Porous coordination network, preparation method of sample for crystal structure analysis, and molecular structure determination method

Abstract

The porous coordination network is represented by the following formulae (I) to (VIII), where M < 2 + > is a divalent metal ion, M < 3 + > is a trivalent metal ion, L < 1a > and L < 1b > are tridentate ligands having a hexaazaphenanthrene alkenyl group, L < 2a > and L < 2b > are bidentate or tridentate ligands containing a carboxyl group, L < 3-> is a third ligand ion which is an anion of a triazole or a triazole derivative, and Y is a cation. Formula (I) (M2 +) 4 (L1a-) 2 (L2a 2-) 3 (Formula (II)) 11 (L1a-) 6 (L2a 2-) 8 (Formula (II)) [(M2 +) 5 (L1a-) 4 (L2a 2-) 4] Y2p formula (III) [(M2 +) 2 (L1a-) 1 (L2a 2-) 2] Yp formula (IV) [(M2 +) 3 (L1a-) 2 (L2b 3-) 2] Y2p formula (VI) [(M2 +) 8 (L1b 3-) 2 (L2a 2-) 3 (L3-) 6] Y2p formula (VII) (M2 +) 5 (M3 +) 1 (L1a-) 3 (L2a 2-) 5 (VIII).

Description

Technical Field

[0001] The present disclosure relates to a porous coordination network and also to a method for preparing a sample for crystal structure analysis and a method for determining a molecular structure using the porous coordination network. Background Art

[0002] A porous coordination network (PCN) composed of metal ions and organic ligands has an infinite structure that can maintain its structure even if the solvent is removed, and technologies that utilize its pores have been proposed. For example, PCN that undergoes reversible structural changes according to the adsorption and desorption of guests in the pores (non-patent document 1), PCN composed of a ligand of 2,4,6-tri(4-pyridyl)triazine and ZnBr2 (non-patent documents 2 and 3), and PCN composed of a ligand of tripyridylhexaazaphenalenate (K + TPHAP - ) ligand and ZnI2 combined PCN (Non-Patent Document 4). In addition, the inventors of the present application recently disclosed a porous coordination network formed by the first ligand and the second ligand in which the nitrogen atom of the pyridine group functions as a ligand and is coordinated with the metal (Non-Patent Document 5, Patent Documents 1, 2).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2020-147521

[0006] Patent Document 2: Japanese Patent Application Publication No. 2022-11418

[0007] Non-patent literature

[0008] Non-patent document 1: Sujit K. Ghosh et al., Angew. Chem., 2013, 125, 1032

[0009] Non-patent document 2: Masaki Kawano et al., Angew. Chem. Int. Ed. 2008, 47, 1269-1271

[0010] Non-patent document 3: Makoto Fujita et al. NATURE CHEMISTRY, VOL 3, 2011

[0011] Non-patent document 4: Masaki Kawano, et al. CrystEngComm., 2014, 16, 6335

[0012] Non-patent literature 5: Masaki Kawano, et al. Inorg. Chem., 2021, 60, 17858-17864 Summary of the invention

[0013] Problems to be solved by the invention

[0014] PCN has a very large surface area compared to zeolite and activated carbon, and can generate an equipotential structure through structural customization, so it has attracted much attention in the fields of catalyst carriers, adsorption, and separation and purification. In addition, if a PCN that can analyze middle molecules (molecules with a molecular weight of about 500 to 3000) that have been considered difficult to analyze so far can be provided, a leap-forward acceleration in the development of pharmaceuticals can be expected. However, the inventors of this application have repeatedly conducted in-depth research and found that in order to incorporate middle molecules as guest molecules, it is not enough to consider only the molecular size of the guest molecule and the size of the PCN, but there is also compatibility between the shape of the guest molecule and the pore structure of the PCN. That is, it is understood that it is necessary not only to simply adjust the size of the pore diameter, but also to select a PCN corresponding to the chemical structure of the guest molecule. If a variety of PCNs with different pore shapes can be provided, the number of middle molecules that can be structurally analyzed by PCN can be increased, which can make a significant contribution to the structural analysis of middle molecules.

[0015] It should be noted that, in the above, the case of using a middle molecule as a guest molecule is described, but similar problems will occur regardless of the molecular weight.

[0016] The present invention is accomplished in view of the above background, and its purpose is to provide a porous coordination network with a new structure, a method for preparing a sample for crystal structure analysis, and a method for determining a molecular structure.

[0017] Means of solving problems

[0018] The inventors of the present application have conducted intensive studies and have found that the problems of the present disclosure can be solved in the following manner, thereby completing the present disclosure.

[0019] [1]: A porous coordination network, wherein the porous coordination network has a three-dimensional network structure, forming pores capable of enclosing guest molecules,

[0020] The porous coordination network has a crystal structure, and the crystal structure has a unit structure of any one of the following formulas (I) to (VIII):

[0021] (M 2+ )4(L1a - )2(L2a 2- )3 Formula (I)

[0022] (M 2+ ) 11 (L1a - )6(L2a 2- )8 Formula (II)

[0023] [(M 2+ )5(L1a - )4(L2a 2- )4]·Y 2p Formula (III)

[0024] [(M 2+ )2(L1a - )1(L2a 2- )2]·Y p Formula (IV)

[0025] (M 2+ )2(L1a - )1(L2b 3- )1 Formula (V)

[0026] [(M 2+ )3(L1a - )2(L2b 3- )2]·Y 2p Formula (VI)

[0027] [(M 2+ )8(L1b 3- )2(L2a 2- )3(L3 - )6]·Y 2p Formula (VII)

[0028] (M 2+ )5(M 3+ )1(L1a - )3(L2a 2- )5 Formula (VIII)

[0029] Among them, in formula (I) to formula (VIII),

[0030] M 2+ is a divalent metal ion, M 3+ It is a trivalent metal ion.

[0031] L1a and L1b are tridentate ligands having a hexaazaphenalenyl group.

[0032] L1a -is a first ligand ion of the following formula (1), or a first ligand ion in which 1 to 12 hydrogen atoms of the aromatic ring of formula (1) are independently replaced by a group selected from an alkyl group having 1 to 4 carbon atoms, a halogen group, a hydroxyl group and an amino group,

[0033] [Chemical formula 1]

[0034]

[0035] L1b 3- is a first ligand ion of the following formula (2), or a first ligand ion in which 1 to 12 hydrogen atoms of the aromatic ring of formula (2) are independently replaced by a group selected from an alkyl group having 1 to 4 carbon atoms, a halogen group, a hydroxyl group and an amino group,

[0036] [Chemical formula 2]

[0037]

[0038] L2a is a bidentate ligand containing more than two carboxyl groups.

[0039] L2a 2- The two carboxyl groups serve as a second ligand ion coordinated with the metal ion by a carboxylate anion,

[0040] L2b is a tridentate ligand containing more than three carboxyl groups.

[0041] L2b3- is a second ligand ion in which the three carboxyl groups act as carboxylate anions coordinated with the metal ion,

[0042] L3 - is a third ligand ion which is an anion of triazole or a triazole derivative,

[0043] Y is a cation, p is 1 / (charge of Y),

[0044] A solvent may be further coordinated to the unit structures of formula (I) to (VII).

[0045] [2]: The porous coordination network according to [1], wherein the metal is at least one selected from Mg, Ca, Mn, Fe, Co, Ni, Cu, Zn, Rh, Ag, Cd, Ir, Pt, and Au.

[0046] [3]: The porous coordination network according to [1] or [2], wherein the molecular weight of L2a and L2b is 90 to 1000 and is at least one selected from the following formula (3),

[0047] [Chemical formula 3]

[0048] R 1 -(COOH) n(3)

[0049] Wherein, for said L2a, n is an integer greater than 2, and for said L2b, n is an integer greater than 3,

[0050] R 1 Having: a linear or branched aliphatic group having 2 to 20 carbon atoms, which may have an unsaturated bond, a bond containing a hetero atom, or a substituent;

[0051] An aromatic group having 6 to 72 carbon atoms; and

[0052] At least one structure of a heterocyclic ring having 2 to 60 carbon atoms.

[0053] [4]: The porous coordination network according to any one of [1] to [3], wherein the porous coordination network is used for guest molecule analysis.

[0054] [5]: The porous coordination network according to any one of [1] to [4], wherein the guest molecule is a middle molecule having a molecular weight of 50 to 7000.

[0055] [6]: A method for preparing a sample for crystal structure analysis, wherein:

[0056] Prepare a sample by dissolving the target compound in a solvent.

[0057] The porous coordination network described in any one of [1] to [5] is dispersed in the sample,

[0058] The analyte compound is incorporated into the pores of the porous coordination network.

[0059] [7]: A method for determining the molecular structure of an analysis target compound, characterized in that a crystal structure analysis is performed using a sample for crystal structure analysis obtained by the method for preparing a sample for crystal structure analysis described in [6].

[0060] Effects of the Invention

[0061] According to the present disclosure, there are the following excellent effects: a porous coordination network with a new structure, a method for preparing a sample for crystal structure analysis, and a method for determining a molecular structure can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0062] Figure 1 This is a diagram showing the coordination environment of PCNI-1 obtained in Example 1.

[0063] Figure 2 This is a diagram showing the state of the pores of PCNI-1 obtained in Example 1 when observed from the a-axis.

[0064] Figure 3 This is a diagram showing the coordination environment of PCNI-2 obtained in Example 2.

[0065] Figure 4 This is a diagram showing the state of the pores of PCNI-2 obtained in Example 2 when observed from the c-axis.

[0066] Figure 5 This is a diagram showing the coordination environment of PCNI-3 obtained in Example 3.

[0067] Figure 6 This is a diagram showing the state of the pores of PCNI-3 obtained in Example 3 when observed from the b-axis.

[0068] Figure 7 This is a diagram showing the coordination environment of PCNI-4 obtained in Example 4.

[0069] Figure 8 This is a diagram showing the state of the pores of PCNI-4 obtained in Example 4 when observed from the b-axis.

[0070] Fig. 9 This is a diagram showing the coordination environment of PCNII-1 obtained in Example 5.

[0071] Fig.10 This is a diagram showing the state of the pores when PCNII-1 obtained in Example 5 is observed from the c-axis.

[0072] Fig.11 This is a diagram showing the coordination environment of PCNIII-1 obtained in Example 6.

[0073] Fig.12 This is a diagram showing the state of the pores when PCNIII-1 obtained in Example 6 is observed from the a-axis.

[0074] Fig.13 This is a diagram showing the coordination environment of PCNIV-1 obtained in Example 7.

[0075] Fig.14 This is a diagram showing the state of the pores when PCNIV-1 obtained in Example 7 is observed from the a-axis.

[0076] Fig.15 This is a diagram showing the coordination environment of PCNV-1 obtained in Example 8.

[0077] Fig.16 This is a diagram showing the state of pores when PCNV-1 obtained in Example 8 is observed from the c-axis.

[0078] Fig.17This is a diagram showing the coordination environment of PCNVI-1 obtained in Example 9.

[0079] Fig.18 This is a diagram showing the state of the pores when PCNVI-1 obtained in Example 9 is observed from the a-axis.

[0080] Fig.19 This is a diagram showing the coordination environment of PCNVII-1 obtained in Example 10.

[0081] Fig. 20 This is a diagram showing the state of the pores of PCNVII-1 obtained in Example 10 when observed from the c-axis.

[0082] Fig.21 This is a diagram showing the results of Example 11 in which a guest molecule (spironolactone) is included in PCNI-3 (Example 3). The guest molecule is represented by a ball-and-stick model, and PCN is represented by a stick model (the same applies to subsequent figures).

[0083] Fig. 22 This is a diagram showing the results of Example 12 in which a guest molecule (betamethasone) was included in PCNI-3 (Example 3).

[0084] Fig.23 This is a diagram showing the results of Example 13 in which a guest molecule (grisofulvin) was included in PCNV-1 (Example 8).

[0085] Fig.24 This is a diagram showing the results of Example 14 in which a guest molecule (betamethasone) was included in PCNVII-1 (Example 10).

[0086] Fig.25 This is a diagram showing the results of Example 15 in which a guest molecule (ivermectin) was included in the pores of PCNVII-1 (Example 10).

[0087] Fig.26 It is a diagram showing the coordination environment of PCNI-5 (Example 16).

[0088] Fig. 27 This is a diagram showing the state of pores when PCNI-5 obtained in Example 16 was observed.

[0089] Fig.28 This is a diagram showing the result of encapsulating a guest molecule (ROY) in the pores of PCNI-5 (Example 16).

[0090] Fig.29 It is a diagram showing the coordination environment of PCNVIII-1 (Example 18).

[0091] Fig.30 This is a diagram showing the state of pores when PCNVIII-1 obtained in Example 18 was observed.

[0092] Fig.31 This is a diagram showing the results of including a guest molecule (monensin sodium) in the pores of PCNV-1 (Example 19). DETAILED DESCRIPTION

[0093] Hereinafter, an example of an embodiment to which the present disclosure is applied is described. It should be noted that other embodiments are also included in the scope of the present disclosure as long as they are consistent with the main purpose of the present disclosure. In addition, the dimensions and ratios of the various parts in the following figures are for the convenience of description and are not limited thereto.

[0094] The porous coordination network (hereinafter also referred to as the PCN) involved in the present disclosure has a three-dimensional network structure. The three-dimensional network structure is formed by coordinating the ligands described below with the metal. In the PCN, pores capable of enclosing guest molecules are formed.

[0095] The PCN is represented by any one of the following formulae (I) to (VIII): The ligand and the metal are combined and regularly formed by a coordination bond.

[0096] Having a crystal structure having a unit structure of any one of the following formulas (I) to (VIII):

[0097] (M 2+ )4(L1a - )2(L2a 2- )3 Formula (I)

[0098] (M 2+ ) 11 (L1a - )6(L2a 2- )8 Formula (II)

[0099] [(M 2+ )5(L1a - )4(L2a 2- )4]·Y 2p Formula (III)

[0100] [(M 2+ )2(L1a - )1(L2a 2- )2]·Y p Formula (IV)

[0101] (M 2+ )2(L1a - )1(L2b 3- )1 Formula (V)

[0102] [(M 2+ )3(L1a - )2(L2b 3- )2]·Y 2p Formula (VI)

[0103] [(M 2+ )8(L1b 3- )2(L2a 2- )3(L3 - )6]·Y 2p Formula (VII)

[0104] (M 2+ )5(M 3+ )1(L1a - )3(L2a 2- )5 Formula (VIII)

[0105] Wherein, in formula (I) to (VIII), M 2+ is a divalent metal ion, M 3+ is a trivalent metal ion, and L1a and L1b are tridentate ligands having a hexaazaphenanthrenyl group.

[0106] L1a - It is a first ligand ion of the following formula (1), or a first ligand ion in which 1 to 12 hydrogen atoms of the aromatic ring of formula (1) are independently substituted by a group selected from an alkyl group having 1 to 4 carbon atoms, a halogen group, a hydroxyl group and an amino group.

[0107] [Chemical formula 4]

[0108]

[0109] L1b 3- It is a first ligand ion of the following formula (2), or a first ligand ion in which 1 to 12 hydrogen atoms of the aromatic ring of formula (2) are independently substituted by a group selected from an alkyl group having 1 to 4 carbon atoms, a halogen group, a hydroxyl group and an amino group.

[0110] [Chemical formula 5]

[0111]

[0112] L2a is a bidentate ligand containing two or more carboxyl groups. The upper limit of the number of carboxyl groups is not particularly limited, and is, for example, 4, and the preferred upper limit is 3, and particularly preferably 2. 2- The two carboxyl groups serve as a carboxyl anion and are coordinated with the metal ion as a second ligand ion.

[0113] L2b is a bidentate ligand containing 3 or more carboxyl groups. The upper limit of the number of carboxyl groups is not particularly limited, and is, for example, 6, and the preferred upper limit is 4, and particularly preferably 3. 3- The three carboxyl groups serve as carboxylate anions and are coordinated with the metal ions as second ligand ions.

[0114] L3 - is a third ligand ion, which is an anion of triazole or a triazole derivative. The triazole may be any of 1,2,3-triazole or 1,2,4-triazole. A triazole derivative refers to a compound having a triazole. For example, it refers to benzotriazole, or refers to a compound in which one or more hydrogen atoms of benzotriazole are replaced by an amino group, a hydroxyl group, a methyl group, a nitro group, a halogen group, or a carboxyl group. Examples include 4-carboxybenzotriazole, 7-carboxybenzotriazole, benzotriazole butyl ester, 1-hydroxymethylbenzotriazole, and 1-hydroxybenzotriazole.

[0115] Through the present disclosure, a PCN with a new structure can be provided by combining the above-mentioned specific metal with a first ligand and a second ligand, or by combining the above-mentioned specific metal with a first ligand, a second ligand and a third ligand. By using a first ligand ion of formula (1) or a first ligand ion of formula (2) with high symmetry, the periodicity of the structure can be improved and the crystallinity can be improved. Therefore, a crystal suitable for structural analysis can be provided.

[0116] In addition, the first ligand ion of the formula (1) with high symmetry and the second ligand ion with 2 or 3 carboxylic acid anions (carboxylate groups), or the first ligand ion of the formula (2) with high symmetry and the second ligand ion and the third ligand ion with 2 carboxylic acid anions (carboxylate groups) are used to form a metal complex cluster with a divalent metal ion, thereby having the excellent effect of easily obtaining a porous coordination network with a large pore size and high solvent stability. In addition, by using the PCN to form a metal complex cluster with a divalent metal ion, the physical / chemical stability of the structure can be increased. That is, from the perspective of physical stability, even with huge pores, the firmness of the structure can be maintained. In addition, due to the excellent chemical stability, the effect of improving solvent stability can be expected. This PCN can be applied to guest molecule analysis.

[0117] M in formula (I) to (VIII) 2+ is a divalent metal ion, M 3+ It is a trivalent metal ion, and its type is not particularly limited. As a preferred example of the metal, at least one selected from Mg, Ca, Mn, Fe, Co, Ni, Cu, Zn, Rh, Ag, Cd, Ir, Pt, and Au can be listed. Multiple metals can also be used, but from the viewpoint of simplicity of structural analysis, it is preferably used alone.

[0118] The structures of L2a and L2b are not particularly limited as long as they satisfy the above conditions. From the viewpoint of easy formation of PCN, the molecular weight is preferably 90 to 1000, more preferably 100 to 900, further preferably 110 to 850, and particularly preferably 116 to 801.

[0119] Preferred examples of L2a and L2b include at least one selected from the following formula (3) having a molecular weight of 90 to 1000.

[0120] [Chemical formula 6]

[0121] R 1 -(COOH) n (3)

[0122] In which, for L2a, n is an integer greater than or equal to 2, and the preferred upper limit is 4, and the more preferred upper limit is 3. For L2b, n is an integer greater than or equal to 3, and the preferred upper limit is 6, and the more preferred upper limit is 4. 1 It has at least one of: (i) a linear or branched aliphatic group having 2 to 20 carbon atoms which may have an unsaturated bond, a bond containing a heteroatom, or a substituent; (ii) an aromatic group having 6 to 72 carbon atoms which may have an unsaturated bond, a bond containing a heteroatom, or a substituent; and (iii) a heterocyclic ring having 2 to 60 carbon atoms which may have an unsaturated bond, a bond containing a heteroatom, or a substituent. From the viewpoint of the robustness of the PCN structure, it is preferred to have an aromatic ring, an unsaturated bond, or the like. The more preferred range of the number of carbon atoms in (i) is 2 to 16, and particularly preferably 2 to 10. The more preferred range of the number of carbon atoms in (ii) is 6 to 60, and particularly preferably 6 to 55. The more preferred range of the number of carbon atoms in (iii) is 6 to 60, and particularly preferably 6 to 55. The aliphatic group may be chain-shaped or alicyclic.

[0123] Preferred examples of L2a and L2b include compounds having the structure of the following formula (4): The preferred range of the molecular weight is 90 to 1000, and the more preferred range is as described above.

[0124] [Chemical formula 7]

[0125]

[0126] In formula (4), Ar represents a divalent or trivalent aromatic group which may have a substituent. Ha represents a bond consisting of heteroatoms. Sa is an atom which forms four bonds in the vertex direction of a tetrahedron, such as carbon or silicon, or an ion which forms four bonds in the vertex direction of a tetrahedron, such as ammonium or phosphonium ion. Z is a carbonyl group or a sulfonyl group, an aliphatic group which may have a substituent having 1 to 10 carbon atoms, or a single bond which directly connects Ar and Ar. X 1 ~X 4 Each independently represents a divalent organic group, or a single bond directly connecting any one of Ar, Ha, and Sa to a carboxyl group. 1 ~Y 4 Each independently represents a monovalent organic group or a carboxylic acid having one or more carboxyl groups as coordination sites. 1 ~X 4 Preferred examples of X include a single bond, a linear or branched aliphatic group having 2 to 10 carbon atoms which may have a substituent, an alicyclic aliphatic group having 5 to 15 carbon atoms, an aromatic group having 6 to 24 carbon atoms, and a group having a heterocyclic ring having 2 to 20 carbon atoms. 1 ~X 4 Further preferred examples include a single bond, a straight-chain or branched aliphatic group having 2 to 8 carbon atoms which may have a substituent, an alicyclic aliphatic group having 5 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms, and a group having a heterocyclic ring having 2 to 15 carbon atoms.

[0127] Specific examples of L2a include the following compounds.

[0128] [Chemical formula 8]

[0129]

[0130] Specific examples of L2b include the following compounds.

[0131] [Chemical formula 9]

[0132]

[0133] The shape and size of the pores of PCN can be adjusted by changing the ligand. In addition, even when the same ligand is used, the shape and size of the pores can be changed by changing the synthesis method.

[0134] The pore diameter of PCN can be understood as the body diagonal distance when the pores filled with spheres of the van der Waals radius of atoms that are not forming a network structure are regarded as cubes. The maximum diameter of the pores of PCN, which is defined as the distance in the short axis direction when a cut is formed at the opening of the pore and the cut is regarded as a quadrilateral, is not limited, but from the viewpoint of being used as a sample for crystal structure analysis, it is preferably 0.8 nm or more. More preferably, it is 1 nm or more, and further preferably 1 to 5.0 nm. The opening diameter of the pore is mainly determined by the type of the first ligand. By setting the opening diameter size of the pore to 1.5 nm or more, it is possible to selectively incorporate molecular compounds with a molecular weight of, for example, about 100 to 3000 into the hollow, which can be applied to various purposes including crystal structure analysis.

[0135] Y is not particularly limited, but from the viewpoint of existence in PCN pores, the molecular weight is preferably 1 to 600, more preferably 6 to 500. From the viewpoint of interaction between Y and the inclusion guest, it preferably has an alkali metal, an alkaline earth metal, or an organic cation.

[0136] As specific examples of Y, Li as an inorganic cation can be exemplified. + 、Na + , K + , Rb + , Cs + 、Be 2+ Mg 2+ , Ca 2 + , Sr 2+ Or Ba 2+ ; Cationic components of organic salts, for example, cationic components of organic ammonium salts, organic oxonium salts, organic arsonium salts, organic sulfonium salts, organic bromonium salts, organic phosphonium salts, and organic iodonium salts.

[0137] PCN can also be coordinated with a solvent. The type of solvent coordinated with PCN is not limited, but from the perspective of forming hydrogen bonding sites, polar solvents are preferred. Preferred examples of the polar solvent include water; alcohols such as methanol, ethanol, and isopropanol; glycols such as ethylene glycol and polyethylene glycol; ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ketone solvents such as acetone, ethyl methyl ketone, and cyclohexanone; ether solvents such as diethyl ether, diphenyl ether, tetrahydrofuran, 1,4-dioxane, cyclopentyl methyl ether, and methyl tert-butyl ether; N,N'-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone. These can be used alone or in combination of two or more.

[0138] The axis of the 4-carboxybenzyl group used as L1b of formula (VII) is freely rotatable relative to the hexaazaphenanthrenyl group, and has excellent symmetry. Moreover, even in PCN where the oxygen of the carboxylate radical of the 4-carboxybenzyl group is coordinated with the metal, the free rotation of the axis of the 4-carboxybenzyl group itself is not hindered. The 4-pyridyl group used as L1a- of formulas (I) to (VI) is also freely rotatable relative to the hexaazaphenanthrenyl group, and has excellent symmetry.

[0139] The PCN represented by formula (I) has a crystal structure having a unit structure of 4 metals, 2 first ligand ions, and 3 second ligand ions. PCN may further be coordinated with a solvent. As preferred examples of the structural unit of formula (I), (Mn 2+ )4(TPHAP - )2(BDC 2- )3、(Mn 2+ )4(TPHAP - )2(NDC 2- )3、(Mn 2+ )4(TPHAP - )2(BPDC 2- )3、(Fe 2+ )4(TPHAP - )2(BDC 2- )3、(Fe 2+ )4(TPHAP - )2(NDC 2- )3、(Fe 2+ )4(TPHAP - )2(BPDC 2- )3、(Co 2+ )4(TPHAP - )2(BDC 2- )3、(Co 2+ )4(TPHAP - )2(NDC 2- )3、(Co 2+ )4(TPHAP - )2(BPDC 2- )3、(Ni 2+ )4(TPHAP - )2(BDC 2- )3、(Ni 2+ )4(TPHAP - )2(NDC 2- )3、(Ni 2+ )4(TPHAP - )2(BPDC 2- )3.(Cu 2+ )4(TPHAP- )2(BDC 2- )3.(Cu 2+ )4(TPHAP - )2(NDC 2- )3.(Cu 2+ )4(TPHAP - )2(BPDC 2- )3、(Zn 2+ )4(TPHAP - )2(BDC 2- )3、(Zn 2+ )4(TPHAP - )2(NDC 2- )3、(Zn 2+ )4(TPHAP - )2(BPDC 2- )3、(Cd 2+ )4(TPHAP - )2(BDC 2- )3、(Cd 2+ )4(TPHAP - )2(NDC 2- )3、(Cd 2+ )4(TPHAP - )2(BPDC 2- )3. It should be noted that BDC 2- It is the anion of terephthalic acid, NDC 2- It is the anion of 2,6-naphthalenedicarboxylic acid, BPDC 2- It is the anion of biphenyl-4,4'-dicarboxylic acid. In addition, TPHAP - It is the first ligand ion of the above formula (1).

[0140] The PCN represented by formula (II) has a crystal structure having a unit structure of 11 metals, 6 first ligand ions, and 8 second ligand ions. In addition, a solvent may be coordinated. As a preferred example of the unit structure of formula (II), (Mn 2+ ) 11 (TPHAP - )8(MA 2- )8、(Fe 2+ ) 11 (TPHAP - )6(MA 2- )8、(Co 2+ ) 11 (TPHAP - )6(MA 2- )8.(Ni 2+ ) 11(TPHAP - )6(MA 2- )8.(Cu 2+ ) 11 (TPHAP - )6(MA 2- )8、(Zn 2+ ) 11 (TPHAP - )6(MA 2- )8、(Cd 2+ ) 11 (TPHAP - )6(MA 2- )8. It should be noted that MA 2- Represents the anion of trans,trans-muconic acid.

[0141] The PCN represented by formula (III) has a crystal structure having a unit structure of 5 metals, 4 first ligand ions, and 4 second ligand ions. Y is a counter ion. In addition, a solvent may be coordinated. As a preferred example of the unit structure, (Mn 2+ )5(TPHAP - )4(BPDC 2- )4·Y 2p , (Fe 2+ )5(TPHAP - )4(BPDC 2- )4·Y2,(Co 2+ )5(TPHAP - )4(BPDC 2- )4·Y2,(Ni 2+ )5(TPHAP - )4(BPDC 2- )4·Y 2p , (Cu 2+ )5(TPHAP - )4(BPDC 2- )4·Y 2p , (Zn 2+ )5(TPHAP - )4(BPDC 2- )4·Y 2p , (Cd 2+ )5(TPHAP - )4(BPDC 2- )4·Y 2p Y is a cation present as a counter ion. As specific examples of cations, Li + 、Na + , K + , Rb +Mg 2+ , Ca 2+ , Sr 2+ , Tetrabutylammonium (TBA + ), dimethylammonium (DMA + ). The same applies to the preferred Y in (IV), (VI) and (VII) described later.

[0142] The PCN represented by formula (IV) has a crystal structure having a unit structure of two metals, one first ligand ion, and two second ligand ions. Y is a counter ion. In addition, a solvent may be coordinated. As a preferred example of the unit structure, (Mn 2+ )2(TPHAP - )1(DHC 2- )2·Y p , (Fe 2+ )2(TPHAP - )1(DHC 2- )2·Y p , (Co 2+ )2(TPHAP - )1(DHC 2- )2·Y p 、(Ni 2+ )2(TPHAP - )1(DHC 2- )2·Y p , (Cu 2+ )2(TPHAP - )1(DHC 2- )2·Y p 、(Zn 2+ )2(TPHAP - )1(DHC 2- )2·Y p 、(Cd 2+ )2(TPHAP - )1(DHC 2- )2·Y p It should be noted that DHC 2- represents an anion of 2,5-dihydroxyterephthalic acid. In addition, Y is a cation present as a counter ion.

[0143] The PCN represented by formula (V) has a crystal structure having a unit structure of two metals, one first ligand ion, and one second ligand ion. In addition, a solvent may be coordinated. As a preferred example of the unit structure, (Mn 2+ )2(TPHAP - )(TCBM 3- )、(Fe 2+)2(TPHAP - )(TCBM 3- )、(Co 2+ )2(TPHAP - )(TCBM 3- )、(Ni 2+ )2(TPHAP-)(TCBM 3- )、(Cu 2+ )2(TPHAP - )(TCBM 3- )、(Zn 2+ )2(TPHAP - )(TCBM 3- )、(Cd 2+ )2(TPHAP-)(TCBM 3- )。It should be noted that TCBM 3- is the anion of 5’,5”-bis(4-carboxyphenyl)-2’,2”,4’,4”,6’,6”-hexamethylene-[1,1’:3’,1”:3”,1”’-quaterphenyl]-4,4”-dicarboxylic acid.

[0144] The PCN represented by formula (VI) has a crystal structure with a unit structure of 3 metals, 2 first ligand ions, and 1 second ligand ion. In addition, Y is a counterion. Among them, since formula (VI) achieves charge balance through the metal and the second ligand, a crystal structure without the first ligand can also be included. From a macroscopic perspective, it can be seen that considering the defective composition is [(M 2+ )3(L1a - ) (4+2x) / 3 (L2b 3- )2]·Y (4+2x) / 3 (0 < x ≤ 1). In addition, a solvent can also be coordinated. As a preferred example of the unit structure, [(Mn 2+ )3(TPHAP - )2(BTCA 3- )2]·Y 2p 、[(Mn 2+ )3(TPHAP - )2(BTCA 3- )2]·Y 2p 、[(Fe 2+ )3(TPHAP - )2(BTCA 3- )2]·Y 2p 、[(Co 2+ )3(TPHAP - )2(BTCA 3- )2]·Y 2p 、(Ni2 + )3(TPHAP - )2(BTCA 3- )2]·Y 2p 、[(Cu 2+ )3(TPHAP - )2(BTCA 3- )2]·Y 2p 、[(Zn 2+ )3(TP HAP - )2(BTCA 3- )2]·Y 2p 、[(Cd 2+ )3(TPHAP - )2(BTCA 3- )2]·Y 2p It should be noted that BTCA 3- It is the anion of [1,1'-biphenyl]-3,4',5-tricarboxylic acid.

[0145] The PCN represented by formula (VII) has a crystal structure having a unit structure of 2 metals, 2 first ligand ions, 3 second ligand ions, and 6 third ligand ions. Y is a counter ion. In addition, a solvent may be coordinated. As a preferred example of the unit structure, (Mn 2+ )8(HTCHAP 3- )2(TDC 2- )3(TAZ - )6·Y 2p , (Fe 2+ )8(HTCHAP 3- )2(TDC 2- )3(TAZ - )6·Y 2p 、(Ni 2+ )8(HTCHAP 3- )2(TDC 2- )3(TAZ - )6·Y 2p , (Co 2+ )8(HTCHAP 3- )2(TDC 2- )3(TAZ - )6·Y 2p 、(Zn 2+ )8(HTCHAP 3- )2(TDC 2- )3(TAZ - )6·Y 2p 、(Cd 2+ )8(HTCHAP 3-)2(TD C 2- )3(TAZ - )6·Y 2p It should be noted that TDB 2- It is the anion of 2,5-(thiophenediyl)dibenzoic acid, TDC 2- It is the anion of 2,5-thiophenedicarboxylic acid, TAZ - It is the anion of 1,2,3-triazole. 3- It is the first ligand ion of the above formula (2).

[0146] The PCN represented by formula (VIII) has a crystal structure having a unit structure of 6 metals (5 divalent metal ions and 1 trivalent metal ion), 3 first ligand ions, and 5 second ligand ions. In addition, a solvent may be coordinated. As a preferred example of the unit structure, (Co 2+ )5(Co 3+ )1(TPHAP - )3(FDCA 2- )5、(Mn 2+ )5(Mn 3+ )1(TPHAP - )3(FDCA 2- )5、(Fe 2+ )5(Fe 3+ )1(TPHAP - )3(FDCA 2- )5. It should be noted that FDCA 2- It is the anion of 2,5-furandicarboxylic acid.

[0147] The shape of the pores of PCN varies depending on the raw material molecules used. The size of the opening diameter of the pores can be easily adjusted according to the types of ligands and metals. For the analysis of medium molecules, it is preferred to have an opening diameter size as large as possible.

[0148] Solvent molecules such as DMF can also be coordinated with the metal. The bond between the solvent molecule and the metal incorporated into the unit crystal is preferably weaker than the coordination bond between the metal and the first ligand and the coordination bond between the metal and the second ligand, or the second ligand and the third ligand. By incorporating solvent molecules into the crystal structure unit of PCN, it is possible to expect the effect of reducing structural fluctuations when analyzing guest molecules and improving analysis accuracy. In addition, solvent replacement can also be performed according to the incorporated guest molecules, and it is possible to expect to increase the analysis object. In addition, these solvent molecules inside the pores can be confirmed based on analysis.

[0149] This PCN is suitable as a crystal for crystal structure analysis of high molecular weight guest molecules such as pharmaceuticals or peptides. In addition, by forming a crystal with an organic solvent as a ligand, the position of the guest molecule relative to the solvent molecule can also be analyzed. Furthermore, by making the bond between the organic solvent and the metal weaker than the coordination bond between the first ligand and the metal, and the coordination bond between the second ligand and the metal, or the coordination bond between the second ligand and the third ligand and the metal, the degree of freedom of substitution with other solvent molecules can be increased. Therefore, the environmental field of the pores of PCN can be adjusted according to the guest molecule. Through these effects, it can be expected to improve the accuracy of crystal structure analysis.

[0150] Furthermore, according to the present PCN, various PCNs with new structures can be provided by combining a metal, a first ligand, and a second ligand, or by combining a metal, a first ligand, a second ligand, and a third ligand. In addition, as shown in the examples described later, the structure of the PCN obtained by the synthesis method can be changed even within the same combination. Therefore, for example, by preparing a plurality of test tubes to which different types of PCN and solvents are added and adding guest molecules thereto, PCNs suitable for the guest molecules can be easily screened. As a result, it can be expected that structural analysis of middle molecules, which have been difficult to analyze so far, can be easily performed.

[0151] In the above, examples for analysis are listed, but it is also applicable to the purification of substances or as a reaction field in a closed space. In addition, since the surface area is much higher than that of zeolite, it can be expected to be applied to adsorption materials, purification purposes, etc. In addition, it can be used for sensing organic matter, that is, chemical sensor materials. In addition, it can be expected to be applied to drug delivery systems (Drug Delivery System) that release adsorbed guest molecules in response to external stimuli such as ultraviolet (UV) light.

[0152] (Manufacturing method)

[0153] Next, an example of a method for producing PCN will be described. However, the method for producing PCN of the present disclosure is not limited to the following method.

[0154] First, a metal or metal compound, a ligand (first ligand / second ligand or first ligand / second ligand / third ligand) and a solvent can be placed in a container and heated to synthesize by a solvothermal method. In this way, PCN with fine pores can be produced by a one-step reaction of self-assembly. After the PCN is synthesized, crystals are obtained by sufficient washing. Instead of the solvothermal method, PCN can be synthesized by a solution diffusion method, an electrochemical synthesis method, a microwave irradiation method, a mechanochemical synthesis method, or an ultrasonic synthesis method. Various PCNs can be synthesized by changing the solvent and its concentration, the molar ratio of the metal to the ligand, the temperature, and the metal ions.

[0155] The molar ratio of the first ligand to the metal used is 1:1 to 1:10, preferably 1:1 to 1:5, more preferably 1:1 to 1:3. The molar ratio of the second ligand (if the third ligand is used, the second ligand and the third ligand) to the metal is 1:1 to 1:7, preferably 1:1 to 1:5, more preferably 1:1 to 1:3.

[0156] The organic solvent used is not particularly limited as long as it is a solvent that can uniformly dissolve the first ligand and the metal. 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, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; ethers such as tetrahydrofuran, 1,2-dimethoxyethane, and 1,4-dioxane; alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone and methyl ethyl ketone, etc. The solvent can be used alone or in combination of two or more.

[0157] Among them, since the porous coordination network disclosed herein can be synthesized at a higher yield, an amide-based reaction solvent is preferred as the reaction solvent, and DMF, DMA, or NMP is particularly preferred.

[0158] The precipitated PCN can be recovered by filtration. The structure of PCN can be confirmed by elemental analysis, infrared spectra (IR), UV absorption spectrum, visible light absorption spectrum, single crystal X-ray structure analysis, etc.

[0159] (Method for preparing samples for crystal structure analysis)

[0160] Next, the method for preparing a sample for crystal structure analysis according to the present embodiment is described. In the preparation of the sample for crystal structure analysis, an analysis target compound (guest molecule) is doped into the pores of the present PCN to prepare a sample for structure analysis of the compound.

[0161] First, a sample is prepared by dissolving the target compound in a solvent, and the PCN is dispersed in the sample. Then, the target compound is doped into the pores of the PCN, and the solvent is removed to prepare the PCN.

[0162] As a method of bringing a mixture containing the compound to be analyzed into contact with PCN to allow the molecules of the compound to be analyzed to be incorporated into the pores of PCN, a known method can be used.

[0163] The analysis target compound is not particularly limited as long as it is of a size that can enter the PCN pores. It can be applied to a variety of compounds such as low molecular weight compounds, medium molecular weight compounds such as pharmaceuticals, and chiral compounds. For example, molecules with a molecular weight of about 50 to 7000 can be analyzed. Compounds with a molecular weight of 5000 or less are preferred, 480 to 4000 are more preferred, and 500 to 3000 are particularly preferred.

[0164] The method of bringing PCN into contact with the compound to be analyzed is not particularly limited. For example, the molecules of the compound to be analyzed can be incorporated into the pores of PCN by preparing a solution of the compound to be analyzed and bringing PCN into contact with the solution, or by directly bringing PCN into contact with the compound to be analyzed when the compound to be analyzed is a liquid or a gas. Among them, the method of preparing a solution of the compound to be analyzed and bringing PCN into contact with the solution is preferred because it is easy to obtain a sample for crystal structure analysis of higher quality.

[0165] In addition, the contact operation can be performed by a method in which a solution containing the compound to be analyzed is used, or in which the compound to be analyzed is a liquid, the single crystal is immersed in a solution containing the compound to be analyzed, or by a method in which a solution containing the compound to be analyzed is passed through a capillary after the single crystal is filled.

[0166] The solvent of the solution containing the compound to be analyzed may be a solvent that does not dissolve the single crystal used but dissolves the compound to be analyzed. Examples of the solvent 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 isopropanol; 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. The solvents may be used alone or in combination of two or more.

[0167] The contact time between the analyte compound and the PCN is not particularly limited, and is generally a few minutes to several months. Depending on the compound, the contact time can be appropriately shortened or extended. The contact temperature can be, for example, in the range of -30 to 200° C., and is not particularly limited. It is preferred to contact at a temperature that is easy to handle the analyte compound.

[0168] The sample for crystal structure analysis is obtained by doping the molecules of the compound to be analyzed into the pores of PCN. The compound to be analyzed is regularly arranged in the pores according to the size of the opening diameter of the pores. In addition, the regular arrangement mentioned here means that the molecules of the compound to be analyzed are doped into the pores to such an extent that the structure can be determined by crystal structure analysis.

[0169] The sample for crystal structure analysis can be any sample that can determine the molecular structure of the compound to be analyzed, and it is not necessary to incorporate the molecules of the compound to be analyzed into all the pores of PCN. The molecular structure of the compound to be analyzed is determined by using the above-mentioned sample for crystal structure analysis to perform crystal structure analysis of the compound to be analyzed. Structural analysis can use X-ray diffraction, neutron beam diffraction, etc. The molecular structure of the compound to be analyzed can be determined by performing crystal structure analysis using the sample for crystal structure analysis obtained by the method for preparing the sample for crystal structure analysis. According to the present disclosure, the sample for crystal structure analysis obtained by the method for preparing the sample for crystal structure analysis can be used to perform crystal structure analysis.

[0170] <<Example>>

[0171] Hereinafter, the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited to the following examples.

[0172] [Physical property evaluation]

[0173] (Solvent stability)

[0174] Add a drop of PCN-containing solvent to the glass bottle. Then, add about 2 cm 3 The solvent to be tested for stability was added, and the supernatant was immediately removed by decantation. This operation was repeated three times in total, and then the solvent was added and the mixture was allowed to stand at room temperature. After standing for several days, an optical microscope was used to confirm whether the crystalline shape of PCN changed.

[0175] (Single Crystal X-ray Structure Analysis)

[0176] The single crystal X-ray diffraction of the PCN after the guest inclusion was measured using Varimax Saturn manufactured by Rigaku Corporation, Synergy-R / DWTI APEX II manufactured by Rigaku Corporation, or synchrotron KEK-BL5A.

[0177] [Example 1]

[0178] 5 mg of terephthalic acid (H2BDC) (0.03 mmol), 6.4 mg of tetra-n-butylammonium 2,5,8-tri(4'-pyridyl)1,3,4,6,7,9-hexaazaphenanthrenyl (TBA + TPHAP- ) (0.01 mmol), 6.6 mg of cobalt bromide (0.03 mmol) were placed in a 2 cm 3 The reaction mixture was added to DMF and heated at 80°C in a vial for 24 hours to obtain square purple-red PCN single crystals (PCNI-1).

[0179] The purple-red single crystal PCNI-1 obtained was identified by X-ray structural analysis and confirmed to have (Co 2+ )4(TPHAP - )2(BDC 2- )3 represents the PCN of the unit structure.

[0180] The X-ray structural analysis results of PCNI-1 are shown in Table 1. Figure 1 and Figure 2 It should be noted that the values ​​in brackets in Table 1 represent statistical errors relative to the values ​​in the table (the same applies to subsequent tables). Figure 2 It is aimed at using Mercury (made by Cambridge Crystal Data Center) Schematic diagram of the size of the pores obtained by simulating the atomic coordinate information obtained by X-ray structural analysis by adding the probe radius of 100 to the van der Waals radius. The arrows in the figure represent the long diameter of the pore and the opening diameter orthogonal to the long diameter. In addition, the numerical values ​​in the figure represent the size of the long diameter and the opening diameter (unit: ). The same is true in the following figures.

[0181] [Table 1]

[0182] Table 1

[0183]

[0184] In PCNI-1, Figure 1 As shown in FIG. 1 , the PCN involved in Example 1 has the following structure: Figure 2 The maximum opening diameter of the pores shown is

[0185] [Example 2]

[0186] 5 mg of terephthalic acid (H2BDC) (0.03 mmol), 6.4 mg of tetra-n-butylammonium 2,5,8-tri(4'-pyridyl)1,3,4,6,7,9-hexaazaphenanthrenyl (TBA + TPHAP - ) (0.01 mmol), 6.6 mg of cobalt bromide (0.03 mmol) were placed in a 2 cm3 The resulting mixture was added to DMF and heated in an autoclave at 90°C for 24 hours to obtain hexagonal purple-red PCNI-2 single crystals.

[0187] When the purple-red single crystal PCNI-2 obtained was identified by X-ray structural analysis, it was confirmed that it had (Co 2+ )4(TPHAP - )2(BDC 2- )3 represents the PCN of the unit structure.

[0188] The X-ray structural analysis results of PCNI-2 are shown in Table 2. Figure 3 and Figure 4 shown.

[0189] [Table 2]

[0190] Table 2

[0191]

[0192] In PCNI-2, if Figure 3 As shown, the unit structure is formed based on a cobalt binuclear cluster composed of three TPHAP-derived pyridyl groups, three BDC-derived carboxyl groups and two solvents. The PCN involved in Example 2 has the following structure: Figure 4 shown of pore diameter.

[0193] [Example 3]

[0194] 65 mg of 2,6-naphthalene dicarboxylic acid (H2NDC) (0.3 mmol), 128 mg of tetra-n-butylammonium 2,5,8-tri(4'-pyridyl)1,3,4,6,7,9-hexaazaphenanthrenyl (TBA + TPHAP - ) (0.2 mmol), 87.5 mg of cobalt bromide (0.4 mmol) were placed at 30 cm 3 of dehydrated DMF and 15 cm 3 The mixture was heated in a pressure vessel at 100° C. for 72 hours in a mixed solvent of dehydrated acetonitrile and MeCN, thereby obtaining a purple-red single crystal of PCNI-3.

[0195] The purple-red single crystal PCNI-3 obtained was identified by X-ray structural analysis and confirmed to have (Co 2+ )4(TPHAP - )2(NDC 2- )3 represents the PCN of the structural unit.

[0196] The X-ray structural analysis results of PCNI-3 are shown in Table 3. Figure 5 and Figure 6 shown.

[0197] [Table 3]

[0198] Table 3

[0199]

[0200] In PCNI-3, if Figure 5 As shown in FIG, the structure is composed of three pyridyl groups derived from TPHAP, three carboxyl groups derived from NDC, and two DMF-coordinated cobalt binuclear clusters. Figure 6 As shown, PCNI-3 has of pores.

[0201] [Example 4]

[0202] 6.5 mg of 2,6-naphthalenedicarboxylic acid (H2NDC) (0.03 mmol), 6.4 mg of tetra-n-butylammonium 2,5,8-tri(4'-pyridyl)1,3,4,6,7,9-hexaazaphenanthrenyl (TBA + TPHAP - ) (0.01 mmol), 6.6 mg of cobalt bromide (0.03 mmol) were placed in a 2 cm 3 DMF and 0.1cm 3 The mixture was heated in a vial at 80° C. for 24 hours in a mixed solvent of methanol (MeOH), thereby obtaining a square orange PCN single crystal (PCNI-4).

[0203] The purple-red single crystal PCNI-4 obtained was identified by X-ray structural analysis and confirmed to have (Co 2+ )4(TPHAP - )2(NDC 2- )3 represents the PCN of the structural unit.

[0204] The X-ray structural analysis results of PCNI-4 are shown in Table 4. Figure 7 and Figure 8 shown.

[0205] [Table 4]

[0206] Table 4

[0207]

[0208] In PCNI-4, if Figure 7 As shown in FIG. 1 , it has a unit structure of three pyridyl groups derived from TPHAP and three carboxyl groups derived from NDC formed by a cobalt binuclear cluster. Figure 8 The maximum opening diameter of the pores shown is

[0209] [Example 5]

[0210] 4.3 mg of trans, trans-muconic acid (H2MA) (0.03 mmol), 6.4 mg of tetra-n-butylammonium 2,5,8-tri(4'-pyridyl)1,3,4,6,7,9-hexaazaphenanthrenyl (TBA + TPHAP - ) (0.01 mmol), 6.6 mg of cobalt bromide (0.03 mmol) were placed in a 2 cm 3 The reaction mixture was added to DMF and heated at 80° C. in a vial for 24 hours to obtain a tetrahedral orange PCN single crystal (PCNII-1).

[0211] The obtained orange single crystal PCNII-1 was identified by X-ray structural analysis and confirmed to have (Co 2+ ) 11 (TPHAP - )6(MA 2- )8 represents the PCN of the structural unit.

[0212] The X-ray structural analysis results of PCNII-1 are shown in Table 5. Fig. 9 and Fig.10 shown.

[0213] [Table 5]

[0214] Table 5

[0215]

[0216] In PCNII-1, Fig. 9 As shown, the PCN of Example 5 has a unit structure formed by a five-core cluster including 6 pyridyl groups derived from TPHAP, 8 carboxyl groups derived from MA, and 5 cobalt ions. Fig.10 The isolated pores shown have a maximum opening diameter of

[0217] [Example 6]

[0218] 7.3 mg of 4,4'-biphenyldicarboxylic acid (H2BPDC) (0.03 mmol), 6.4 mg of tetra-n-butylammonium 2,5,8-tri(4'-pyridyl)1,3,4,6,7,9-hexaazaphenanthrenyl (TBA + TPHAP - ) (0.01 mmol), 6.6 mg of cobalt bromide (0.03 mmol) were placed in a 2 cm 3 DMF and 0.1cm 3The mixture was heated in a vial at 80° C. for 24 hours in a mixed solvent of methanol (MeOH), thereby obtaining a square purple-red PCN single crystal (PCNIII-1).

[0219] The obtained orange single crystal PCNIII-1 was identified by X-ray structural analysis and was confirmed to have [(Co 2+ )5(TPHAP - )4(BPDC 2- )4]·(TBA + )2 represents the PCN of the unit structure.

[0220] The X-ray structural analysis results of PCNIII-1 are shown in Table 6. Fig.11 and Fig.12 It should be noted that the values ​​in brackets in Table 6 represent statistical errors relative to the values ​​in the table.

[0221] [Table 6]

[0222] Table 6

[0223]

[0224] like Fig.11 As shown in FIG. 1 , PCNIII-1 has a unit structure formed by a cobalt binuclear cluster and a cobalt mononuclear cluster. The cobalt binuclear cluster is composed of four TPHAP-derived pyridyl groups and four BPDC-derived carboxyl groups, and the cobalt mononuclear cluster is composed of two TPHAP-derived pyridyl groups, two DMFs, and two water groups. PCNIII-1 involved in Example 6 has the following structure: Fig.12 The maximum opening diameter of the pores shown is

[0225] [Example 7]

[0226] 5.9 mg of 2,5-dihydroxyterephthalic acid (H2DHC) (0.03 mmol), 6.4 mg of tetra-n-butylammonium 2,5,8-tri(4'-pyridyl)1,3,4,6,7,9-hexaazaphenanthrenyl (TBA + TPHAP - ) (0.01 mmol), 6.6 mg of cobalt bromide (0.03 mmol) were placed in a 2 cm 3 The reaction mixture was added to DMF and heated in a vial at 80° C. for 18 hours to obtain a square orange PCN single crystal (PCNIV-1).

[0227] The obtained orange single crystal PCNIV-1 was identified by X-ray structural analysis and confirmed to have [(Co 2+ )2(TPHAP - )1(DHC2- )2]·TBA + Represents the composition of the PCN.

[0228] The X-ray structural analysis results of PCNIV-1 are shown in Table 7. Fig.13 and Fig.14 shown.

[0229] [Table 7]

[0230] Table 7

[0231]

[0232] like Fig.13 As shown in FIG. 1 , PCNIV-1 is composed of two cobalt binuclear clusters, one of which is composed of four TPHAP-derived pyridyl groups and four DHC-derived carboxyl groups, and the other is composed of two TPHAP-derived pyridyl groups, two DMF groups, and four DHC-derived carboxyl groups. Fig.14 The maximum opening diameter of the pores shown is

[0233] [Example 8]

[0234] 71.8 mg of 5',5"-bis(4-carboxyphenyl)-2',2",4',4",6',6"-hexamethylene-[1,1':3',1":3",1"'-quadrphenyl]-4,4"'-dicarboxylic acid (H4TCBM) (0.1 mmol), 64 mg of tetra-n-butylammonium 2,5,8-tri(4'-pyridyl)1,3,4,6,7,9-hexaazaphenanthrenyl (TBA + TPHAP - ) (0.1 mmol), 43.7 mg of cobalt bromide (0.2 mmol) were placed at 20 cm 3 The mixture was heated in a pressure vessel at 100° C. for 72 hours in dehydrated DMF to obtain a purple-red single crystal of PCNV-1.

[0235] When the obtained PCNV-1 was identified by single crystal X-ray diffraction, it was confirmed that it had (Co 2+ )2(TPHAP - )(TCBM 3- ) represents the PCN of the unit structure.

[0236] The X-ray structural analysis results of PCNV-1 are shown in Table 8. Fig.15 and Fig.16 shown.

[0237] [Table 8]

[0238] Table 8

[0239]

[0240] In PCNV-1, as Fig.15 shown, a unit structure formed by a cobalt binuclear cluster was confirmed. The cobalt binuclear cluster consists of 4 TPHAP-derived pyridine sites, 4 TCBM-derived carboxyl groups, and 2 DMFs. The PCN involved in Example 8 has pores as Fig.16 shown, with a maximum opening diameter of

[0241] [Example 9]

[0242] 8.6 mg of [1,1'-biphenyl]-3,4',5-tricarboxylic acid (H3BTCA) (0.03 mmol), 6.6 mg of tetra-n-butylammonium 2,5,8-tris(4'-pyridyl)-1,3,4,6,7,9-hexaazaphenalenyl (TBA + TPHAP - )(0.03 mmol), and 8.6 mg of cobalt bromide (0.03 mmol) were placed in 2 cm 3 of dehydrated DMF and heated in a vial at 100 °C for 72 hours to obtain purple-red single crystals of PCNVI-1.

[0243] When the obtained PCNVI-1 was identified by single crystal X-ray diffraction, it was confirmed to be a PCN with a unit structure represented by [(Co 2+ )3(TPHAP - ) (4+2x) / 3 (BTCA 3- )2]·Y (4+2x) / 3 (where m is an arbitrary integer). Among them, 0 < x ≤ 1. As the unit structure, [(Co 2+ )3(TPHAP - )2(BTCA 3- )2]·TBA + 2 was confirmed.

[0244] The X-ray structural analysis results of PCNVI-1 are shown in Table 9, Fig.17 and Fig.18 shown.

[0245] [Table 9]

[0246] Table 9

[0247]

[0248] In PCNVI-1, as Fig.17As shown, the PCN involved in Example 9 has a unit structure formed by a cobalt binuclear cluster and a cobalt mononuclear cluster. The cobalt binuclear cluster is formed by 4 TPHAP-derived pyridine sites and 4 BTCA-derived carboxyl groups, and the cobalt mononuclear cluster is formed by 2 TPHAP-derived pyridine groups, 2 BTCA-derived carboxyl groups, and 1 molecule of water. Fig.18 The maximum opening diameter of the pores shown is

[0249] [Example 10]

[0250] 8.9 mg of 2,5,8-tris(4'-carboxybenzyl)-1,3,4,6,7,9-hexaazaphenanthrenyl (H4TCHAP) (16.7 mol), 4.3 mg of 2,5-thiophenedicarboxylic acid (H2TDC) (24.4 mol), 3.6 mg of 1H-1,2,3-triazole (HTAZ) (52.1 mol), and 26.6 mg of zinc (II) iodide (83.33 mol) were placed in a pressure vessel, and 2 cm 3 of dehydrated DMF and 0.030 cm 3 acetic acid and heated at 120°C for 40 hours to obtain colorless crystals of PCNVII-1.

[0251] When the obtained PCNVII-1 was identified by single crystal X-ray diffraction, it was confirmed that it had [(Zn 2+ )8(HTCHAP 3- )2(TDC 2- )3(TAZ - )6]·(Y + )2 represents a PCN unit structure. Immediately after synthesis, the cation Y + It is dimethylammonium ion (DMA) generated by the decomposition of N,N-dimethylformamide as a solvent. + ).

[0252] The X-ray structural analysis results of PCNVII-1 are shown in Table 10. Fig.19 and Fig. 20 shown.

[0253] [Table 10]

[0254] Table 10

[0255]

[0256] The PCN involved in Example 10 has the following Fig. 20 The maximum opening diameter of the pores shown is 0 Fig.19As shown, PCNVII-1 has the following structure: a metal cluster consisting of 8 zinc ions, 3 molecules of 2,5-thiophenedicarboxylic acid, and 6 molecules of 1,2,3-triazole is formed, and these metal clusters are cross-linked by TCHAP.

[0257] The PCN synthesized in Examples 1 to 10 is stable in DMF for more than one week. In addition, it is shown that it has special stability. When the solvent stability in PCNI-3 of Example 3 was evaluated, it was stable in acetonitrile, ethyl acetate, acetone, heptane, kerosene, octane, cyclooctane, cyclohexane, toluene, monochlorobenzene, mesitylene, 2,2,4-trimethylpentane, and tert-butyl methyl ether. Among these solvents, it is stable in ethyl acetate for about five days and in other organic solvents for more than one month. When the solvent stability in PCNV-1 of Example 8 was evaluated, PCNV-1 was stable in methanol, ethyl acetate, acetone, hexane, heptane, kerosene, and cyclohexane for at least five days. In particular, it was confirmed that a single crystal was maintained even after more than one month in solvents other than methanol. When the solvent stability in PCNVII-1 of Example 10 was evaluated, it was confirmed that it was stable in acetone and heptane, and the single crystallinity was maintained in these solvents for more than one week.

[0258] An example of guest inclusion structure analysis using the synthesized PCN is described below.

[0259] [Example 11]

[0260] Using the PCNI-3 obtained in Example 3, spironolactone (C 24 H 32 O4S, 416.57g / mol) crystal structure analysis. First, PCNI-3 was washed three times with ethyl acetate and solvent replacement was performed for one day. Then, just before the inclusion of spironolactone, the ethyl acetate solvent was replaced with heptane. 2 mg of spironolactone was dissolved in 1 cm 3 of heptane and 0.1cm 3 A plurality of PCNI-3 crystals were added to the mixed solution of acetone and spironolactone. After standing at 40°C for three days, the inclusion of spironolactone into PCNI-3 was performed and single crystal X-ray diffraction was measured. The measurement results are shown in Table 11 and Fig.21 shown.

[0261] [Table 11]

[0262] Table 11

[0263]

[0264] [Example 12]

[0265] Using the PCNI-3 obtained in Example 3, betamethasone (C 22 H 29 FO5, 392.46 g / mol). First, PCNI-3 was washed three times with ethyl acetate and solvent replacement was performed for one day. Then, just before inclusion of betamethasone, the ethyl acetate solvent was replaced with toluene. 2 mg of betamethasone was dissolved in 1 cm 3 A plurality of PCNI-3 crystals were added to the solution of toluene, and after standing at 40°C for three days, betamethasone was included in PCNI-3 and single crystal X-ray diffraction was measured. The measurement results are shown in Table 12 and Fig. 22 shown.

[0266] [Table 12]

[0267] Table 12

[0268]

[0269] [Example 13]

[0270] PCNV-1 obtained in Example 8 was used to perform griseofulvin (C 17 H 17 ClO6, 352.77g / mol) crystal structure analysis. First, PCNV-1 was washed with ethyl acetate three times and solvent replacement was performed for one day. Then, before inclusion of griseofulvin, the ethyl acetate solvent was replaced with hexane. 2 mg of griseofulvin was added to 1 cm 3 A plurality of PCNV-1 crystals were added to the solution of n-heptane and allowed to stand at 40°C for three days before inclusion of griseofulvin into PCNV-1 and single crystal X-ray diffraction was measured. The measurement results are shown in Table 13 and Fig.23 shown.

[0271] [Table 13]

[0272] Table 13

[0273]

[0274] [Example 14]

[0275] Using PCNVII-1 obtained in Example 10, betamethasone (C 22 H 29 First, PCNVII-1 was washed three times with DMF, and then the solvent was replaced with acetone and allowed to stand at room temperature for three days. 3Several PCNVII-1 crystals were added to a solution obtained by dissolving a saturated amount of betamethasone in heptane to carry out inclusion of betamethasone. After three days at 40°C, the structure was analyzed by single crystal X-ray structure analysis (KEK BL-5A). The measurement results are shown in Table 14 and Fig.24 shown.

[0276] [Table 14]

[0277] Table 14

[0278]

[0279] [Example 15]

[0280] Using PCNVII-1 obtained in Example 10, ivermectin (C 48 H 74 O 14 , 875.11 g / mol) of crystal structure analysis. First, PCNVII-1 was washed three times with DMF, and then the solvent was replaced with acetone and left at room temperature for three days. Then, the 0.1 cm 3 of acetone and 1cm 3 A saturated amount of ivermectin was dissolved in a mixed solution of heptane and several PCNVII-1 crystals were added to the solution to carry out ivermectin inclusion. After three days at room temperature, single crystal X-ray structure analysis was performed. The measurement results are shown in Table 15 and Fig.25 shown.

[0281] [Table 15]

[0282] Table 15

[0283]

[0284] like Figure 21 to Figure 25 et al., it was confirmed that the guest molecule as the analysis target compound was included in various PCNs, and its structure analysis could be performed.

[0285] [Example 16]

[0286] 5.2 mg of 2,5-thiophenedicarboxylic acid (H2TDCA) (0.03 mmol), 6.4 mg of 2,5,8-tris(4'-pyridyl)1,3,4,6,7,9-hexaazaphenanthrenyl (4TPHAP - ) (0.01 mmol), 6.6 mg of cobalt bromide (0.03 mmol) were placed in a mixed solution of 2 mL of DMF and 100 μL of acetic acid, and heated in a vial at 100°C for 72 hours to obtain square purple-red PCN single crystals (PCNI-5, TDCA-PCN).

[0287] The obtained purple-red PCN single crystal PCNI-5 was identified by X-ray structural analysis and confirmed to have (Co 2+ )4(TPHAP - )2(TDCA 2- )3 represents a unit structure PCN. The X-ray structural analysis results of PCNI-5 are shown in Table 16. Fig.26 and Fig. 27 shown.

[0288] [Table 16]

[0289] Table 16

[0290]

[0291] In PCNI-5, if Fig.26 As shown, the PCN involved in Example 16 has the following structure: Fig. 27 The maximum opening diameter of the pores shown is In addition, the porosity is 50.6%

[0292] [Example 17]

[0293] Using the PCNI-5 obtained in Example 16, the crystal structure of 5-methyl-2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile (ROY) as the guest molecule was analyzed. First, PCNI-5 was washed three times with ethyl acetate and the solvent was replaced for one day. Then, just before the inclusion of ROY, the ethyl acetate solvent was replaced with heptane. 1 mg of ROY was dissolved in 1 cm 3 A plurality of PCNI-5 was added to the solution of heptane, and after standing at 40°C for three days, ROY was included in the PCNI-5, and single crystal X-ray diffraction was measured. The measurement results are shown in Table 17. Fig.28 shown.

[0294] [Table 17]

[0295] Table 17

[0296]

[0297] [Example 18]

[0298] 4.7 mg of 2,5-furandicarboxylic acid (H2FDCA) (0.03 mmol), 6.4 mg of 2,5,8-tris(4'-pyridyl)1,3,4,6,7,9-hexaazaphenanthrenyl (4TPHAP -) (0.01 mmol), 6.6 mg of cobalt bromide (0.03 mmol) were placed in a mixed solution of 2 mL of DMF and 100 μL of acetic acid, and heated in a vial at 100°C for 72 hours to obtain square purple-red PCN single crystals (PCNVIII-1, FDCA-PCN).

[0299] The purple-red PCN single crystal PCNVIII-1 obtained was identified by X-ray structural analysis and confirmed to have (Co 2+ )5(Co 3+ )1(TPHAP - )3(FDCA 2- )5 represents the PCN of the unit structure.

[0300] The X-ray structural analysis results of PCN-18 are shown in Table 18. Fig.29 and Fig.30 shown.

[0301] [Table 18]

[0302] Table 18

[0303]

[0304] PCNVIII-1 involved in Example 18 has the following Fig.30 The maximum opening diameter of the pores shown is

[0305] In addition, the porosity is 49.7%

[0306] [Example 19]

[0307] Using the PCNV-1 obtained in Example 8, monensin sodium (C 36 H 61 NaO 11 , 682.86 g / mol) of crystal structure analysis. First, PCNV-1 was washed with ethyl acetate three times and solvent replacement was performed for one day. Then, before inclusion of monensin sodium, the ethyl acetate solvent was replaced with heptane. 1 mg of monensin sodium was added to 1 cm 3 A plurality of PCNV-1s were added to the solution of 1% heptane and the solution was left to stand at 40°C for three days. Then, sodium monensin was included in PCNV-1 and single crystal X-ray diffraction was measured.

[0308] The measurement results are shown in Table 19 and Fig.31 shown.

[0309] [Table 19]

[0310] Table 19

[0311]

[0312] Industrial Applicability

[0313] The PCN can be used as a crystal for crystal structure analysis of high molecular weight guest molecules such as pharmaceuticals or peptides. In particular, it can be expected to easily perform structural analysis of middle molecules that have been difficult to analyze. In addition, it can be used for purification of substances or as a reaction field in a closed space, adsorption material, chemical sensor material, etc.

[0314] This application claims the priority based on Japanese patent application No. 2022-140327 for which it applied on September 2, 2022, and all the contents disclosed therein are incorporated into the present disclosure by reference.

Claims

1. A porous coordination network, wherein: The porous coordination network has a three-dimensional network structure, forming pores capable of enclosing guest molecules. The porous coordination network has a crystal structure, and the crystal structure has a unit structure of any one of the following formulas (I) to (VIII): (M 2+ )4(L1a – )2(L2a 2- )3 Formula (I) (M 2+ ) 11 (L1a - )6(L2a 2- )8 Formula (II) [(M 2+ )5(L1a - )4(L2a 2- )4]·Y 2p Formula (III) [(M 2+ )2(L1a - )1(L2a 2- )2]·Y p Formula (IV) (M 2+ )2(L1a - )1(L2b 3- )1 formula (V) [(M 2+ )3(L1a - )2(L2b 3- )2]·And 2p (VI) [(M 2+ )8(L1b 3- )2(L2a 2- )3(L3 - )6]·Y 2p Formula (VII) (M 2+ )5(M 3+ )1(L1a - )3(L2a 2- )5 Formula (VII) Among them, in formula (I) to formula (VIII), M 2+ is a divalent metal ion, M 3+ It is a trivalent metal ion. L1a and L1b are tridentate ligands with a hexaazaphenanthrenyl group. L1a - is a first ligand ion of the following formula (1), or a first ligand ion in which 1 to 12 hydrogen atoms of the aromatic ring of formula (1) are independently replaced by a group selected from an alkyl group having 1 to 4 carbon atoms, a halogen group, a hydroxyl group and an amino group, [Chemical formula 1] L1b 3- is a first ligand ion of the following formula (2), or a first ligand ion in which 1 to 12 hydrogen atoms of the aromatic ring of formula (2) are independently replaced by a group selected from an alkyl group having 1 to 4 carbon atoms, a halogen group, a hydroxyl group and an amino group, [Chemical formula 2] L2a is a bidentate ligand containing more than two carboxyl groups. L2a 2- The two carboxyl groups serve as a second ligand ion coordinated with the metal ion by a carboxylate anion, L2b is a tridentate ligand containing more than three carboxyl groups. L2b 3- The three carboxyl groups serve as a second ligand ion coordinated with the metal ion by a carboxylate anion, L3 - is a third ligand ion which is an anion of triazole or a triazole derivative, Y is a cation, p is 1 / (charge of Y), A solvent may be further coordinated to the unit structures of formula (I) to (VII).

2. The porous coordination network according to claim 1, wherein: The metal is at least one selected from Mg, Ca, Mn, Fe, Co, Ni, Cu, Zn, Rh, Ag, Cd, Ir, Pt, and Au.

3. The porous coordination network according to claim 1, wherein: The molecular weight of L2a and L2b is 90 to 1000, and they are at least one selected from the following formula (3), [Chemical formula 3] R 1 -(COOH) n (3) Wherein, for said L2a, n is an integer greater than 2, and for said L2b, n is an integer greater than 3, R 1 Having: may have an unsaturated bond, may have a bond containing a heteroatom, may have a substituent, A straight-chain or branched aliphatic group having 2 to 20 carbon atoms; An aromatic group having 6 to 72 carbon atoms; and At least one structure of a heterocyclic ring having 2 to 60 carbon atoms.

4. The porous coordination network according to claim 1, wherein: The porous coordination network is used for guest molecule analysis.

5. The porous coordination network according to claim 1, wherein: The guest molecule is a medium molecule with a molecular weight of 50 to 7000.

6. A method for preparing a sample for crystal structure analysis, wherein: Prepare a sample by dissolving the target compound in a solvent. The porous coordination network according to any one of claims 1 to 5 is dispersed in the sample, The analyte compound is incorporated into the pores of the porous coordination network.

7. A method for determining the molecular structure of an analytical target compound, characterized in that: Using the sample for crystal structure analysis obtained by the method for preparing a sample for crystal structure analysis according to claim 6, crystal structure analysis is performed.

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