of tridentate ligand. By making the opening diameter of the network opening 1.5 nm or larger, it is possible to selectively incorporate medium-molecular compounds, for example, with a molecular weight of approximately 400 to 7,000, into the hollow space, making it possible to apply this PCN to a variety of applications, including crystal structure analysis.

[0041] The connector is not limited as long as it can form a PCN by coordinating with a ligand such as a nitrogen atom of the phenalenyl derivative. The tridentate ligand and the connector may each be used independently, either alone or in combination of two or more.

[0042] An example of a method for producing PCN crystals is described below. However, the method for producing this PCN is not limited to the following method. First, the phenalenyl derivative and a connector, which is a transition metal compound, are dissolved in a solvent and heated. In some cases, an additive for structure formation is added. This results in the formation of a self-organized, aligned PCN.

[0043] The connector to be used can be any transition metal compound used in the synthesis of PCN without any restrictions. ４ X ４ (PPh ３ ) ４ ] (X=I, Br, Cl), Cu ２ X ２ (PPh ３ ) ５ , ZnX ２ , CoX ２ , NiX ２, RhX3, AgX ２ , IrX3, PtX4, and AuX4. ３ is triphenylphosphine.

[0044] The molar ratio of the present phenalenyl derivative to the connector is not particularly limited.

[0045] The organic solvent used is not particularly limited as long as it can uniformly dissolve the present phenalenyl derivative and the connector. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, 1,2-dichlorobenzene, mesitylene, and nitrobenzene; sulfoxides such as dimethyl sulfoxide (DMSO); amides such as N,N-dimethylformamide; ethers such as tetrahydrofuran, 1,2-dimethoxyethane, and 1,4-dioxane; alcohols such as methanol, ethanol, and isopropyl alcohol; and ketones such as acetone and methyl ethyl ketone. The solvent may be used alone or in combination with two or more. Among these, polar solvents are preferred as the solvent for the connector, as they enable the present PCN to be synthesized in a higher yield, with dimethylformamide and dimethylacetamide being particularly preferred. Furthermore, polar solvents are preferred as the solvent for the present phenalenyl derivative, with dimethylformamide and dimethylacetamide being particularly preferred.

[0046] The structure of PCN can be confirmed by elemental analysis, IR, UV absorption spectrum, visible light absorption spectrum, X-ray single crystal structure analysis, and the like.

[0047] <4> Method for preparing a sample for crystal structure analysis and method for determining the molecular structure of a compound to be analyzed Next, a method for preparing a sample for crystal structure analysis according to the present disclosure will be described. The preparation of the sample for crystal structure analysis involves incorporating a compound to be analyzed into the pores of the PCN to provide a sample for structural analysis of the compound.

[0048] First, a sample is prepared by dissolving the target compound in a solvent, and a single crystal of the present PCN is immersed in the sample.The target compound is then incorporated into the pores of the PCN, and the porous network complex is then extracted from the solution.

[0049] A method for bringing PCN into contact with a mixture containing a compound to be analyzed and incorporating molecules of the compound to be analyzed into the pores of PCN can be performed by a known method such as that described in Patent Document 1.

[0050] The compound to be analyzed is not particularly limited as long as it is of a size that can enter the pores of the single crystal, and can be applied to a wide variety of compounds, including low-molecular-weight compounds, medium-molecular-weight compounds such as pharmaceuticals (e.g., molecular weights of 400 to 7000), and chiral compounds.

[0051] The method for contacting the single crystal with the target compound is not particularly limited. For example, a solution of the target compound is prepared and the single crystal is brought into contact with this solution, or when the target compound is a liquid or gas, the molecules of the target compound can be incorporated into the pores of the PCN by directly contacting the single crystal with the target compound. Among these, the method of preparing a solution of the target compound and contacting the single crystal with this solution is preferred because it is easier to obtain a sample for crystal structure analysis of higher quality.

[0052] Furthermore, when a solution containing the compound to be analyzed is used or when the compound to be analyzed is liquid, the contacting operation can be performed by immersing the single crystal in a solution containing the compound to be analyzed, or by packing the single crystal into a capillary and then passing a solution containing the compound to be analyzed through the capillary.

[0053] The solvent for the solution containing the target compound may be any solvent that does not dissolve the single crystal used but dissolves the target compound. Since the PCN has excellent stability in water, water can be suitably used as the solvent. Examples of organic solvents include aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, 1,2-dichlorobenzene, nitrobenzene, and mesitylene; aliphatic hydrocarbons such as n-butane, n-pentane, n-hexane, and n-heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and cycloheptane; nitriles such as acetonitrile and benzonitrile; sulfoxides such as dimethyl sulfoxide (DMSO); amides such as N,N-dimethylformamide and n-methylpyrrolidone; ethers such as diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, and 1,4-dioxane; alcohols such as methanol, ethanol, and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane; esters such as methyl acetate, ethyl acetate, ethyl lactate, and ethyl propionate; and water. These solvents can be used alone or in combination.

[0054] The contact time between the target compound and the PCN is not particularly limited, but is usually several minutes to several days. Depending on the compound, the contact time can be shortened or lengthened as appropriate. The contact temperature can be, for example, in the range of -30 to 200°C, and is not particularly limited. It is preferable to contact the target compound at a temperature that makes it easy to handle.

[0055] The sample for crystal structure analysis is formed by incorporating molecules of the target compound into the pores of a single crystal of PCN. Due to the size of the opening diameter of the pores, the target compound is regularly arranged within the pores. Here, regularly arranged means that the molecules of the target compound are incorporated into the pores to an extent that their structure can be determined by crystal structure analysis.

[0056] The sample for crystal structure analysis may be any sample capable of determining the molecular structure of the target compound, and it is not necessary for the molecules of the target compound to be incorporated into all of the pores of the PCN. The molecular structure of the target compound is determined by carrying out crystal structure analysis of the target compound using the sample for crystal structure analysis. X-ray diffraction, neutron diffraction, etc. can be used for the structural analysis. In addition, the PCN can be used with Y １ By changing the pore size of the PCN, the pore size can be changed.

[0057] [Examples] The present disclosure will be described in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present disclosure. The scope of the embodiments of the present disclosure is not limited to the specific examples shown below.

[0058] (Synthesis Example 1 of Compound Having Amidino Group) 21.1 g of starting material (a) having a nitrile group in formula (11a) and 12.1 g of sodium methoxide were dissolved in 400 mL of methanol and stirred at 80°C for 2 hours. 22.8 g of ammonium chloride was then added, and the mixture was further stirred at 80°C overnight. The solid was removed by filtration, and the filtrate was evaporated to dryness using a rotary evaporator. The resulting white solid was purified by recrystallization with water to obtain a white powder. The yield was 24.8 g, a 78% yield. 1 H NMR(DMSO-d6):δ= 7.773 (dd, J = 1.2, 6.0 Hz, 2H), 8.868 (dd, J = 1.2, 6.0 Hz, 2H)

[0059] (Synthesis Example 2 of Compound Having Amidino Group) 300 mg of sodium methoxide was added to a dried flask, and 10 cm of dehydrated methanol was added. ３ 9.0 g of the starting material (a) having a nitrile group in formula (11b) was dissolved in 70 cm of dehydrated methanol and cooled on ice. ３ The solution was dissolved in 100 ml of ammonium chloride, which was slowly added to the solution in the flask and then left to stand overnight with stirring at room temperature. 5.8 g of ammonium chloride was added to the solution, which was then heated and stirred at 40°C for 8 hours. After cooling, 200 cm of diethyl ether was added.３ The mixture was filtered, washed with diethyl ether and dried under reduced pressure to obtain white crystals, weighing 11.6 g and representing a yield of 85%. 1 H NMR (DMSO-d6): δ = 8.98 ( d , J = 2.5 Hz, 1H ), δ = 8.87 ( dd , J = 1.5 Hz, 1.5 Hz, 1H ), δ = 8.53 ( br , 4H ), δ = 8.22 ( tt , J = 8 Hz, 2.5 Hz, 1.5 Hz, 1H ), δ = 7.65 ( q, 1H)

[0060] [Synthesis of 4,6-diamino-2-(3-pyridyl)-5-primidinecarbonitrile] 3.0 g (19 mmol) of 3-amidinopyridine hydrochloride (compound (b) represented by formula (11b)) and 2.0 g (18 mmol) of sodium tricyanomethanide were thoroughly mixed in a mortar and heated in a pressure vessel at 150°C for 2 days. The resulting black solid was purified by silica gel column chromatography using ethyl acetate to obtain 543.6 mg (yield 14%) of a pale yellow solid powder.

[0061] The results of NMR and elemental analysis are as follows, and it was confirmed that the product represented by formula (13a) was obtained. 1 H NMR(DMSO-d6):δ= 7.356 (br, 4H), 7.503 (ddd, 1H, J = 1.2, 5.2, 3.2 Hz), 8.473 (dt, 1H, J = 2.0, 8.4 Hz), 8.664 (dd, 1H, J = 1.6, 4.8 Hz), 9.349 (d, 1H, J = 1.6 Hz) Elemental Analysis: CHN calc.: C:54.86; H:3.91; N:39.19; (= C10H8N6(NH4Cl) 0.13 ) obs:C:54.86; H:4.23; N:39.81

[0062] [Synthesis of 4,6-diamino-2-(4-pyridyl)primidine-5-carbonitrile] 3.2 g (20 mmol) of 4-amidinopyridine hydrochloride (compound (b) represented by formula (11a)) and 2.3 g (20 mmol) of sodium tricyanomethanide were thoroughly mixed in a mortar and heated in a pressure vessel at 150°C for 2 days. The resulting ochre solid was purified by silica gel column chromatography using ethyl acetate, yielding 3.9 g (yield 41%) of a white solid powder.

[0063] The results of NMR and elemental analysis are as follows, and it was confirmed that the product represented by formula (13b) was obtained. 1 H NMR(DMSO-d6):δ= 7.287 (br, 4H), 8.060 (dd, 2H, J = 1.6, 4.4 Hz), 8.701 (dd, 2H, J = 2.0, 4.4 Hz) Elemental Analysis: CHN calc.: C:56.59; H:3.86; N:39.19; (= C10H8N6(CH3COOH) 0.03 ) obs:C:56.71; H:3.93; N:39.19

[0064] Example 3: Synthesis of the present phenalenyl derivative [Synthesis of 2-(3-pyridyl)-5,8-di(4-pyridyl)-1,3,4,6,7,9-hexaazaphenalene (344-TPHAP)] 475.4 mg (3 mmol) of 4-amidinopyridine hydrochloride and 214.6 mg (1 mmol) of the compound obtained by formula (13a) were thoroughly mixed in a mortar and heated in a pressure vessel at 200°C for 20 hours. The resulting brown solid was dissolved in 2 M hydrochloric acid to form a saturated solution. Next, 30 mL of 5 M aqueous potassium hydroxide solution was added, and this solution was added to a saturated aqueous solution of 419.3 mg (1 mmol) of tetraphenylphosphonium bromide. The precipitated solid was collected by suction filtration to obtain 168.4 mg of a yellow solid (yield 24%).

[0065] The results of NMR and elemental analysis are as follows. The compound represented by formula (2a) (hereinafter referred to as (TPP) ＋ (344TPHAP)－ It was confirmed that the above-mentioned 1 H NMR(DMSO-d6):δ= 7.571 (ddd, 1H, J = 0.8, 4.4, 7.6 Hz), 7.722 (ddd, 8H, J = 1.2, 8.4, 12.8 Hz), 7.801 (td, 8H, J = 3.6, 8.0 Hz), 7.952 (tq, 4H, J = 1.6, 7.2 Hz), 8.393 (dd, 4H, J = 1.6, 4.4 Hz), 8.709 (dd, 1H, J = 1.6, 4.8 Hz), 8.764 (dd, 4H, J = 1.6, 4.8), 8.810 (dt, 1H, J = 2.0, 7.6 Hz), 9.630 (d, 1H, J = 1.6Hz) Elemental Analysis: CHN calc.: C:71.37;H:4.63;N:16.28(=C46H32N9P(H2O) 1.80 obs:C:71.37; H:5.08; N:16.87

[0066] (Example 4: Synthesis of the present phenalenyl derivative) [Synthesis of 5,8-di(3-pyridyl)-2-(4-pyridyl)-1,3,4,6,7,9-hexaazaphenalene (334-TPHAP)] 2.4 g (15 mmol) of 3-amidinopyridine hydrochloride and 1.1 g (5 mmol) of the compound obtained by formula (13b) were thoroughly mixed in a mortar and heated in a pressure vessel at 200°C for 20 hours. The resulting black solid was dissolved in 5 M hydrochloric acid to form a saturated solution. Next, 30 mL of 5 M aqueous potassium hydroxide solution was added, and this solution was added to a saturated aqueous solution of 1.3 g (3 mmol) of tetraphenylphosphonium bromide. The precipitated solid was collected by suction filtration to obtain 40.3 mg of a yellow solid (yield 1%).

[0067] The results of NMR and elemental analysis are as follows. The compound represented by formula (3a) (hereinafter referred to as (TPP) ＋ (334TPHAP) － It was confirmed that the above-mentioned 1H NMR(DMSO-d6):δ= 7.573 (ddd, 2H, J = 0.8, 4.4, 8.4 Hz), 7.738 (ddd, 8H, J = 1.2, 7.6, 13.2 Hz), 7.814 (td, 8H, J = 3.6, 8.0 Hz), 7.965 (tq, 4H, J = 1.6, 7.2 Hz), 8.391 (dd, 2H, J = 1.6, 4.4 Hz), 8.714 (dd, 2H, J = 1.6, 4.4 Hz), 8.769 (dd, 2H, J = 1.6, 4.8), 8.807 (dt, 2H, J = 2.0, 8.0 Hz), 9.630 (d, 2H, J = 1.6Hz)

[0068] (Example 5: Synthesis of present PCN) (TPP) represented by formula (2a) ＋ (344TPHAP) － 7.4 mg (0.01 mmol) of PCN, 5.0 mg (0.03 mmol) of terephthalic acid (BDC), 6.6 mg (0.03 mmol) of cobalt bromide, and 2 ml of dehydrated dimethylacetamide (DMA) were placed in a vial and heated at 100°C for 2 days to obtain reddish-purple PCN crystals (hereinafter also referred to as APF-80).

[0069] The structural parameters of the obtained PCN crystals determined by X-ray analysis are shown in Table 1. The porosity was 67.5%, the minimum opening diameter was 4.38 Å, and the maximum opening diameter was 8.14 Å.

[0070]

[0071] Figure 1 shows the structure around the connector identified by X-ray structural analysis of the PCN crystal of Example 5. Figure 2 shows a structural diagram of the PCN crystal of Example 5 from the a-axis, which has the largest opening. Note that the a-axis, b-axis, and c-axis referred to in this specification are axes that form a crystallographic real lattice, and correspond to the x-, y-, and z-axes in a unit lattice.

[0072] (Example 6: Synthesis of PCN) (TPP) represented by formula (2a) ＋ (344TPHAP) －3.7 mg (0.005 mmol) of PCN, 2.5 mg (0.015 mmol) of terephthalic acid (BDC), 3.3 mg (0.015 mmol) of cobalt bromide, 1 mL of dimethylacetamide (DMA), and 0.1 mL of distilled water were placed in a vial and heated at 80°C for 40 hours to obtain pale red PCN crystals (hereinafter also referred to as AFP-81).

[0073] The structural parameters of the obtained PCN crystals determined by X-ray analysis are shown in Table 2. The porosity was 67.5%, the minimum opening diameter was 5.46 Å, and the maximum opening diameter was 7.49 Å.

[0074] Figure 3 shows the structure around the connector identified by X-ray structural analysis of the PCN crystal of Example 6. Figure 4 shows the structure of the PCN crystal of Example 6 from the c-axis direction with the largest opening.

[0075] (Example 7: Synthesis of PCN) (TPP) represented by formula (2a) ＋ (344TPHAP) － 3.7 mg (0.005 mmol) of PCN, 2.5 mg (0.015 mmol) of terephthalic acid (BDC), 3.3 mg (0.015 mmol) of cobalt bromide, 1 mL of dehydrated dimethylformamide (DMF), and 0.1 mL of ethanol were placed in a vial and heated at 80°C for 40 hours to obtain pale red PCN crystals (hereinafter also referred to as AFP-82).

[0076] The structural parameters of the obtained PCN crystals determined by X-ray analysis are shown in Table 3. The porosity was 64.8%, the minimum opening diameter was 5.46 Å, and the maximum opening diameter was 7.12 Å.

[0077]

[0078] Figure 5 shows the structure around the connector identified by X-ray structural analysis of the PCN crystal of Example 7. Figure 6 shows the structure of the PCN crystal of Example 7 from the a-axis direction with the largest opening.

[0079] (Example 8: Synthesis of PCN) (TPP) represented by formula (2a) ＋ (344TPHAP) －7.4 mg (0.01 mmol) of PCN, 6.5 mg (0.03 mmol) of 2,6-naphthalenedicarboxylic acid (NDC), 6.6 mg (0.03 mmol) of cobalt bromide, and 2 mL of dehydrated dimethylformamide (DMF) were placed in a vial and heated at 100°C for 2 days to obtain reddish-purple PCN crystals (hereinafter also referred to as APF-83).

[0080] The structural parameters of the obtained PCN crystals determined by X-ray analysis are shown in Table 4. The porosity was 73.9%, the minimum opening diameter was 9.19 Å, and the maximum opening diameter was 11.09 Å.

[0081]

[0082] Figure 7 shows the structure around the connector identified by X-ray structural analysis of the PCN crystal of Example 8. Figure 8 also shows the structure of the PCN crystal of Example 8 from the a-axis direction with the largest opening.

[0083] (Example 10: Inclusion of artemisinin) The PCN crystals (APF-80) immediately after synthesis obtained in Example 5 were washed three times with DMA, and then washed three times with ethyl acetate. The washed APF-80 was allowed to stand in ethyl acetate for three days at 40°C. Thereafter, APF-80 was placed in 1 mL of heptane containing 2.1 mg (7.4 µmol) of artemisinin represented by the following chemical formula, and allowed to stand for two days. The results of X-ray structural analysis of the PCN crystals encapsulating artemisinin are shown in Table 6. The structural formula of artemisinin is shown in Figure 9. Furthermore, the electron density of the encapsulated artemisinin is shown in Figure 10, and the temperature factor of the encapsulated artemisinin is shown in Figure 11. Furthermore, Figure 12 shows the Co in the PCN crystals (APF-80). ２＋ , 344-TPHAP and the interaction between water molecules and the guest (artemisinin).

[0084]

[0085] (Example 11: Inclusion of quinine) The PCN crystals (APF-80) immediately after synthesis obtained in Example 5 were washed three times with DMA, and then washed three times with ethyl acetate. The washed APF-80 was allowed to stand in ethyl acetate for three days at 40°C. Thereafter, APF-80 was placed in 1 mL of heptane containing 0.8 mg (2.5 μmol) of quinine represented by the following chemical formula (a), and allowed to stand at 40°C for three days. The results of X-ray structural analysis of the PCN crystals containing quinine are shown in Table 7. Furthermore, FIG. 13 shows the electron density of the encapsulated quinine, and FIG. 14 shows the temperature factor of the encapsulated quinine. Furthermore, FIG. 15 shows the Co in the PCN crystals (APF-80). ２＋ , 344-TPHAP and the interaction between water molecules and the guest (quinine). (a)

[0086]

[0087] (Example 12: Inclusion of Quinidine) The PCN crystals (APF-80) immediately after synthesis obtained in Example 5 were washed three times with DMA, and then washed three times with ethyl acetate. The washed APF-80 was allowed to stand in ethyl acetate for three days at 40°C. Thereafter, APF-80 was placed in 1 mL of heptane containing 0.8 mg (2.5 μmol) of quinidine represented by the following chemical formula (b), and allowed to stand at 40°C for three days. The results of X-ray structural analysis of the PCN crystals containing quinidine are shown in Table 8. The electron density of the quinidine encapsulated is shown in Figure 16, and the temperature factor of the quinidine encapsulated is shown in Figure 17. Furthermore, the Co in the PCN crystals (APF-80) is shown in Figure 18. ２＋ , 344-TPHAP and the interaction between water molecules and the guest (quinidine). (b)

[0088]

[0089] (Example 13: Caffeine inclusion) The PCN crystals (APF-80) immediately after synthesis obtained in Example 5 were washed three times with DMA, and then washed three times with ethyl acetate. The washed APF-80 was allowed to stand in ethyl acetate for three days at 40°C. Then, 1.1 mg (5.7 μmol) of caffeine represented by the following chemical formula (c) and APF-80 were added to a mixed solvent containing 0.9 mL of heptane and 0.1 mL of acetone, and the mixture was allowed to stand at 40°C for four days. Table 9 shows the results of X-ray structural analysis of the PCN crystals containing caffeine. Furthermore, Figure 19 shows the electron density of the encapsulated caffeine, and Figure 20 shows the temperature factor of the encapsulated caffeine. Furthermore, Figure 21 shows the Co in the PCN crystals (APF-80). ２＋ , 344-TPHAP and the interaction between water molecules and the guest (caffeine). (c)

[0090]

[0091] (Example 14: Inclusion of omeprazole) The PCN crystals (APF-80) immediately after synthesis obtained in Example 5 were washed three times with DMA, and then washed three times with ethyl acetate. The washed APF-80 was allowed to stand in ethyl acetate for three days at 40°C. Thereafter, 1.2 mg (3.5 µmol) of omeprazole represented by the following chemical formula (d) and APF-80 were added to a mixed solvent containing 0.9 mL of heptane and 0.1 mL of acetone, and the mixture was allowed to stand at 40°C for four days. The results of X-ray structural analysis of the PCN crystals containing omeprazole are shown in Table 10. The electron density of the encapsulated omeprazole is shown in Figure 22, and the temperature factor of the encapsulated omeprazole is shown in Figure 23. Furthermore, the Co in the PCN crystals (APF-80) is shown in Figure 24. ２＋ , 344-TPHAP and the interaction between water molecules and the guest (omeprazole). (d)

[0092]

[0093] (Example 16: Inclusion of Nicotine) The PCN crystals (APF-80) immediately after synthesis obtained in Example 5 were washed three times with DMA, and then washed three times with ethyl acetate. The washed APF-80 was allowed to stand in ethyl acetate for three days at 40°C. Thereafter, 1.2 mg (3.5 μmol) of nicotine represented by the following chemical formula (e) and APF-80 were added to 1.0 mL of heptane, and the mixture was allowed to stand at 40°C for four days. The results of X-ray structural analysis of the PCN crystals containing nicotine are shown in Table 11. Furthermore, FIG. 25 shows the electron density of the nicotine encapsulated, and FIG. 26 shows the temperature factor of the nicotine encapsulated. Furthermore, FIG. 27 shows the Co in the PCN crystals (APF-80). ２＋ , 344-TPHAP and the interaction between water molecules and the guest (nicotine). (e)

[0094]

[0095] (Example 17: Inclusion of cytisine) The PCN crystals (APF-80) immediately after synthesis obtained in Example 5 were washed three times with DMA, and then washed three times with ethyl acetate. The washed APF-80 was allowed to stand in ethyl acetate for three days at 40°C. Thereafter, 1.4 mg (7.4 µmol) of cytisine represented by the following chemical formula (f) and APF-80 were added to 2.0 mL of heptane, and the mixture was allowed to stand at 40°C for four days. The results of X-ray structural analysis of the PCN crystals containing cytisine are shown in Table 12. Furthermore, the electron density of the encapsulated cytisine is shown in Figure 28, and the temperature factor of the encapsulated cytisine is shown in Figure 29. Furthermore, Figure 30 shows the Co in the PCN crystals (APF-80). ２＋ , 344-TPHAP and the interaction between water molecules and the guest (cytisine). (f)

[0096]

[0097] (Example 18: Inclusion of voriconazole) The PCN crystals (APF-80) immediately after synthesis obtained in Example 5 were washed three times with DMA and then three times with ethyl acetate. The washed APF-80 was allowed to stand in ethyl acetate for three days at 40°C. Then, 1.2 mg (3.4 μmol) of voriconazole represented by the following chemical formula (g) and APF-80 were added to 0.90 mL of heptane and 0.1 mL of acetone, and the mixture was allowed to stand at 40°C for four days. The results of X-ray structural analysis of the PCN crystals encapsulating voriconazole are shown in Table 13. The electron density of the encapsulated voriconazole is shown in Figure 31, and the temperature factor of the encapsulated voriconazole is shown in Figure 32. Furthermore, the Co in the PCN crystals (APF-80) is shown in Figure 33. ２＋ , 344-TPHAP and the interaction between water molecules and the guest (voriconazole). (g)

[0098]

[0099] (Example 19: Inclusion of cyclopenthiazide) The PCN crystals (APF-80) immediately after synthesis obtained in Example 5 were washed three times with DMA, and then washed three times with ethyl acetate. The washed APF-80 was allowed to stand in ethyl acetate for three days at 40°C. Thereafter, 1.0 mg (2.6 μmol) of cyclopenthiazide represented by the following chemical formula (h) and APF-80 were added to 0.90 mL of heptane and 0.1 mL of acetone, and the mixture was allowed to stand at 40°C for four days. The results of X-ray structural analysis of the PCN crystals containing cyclopenthiazide are shown in Table 14. The electron density of the included cyclopenthiazide is shown in Figure 34, and the temperature factor of the included cyclopenthiazide is shown in Figure 35. Furthermore, the Co in the PCN crystals (APF-80) is shown in Figure 36. ２＋ , 344-TPHAP and the interaction between water molecules and the guest (cyclopenthiazide). (h)

[0100]

[0101] (Example 20: Inclusion of abacavir) The PCN crystals (APF-80) immediately after synthesis obtained in Example 5 were washed three times with DMA, and then washed three times with ethyl acetate. The washed APF-80 was allowed to stand in ethyl acetate for three days at 40°C. Then, 0.7 mg (2.4 μmol) of abacavir represented by the following chemical formula (i) and APF-80 were added to 1.8 mL of heptane and 0.2 mL of acetone, and the mixture was allowed to stand at 40°C for three days. The results of X-ray structural analysis of the PCN crystals encapsulating abacavir are shown in Table 15. The electron density of the encapsulated abacavir is shown in Figure 37, and the temperature factor of the encapsulated abacavir is shown in Figure 38. Furthermore, Figure 39 shows the Co in the PCN crystals (APF-80). ２＋ , 344-TPHAP and the interaction between water molecules and the guest (abacavir). (i)

[0102]

[0103] (Example 21: Inclusion of Compound A) The PCN crystals (APF-80) immediately after synthesis obtained in Example 5 were washed three times with DMA, and then washed three times with ethyl acetate. The washed APF-80 was allowed to stand in ethyl acetate for three days at 40°C. Thereafter, 1.2 mg (4.8 µmol) of compound A represented by the following chemical formula (j) and APF-80 were added to 1.8 mL of heptane and 0.2 mL of acetone, and the mixture was allowed to stand at 40°C for three days. The results of X-ray structural analysis of the PCN crystals encapsulating compound A are shown in Table 16. Furthermore, Figure 40 shows the electron density of the encapsulated compound A, and Figure 41 shows the temperature factor of the encapsulated compound A. Furthermore, Figure 42 shows the Co in the PCN crystals (APF-80). ２＋ , 344-TPHAP and the interaction between water molecules and the guest (compound A). (j)

[0104]

[0105] (Example 23: Inclusion of artemisinin) The PCN crystals (APF-82) immediately after synthesis obtained in Example 7 were washed three times with DMA, and then washed three times with ethyl acetate. The washed APF-80 was allowed to stand in ethyl acetate for three days at 40°C. Thereafter, 2.3 mg (8.1 µmol) of artemisinin and APF-82 were added to 1.8 mL of heptane and 0.2 mL of acetone, and the mixture was allowed to stand at 40°C for two days. The results of X-ray structural analysis of the PCN crystals encapsulating artemisinin are shown in Table 17. Figure 43 shows the Co in the PCN crystals (APF-82). ２＋ , 344-TPHAP and the interaction between water molecules and the guest (artemisinin).

[0106] This application claims priority based on Japanese Patent Application No. 2024-030775, filed February 29, 2024, the disclosure of which is incorporated herein in its entirety by reference.

Claims

1. A 4,6-diamino-5-pyrimidinecarbonitrile derivative represented by any one of the following general formulas (1A) to (1C): (In general formula (1A), X １ is any X １ One of the groups is a nitrogen atom and the other is CH, or any X １ Two of them are nitrogen atoms, and the others are CH. １ represents a divalent group selected from the group consisting of optionally substituted arylene, optionally substituted heteroarylene, a single bond, optionally substituted alkylene, optionally substituted cycloalkylene, optionally substituted alkenylene, optionally substituted alkynylene, and -C(=O)-, or a divalent group formed by combining two or more of the same or different groups selected from the above group. (In general formula (1B), X ２ are each independently a nitrogen atom or CH, and X ３ is NH, N-alkyl, or N-aryl, and at least X ２ Either of the nitrogen atom or X ３ is NH. Y １ is the same as in general formula (1A). (In general formula (1C), R １ are each independently selected from a methyl group, a carboxy group, a hydroxy group, an amino group, an aldehyde group, and CH; R １ At least one of Y is a methyl group, a carboxy group, a hydroxy group, an amino group, or an aldehyde group. １ is the same as in general formula (1A).

2. 1,3,4,6,7,9-hexaazaphenalenyl derivatives represented by any of the following general formulas (2A) to (2I) (excluding 2,5,8-tri(4-pyridyl)-1,3,4,6,7,9-hexaazaphenalene, 2,5,8-tri(3-pyridyl)-1,3,4,6,7,9-hexaazaphenalene, and 2,5,8-tri(4-carboxyphenyl)-1,3,4,6,7,9-hexaazaphenalene). (In general formula (2A), X １ Each of the aromatic rings independently represents an arbitrary X １ One of the groups is a nitrogen atom and the other is CH, or any X １ Two of them are nitrogen atoms, and the others are CH. １ are each independently a divalent group selected from the group consisting of optionally substituted arylene, optionally substituted heteroarylene, a single bond, optionally substituted alkylene, optionally substituted cycloalkylene, optionally substituted alkenylene, optionally substituted alkynylene, and —C(═O)—, or a divalent group formed by combining two or more of the same or different groups selected from the above group; M ＋ represents a counter cation.) (In general formula (2B), X ２ are each independently a nitrogen atom or CH for each aromatic ring, and X ３ is NH, N-alkyl, or N-aryl, and at least each aromatic ring independently has X ２ Either of the nitrogen atom or X ３ is NH. Y １ is the same as in general formula (2A), and M ＋ represents a counter cation.) (In general formula (2C), R １ are each independently selected from a methyl group, a carboxy group, a hydroxy group, an amino group, an aldehyde group, and CH for each aromatic ring; R １ At least one of Y is a methyl group, a carboxy group, a hydroxy group, an amino group, or an aldehyde group. １ is the same as in general formula (2A), and M ＋ represents a counter cation.) (In general formula (2D), X １ , Y １ and M ＋ is the same as in general formula (2A), and X ２ and X ３ is the same as in general formula (2B). (In general formula (2E), X １ , Y １ and M ＋ is the same as in general formula (2A), and R １ is the same as in general formula (2C). (In general formula (2F), Y １ and M ＋ is the same as in general formula (2A), and X ２ and X ３ is the same as in general formula (2B), and R １ is the same as in general formula (2C). (In general formula (2G), １ , Y １ and M ＋ is the same as in general formula (2A), and R １ is the same as in general formula (2C). (In general formula (2H), Y １ and M ＋ is the same as in general formula (2A), and X ２ and X ３ is the same as in general formula (2B), and R １ is the same as in general formula (2C). (In general formula (2I), X １ , Y １ and M ＋ is the same as in general formula (2A), and X ２ and X ３ is the same as in general formula (2B).

3. A porous network complex comprising a tridentate ligand and a connector having a transition metal, wherein the tridentate ligand is the 1,3,4,6,7,9-hexaazaphenalenyl derivative according to claim 2, and at least a portion of the transition metal is coordinated to the tridentate ligand.

4. A method for preparing a sample for crystal structure analysis, comprising: preparing a sample in which a compound to be analyzed is dissolved in a solvent; immersing a single crystal of the porous network complex described in claim 3 in the sample; incorporating the compound to be analyzed into the pores of the porous network complex; and removing the porous network complex into which the compound to be analyzed has been incorporated from the solvent.

5. A method for determining the molecular structure of a compound to be analyzed, which comprises performing crystal structure analysis using a sample for crystal structure analysis obtained by the method of claim 4.

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