POROUS COORDINATION NETWORK, METHOD FOR PREPARING SAMPLE FOR CRYSTAL STRUCTURE ANALYSIS, AND METHOD FOR DETERMINING MOLECULAR STRUCTURE
20260079149 ยท 2026-03-19
Assignee
Inventors
- Masaki Kawano (Tokyo, JP)
- Yuki WADA (Tokyo, JP)
- Pavel USOV (Tokyo, JP)
- Yu TAGAMI (Tokyo, JP)
- Yiying ZHU (Tokyo, JP)
Cpc classification
International classification
Abstract
A porous coordination network is represented by the following formulas (I) to (VIII), in which M.sup.2+ is a divalent metal ion, M.sup.3+ is a trivalent metal ion, L1a and L1b are tridentate ligands having hexaazaphenalenyl, L2a and L2b are bidentate or tridentate ligands containing a carboxy group, L3.sup. is a tertiary ligand ion that is an anion of triazole or a triazole derivative, and Y is a cation.
##STR00001##
Claims
1. A porous coordination network which has a three-dimensional network structure and in which pores capable of encapsulating guest molecules are formed, the porous coordination network comprising a crystal structure having a unit structure represented by any one of following formulas (I) to (VIII): ##STR00016## where M.sup.2+ represents a divalent metal ion, M.sup.3+ represents a trivalent metal ion, L1a and L1b represent tridentate ligands having hexaazaphenalenyl, L1a.sup. represents a first ligand ion of a following formula (1), or a first ligand ion in which 1 to 12 hydrogen atoms of an aromatic ring of the formula (1) are each independently replaced by a group selected from an alkyl group having 1 to 4 carbon atoms, a halogen, a hydroxyl group, and an amino group, ##STR00017## L1b.sup.3 represents a first ligand ion represented by a following formula (2), or a first ligand ion in which 1 to 12 hydrogen atoms of an aromatic ring of the formula (2) are each independently replaced by a group selected from an alkyl group having 1 to 4 carbon atoms, a halogen, a hydroxyl group, and an amino group, ##STR00018## L2a represents a bidentate ligand containing two or more carboxy groups, L2a.sup.2 represents a second ligand ion in which two of the carboxy groups are coordinated to the metal ion as carboxylate anions, L2b represents a tridentate ligand containing three or more carboxy groups, L2b.sup.3 represents a second ligand ion in which three of the carboxy groups are coordinated to the metal ion as carboxylate anions, L3.sup. represents a third ligand ion that is an anion of triazole or a triazole derivative, Y represents a cation, p represents 1/(charge of Y), and a solvent is optionally further coordinated to the unit structures of formulas (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 L2a and the L2b each have a molecular weight of 90 to 1000 and are at least one selected from a following formula (3): ##STR00019## where n represents an integer of 2 or more for the L2a, and represents an integer of 3 or more for the L2b, and R.sup.1 has at least any one of structures of a linear or branched aliphatic group having 2 to 20 carbon atoms, an aromatic group having 6 to 72 carbon atoms, and a heterocycle having 2 to 60 carbon atoms, optionally having an unsaturated bond, optionally having a bond including a heteroatom, and optionally having a substituent.
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-sized molecule having a molecular weight of 50 to 7000.
6. A method for preparing a sample for crystal structure analysis, comprising: providing a sample in which a compound to be analyzed is dissolved in a solvent; dispersing the porous coordination network according to claim 1 in the sample; and incorporating the compound to be analyzed into pores of the porous coordination network.
7. A method for determining a molecular structure of a compound to be analyzed, comprising performing crystal structure analysis using a sample for crystal structure analysis obtained by the method for preparing a sample for crystal structure analysis according to claim 6.
Description
BRIEF DESCRIPTION OF DRAWINGS
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DESCRIPTION OF EMBODIMENTS
[0067] An example of an embodiment to which the present disclosure is applied is described below. Other embodiments are also included within the scope of the present disclosure as long as they conform to the spirit of the present disclosure. In addition, the size and ratios of each portion in the following figures are for the convenience of explanation and are not intended to be limiting.
[0068] The porous coordination network (hereinafter also referred to as the present PCN) according to the present disclosure has a three-dimensional network structure. This three-dimensional network structure is formed by coordinating ligands, which will be described later, to a metal. In the present PCN, pores capable of encapsulating guest molecules are formed.
[0069] The present PCN is represented by any of the following formulas (I) to (VIII). Ligands and metals are combined via coordinate bonds to form a regular structure.
[0070] The present PCN has a crystal structure having a unit structure represented by any one of the following formulas (I) to (VIII):
##STR00006##
[0071] In the formulas (I) to (VIII), M.sup.2+ is a divalent metal ion, M.sup.3+ is a trivalent metal ion, and L1a and L1b are tridentate ligands having hexaazaphenalenyl. L1a.sup. is a first ligand ion represented by the following formula (1), or a first ligand ion in which 1 to 12 hydrogen atoms in the aromatic ring of formula (1) are each independently replaced by a group selected from an alkyl group having 1 to 4 carbon atoms, a halogen, a hydroxyl group, and an amino group.
##STR00007##
L1b.sup.3 is a first ligand ion represented by the following formula (2), or a first ligand ion in which 1 to 12 hydrogen atoms of the aromatic ring of formula (2) are each independently replaced by a group selected from an alkyl group having 1 to 4 carbon atoms, a halogen, a hydroxyl group, and an amino group.
##STR00008##
[0072] L2a is a bidentate ligand containing two or more carboxy groups. The upper limit of the number of carboxy groups is not particularly limited, but is, for example, 4, with a preferred upper limit of 3 and particularly preferably 2. L2a.sup.2 is a second ligand ion in which two of the carboxy groups are coordinated to the metal ion as carboxylate anions.
[0073] L2b is a bidentate ligand containing three or more carboxy groups. The upper limit of the number of carboxy groups is not particularly limited, but is, for example, 6, with a preferred upper limit of 4 and particularly preferably 3. L2b.sup.3 is a second ligand ion in which three of the carboxy groups are coordinated to the metal ion as carboxylate anions.
[0074] L3.sup. is a third ligand ion, which is an anion of triazole or a triazole derivative. The triazole may be either 1,2,3-triazole or 1,2,4-triazole. The triazole derivative refers to a compound having a triazole. For example, the triazole derivative refers to benzotriazole or a compound in which one or more hydrogen atoms of benzotriazole are substituted with, for example, an amino group, a hydroxy group, a methyl group, a nitro group, a halogen group, or a carboxy group. Examples thereof include 4-carboxybenzotriazole, 7-carboxybenzotriazole, benzotriazole butyl ester, 1-hydroxymethylbenzotriazole, and 1-hydroxybenzotriazole.
[0075] The present disclosure can provide a PCN with a novel structure by a PCN that combines the specific metal described above with a first ligand and a second ligand, or by a PCN that combines the specific metal described above with a first ligand, a second ligand, and a third ligand. Using a highly symmetric first ligand ion of formula (1) or a first ligand ion of formula (2) can increase the periodicity of the structure and improve the crystallinity. As a result, crystals suitable for structural analysis can be provided.
[0076] In addition, using a highly symmetrical first ligand ion of formula (1) and a second ligand ion having two or three carboxylate anions (carboxylate groups); or using a highly symmetrical first ligand ion of formula (2), a second ligand ion having two carboxylate anions (carboxylate groups), and a third ligand ion, forms a metal complex cluster with a divalent metal ion, thereby providing the excellent effect of easily obtaining a porous coordination network having a large pore size and high solvent stability. Further, the PCN is used to form a metal complex cluster with divalent metal ions, thereby allowing the physical and chemical stability of the structure to be increased. That is, due to the physical stability, it is possible to obtain robustness that allows the structure to be maintained if there are large pores. In addition, because of the excellent chemical stability, it is expected to have the effect of increasing solvent stability. The present PCN can be suitably used for guest molecule analysis.
[0077] In formulas (I) to (VIII), M.sup.2+ is a divalent metal ion, and M.sup.3+ is a trivalent metal ion, and the type is not particularly limited. Preferred examples of metals include at least one selected from Mg, Ca, Mn, Fe, Co, Ni, Cu, Zn, Rh, Ag, Cd, Ir, Pt, and Au. It is possible to use multiple types of metals, but it is preferable to use a single metal from the viewpoint of ease of structural analysis.
[0078] The structures of L2a and L2b are not particularly limited as long as they satisfy the above-described conditions. From the viewpoint of easily forming PCN, the molecular weight is preferably 90 to 1000, more preferably 100 to 900, still more preferably 110 to 850, and particularly preferably 116 to 801.
[0079] Preferred examples of L2a and L2b include at least one having a molecular weight of 90 to 1000 and selected from the following formula (3).
##STR00009##
n is an integer of 2 or more for the L2a, the upper limit of which is preferably 4, and more preferably 3. n is an integer of 3 or more for L2b, the upper limit of which is preferably 6, and more preferably 4. R.sup.1 has at least any one of (i) a linear or branched aliphatic group having 2 to 20 carbon atoms, optionally having an unsaturated bond, optionally having a bond including a heteroatom, and optionally having a substituent; (ii) an aromatic group having 6 to 72 carbon atoms, optionally having an unsaturated bond, optionally having a bond including a heteroatom, and optionally having a substituent; and (iii) a heterocycle having 2 to 60 carbon atoms, optionally having an unsaturated bond, optionally having a bond including a heteroatom, and optionally having a substituent. From the viewpoint of the robustness of the PCN structure, it is preferable that the PCN has an aromatic ring, an unsaturated bond, and the like. The more preferred range for the number of carbon atoms in (i) is 2 to 16, and particularly preferred is 2 to 10. The more preferred range for the number of carbon atoms in (ii) is 6 to 60, and particularly preferred is 6 to 55. The more preferred range for the number of carbon atoms in (iii) is 6 to 60, and particularly preferred is 6 to 55. The aliphatic group may be linear or alicyclic.
[0080] In addition, preferred examples of the L2a and L2b include compounds having the structure of the following general formula (4). The preferred range of the molecular weight is 90 to 1000, and the more preferred range is as described above.
##STR00010##
In formula (4), Ar represents a divalent or trivalent aromatic group optionally having a substituent. Ha represents a bond including a heteroatom. Sa represents an atom that forms four bonds in the directions of vertices of a tetrahedron, such as carbon or silicon, or an ion that forms four bonds in the direction of vertices of a tetrahedron, such as ammonium or phosphonium ion. Z is a carbonyl group, a sulfonyl group, an aliphatic group having 1 to 10 carbon atoms optionally having a substituent, or a single bond directly linking Ar to another Ar. X.sup.1 to X.sup.4 each independently represent a divalent organic group, or a single bond directly linking any of Ar, Ha, or Sa to a carboxy group. Y.sup.1 to Y.sup.4 each independently represent a monovalent organic group having one or more carboxy groups as a coordinating site or a carboxylic acid. Preferred examples of X.sup.1 to X.sup.4 include a single bond, a linear or branched aliphatic group having 2 to 10 carbon atoms, an alicyclic aliphatic group having 5 to 15 carbon atoms, an aromatic group having 6 to 24 carbon atoms, and a group having a heterocycle having 2 to 20 carbon atoms, these groups of which optionally have a substituent. More preferred examples of X.sup.1 to X.sup.4 include a single bond, a linear or branched aliphatic group having 2 to 8 carbon atoms, an alicyclic aliphatic group having 5 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms, and a group having a heterocycle having 2 to 15 carbon atoms, these groups of which optionally have a substituent.
[0081] Specific examples of L2a include the following compound.
##STR00011## ##STR00012## ##STR00013##
[0082] Specific examples of L2b include the following compound.
##STR00014## ##STR00015##
[0083] The shape and size of the pores in PCN can be adjusted by changing the ligands. In addition, when the same ligand is used, the shape and size of the pores can be changed by changing the synthesis method.
[0084] The pore size of PCN can be understood as the body diagonal distance when the pores not being filled with spheres of the van der Waals radius of the atoms to form the network structure are considered to be cubes. The maximum size of the pores of PCN, which is defined as the short-axis distance when a cut is made at the opening of the pore and the cut is considered to be a rectangle, is not limited, but from the viewpoint of use as a sample for crystal structure analysis, the maximum size is preferably 0.8 nm or more. The maximum size is more preferably 1 nm or more, and even more preferably 1 to 5.0 nm. The opening diameter of the pores is determined primarily by the type of first ligand. Making the opening size of the pores 1.5 nm or more allows the compounds with molecular weights of, for example, about 100 to 3,000 to be selectively incorporated into the hollow space, and allows a variety of applications including crystal structure analysis.
[0085] Y is not particularly limited, but from the viewpoint of being present in the PCN pores, the molecular weight is preferably 1 to 600, and more preferably 6 to 500. In addition, from the viewpoint of the interaction between Y and the inclusion guest, it is preferable to have an alkali metal, an alkaline earth metal, or an organic cation.
[0086] Specific examples of Y include inorganic cations such as Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+, Cs.sup.+, Be.sup.2+, Mg.sup.2+, Ca.sup.2+, Sr.sup.2+, and Ba.sup.2+, and cationic components of organic salts, such as 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.
[0087] A solvent may be coordinated to the PCN. There are no limitations on the type of solvent that may be coordinated to the PCN, but polar solvents are preferable from the viewpoint of forming hydrogen bond sites. Suitable examples of the polar solvent include: alcohols such as water, methanol, ethanol, and isopropanol; glycols such as ethylene glycol and polyethylene glycol; ester-based solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ketone-based solvents such as acetone, ethyl methyl ketone, and cyclohexanone; ether-based 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 may be used singly or in combination of two or more.
[0088] The axis of the 4-carboxybenzyl group used as L1b in formula (VII) rotates freely relative to the hexaazaphenalenyl, providing excellent symmetry. In the PCN in which the oxygen of the carboxylate of this 4-carboxybenzyl group is coordinated with a metal, the free rotation of the axis of the 4-carboxybenzyl group is not hindered. The 4-pyridinyl group used as L1a.sup. in formulas (I) to (VI) also rotates freely relative to the hexaazaphenalenyl, providing excellent symmetry.
[0089] The PCN represented by formula (I) has a crystal structure having a unit structure of four metals, two first ligand ions, and three second ligand ions. A solvent may further be coordinated to the PCN. Suitable examples of the structural unit of formula (I) include (Mn.sup.2+).sub.4(TPHAP.sup.).sub.2(BDC.sup.2).sub.3, (Mn.sup.2+).sub.4(TPHAP.sup.).sub.2(NDC.sup.2).sub.3, (Mn.sup.2+).sub.4(TPHAP.sup.).sub.2(BPDC.sup.2).sub.3, (Fe.sup.2+).sub.4(TPHAP.sup.).sub.2(BDC.sup.2).sub.3, (Fe.sup.2+).sub.4(TPHAP.sup.).sub.2(NDC.sup.2).sub.3, (Fe.sup.2+).sub.4(TPHAP.sup.).sub.2(BPDC.sup.2).sub.3, (Co.sup.2+).sub.4(TPHAP.sup.).sub.2(BDC.sup.2).sub.3, (Co.sup.2+).sub.4(TPHAP.sup.).sub.2(NDC.sup.2).sub.3, (Co.sup.2+).sub.4(TPHAP.sup.).sub.2(BPDC.sup.2).sub.3, (Ni.sup.2+).sub.4(TPHAP.sup.).sub.2(BDC.sup.2).sub.3, (Ni.sup.2+).sub.4(TPHAP.sup.).sub.2(NDC.sup.2).sub.3, (Ni.sup.2+).sub.4(TPHAP.sup.).sub.2(BPDC.sup.2).sub.3, (Cu.sup.2+).sub.4(TPHAP.sup.).sub.2(BDC.sup.2).sub.3, (Cu.sup.2+).sub.4(TPHAP.sup.).sub.2(NDC.sup.2).sub.3, (Cu.sup.2+).sub.4(TPHAP.sup.).sub.2(BPDC.sup.2).sub.3, (Zn.sup.2+).sub.4(TPHAP.sup.).sub.2(BDC.sup.2).sub.3, (Zn.sup.2+).sub.4(TPHAP.sup.).sub.2(NDC.sup.2).sub.3, (Zn.sup.2+).sub.4(TPHAP).sub.2(BPDC.sup.2).sub.3, (Cd.sup.2+).sub.4(TPHAP.sup.).sub.2(BDC.sup.2).sub.3, (Cd.sup.2+).sub.4(TPHAP.sup.).sub.2(NDC.sup.2).sub.3, and (Cd.sup.2+).sub.4(TPHAP.sup.).sub.2(BPDC.sup.2).sub.3. BDC.sup.2 is the anion of terephthalic acid, NDC.sup.2 is the anion of 2,6-naphthalenedicarboxylic acid, and BPDC.sup.2 is the anion of biphenyl-4,4-dicarboxylic acid. TPHAP.sup. is the first ligand ion of the above formula (1).
[0090] 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. A solvent may further be coordinated. Suitable examples of the unit structure of formula (II) include (Mn.sup.2+).sub.11(TPHAP.sup.).sub.8(MA.sup.2).sub.8, (Fe.sup.2+).sub.11(TPHAP.sup.).sub.6(MA.sup.2).sub.8, (Co.sup.2+).sub.11(TPHAP.sup.).sub.6(MA.sup.2), (Ni.sup.2+).sub.11(TPHAP.sup.).sub.6(MA.sup.2).sub.8, (Cu.sup.2+).sub.11(TPHAP.sup.).sub.6(MA.sup.2).sub.8, (Zn.sup.2+).sub.11(TPHAP.sup.).sub.6(MA.sup.2).sub.8, and (Cd.sup.2+).sub.11(TPHAP.sup.).sub.6(MA.sup.2).sub.8. MA.sup.2 represents the anion of trans,trans-muconic acid.
[0091] The PCN represented by formula (III) has a crystal structure having a unit structure of five metals, four first ligand ions, and four second ligand ions. Y is a counter ion. Further, a solvent may be coordinated. Suitable examples of the unit structure include (Mn.sup.2+).sub.5(TPHAP.sup.).sub.4(BPDC.sup.2).sub.4.Math.Y.sub.2p, (Fe.sup.2+).sub.5(TPHAP.sup.).sub.4(BPDC.sup.2).sub.4.Math.Y.sub.2, (Co.sup.2+).sub.5(TPHAP.sup.).sub.4(BPDC.sup.2).sub.4.Math.Y.sub.2, (Ni.sup.2+).sub.5(TPHAP.sup.).sub.4(BPDC.sup.2).sub.4.Math.Y.sub.2p, (Cu.sup.2+).sub.5(TPHAP.sup.).sub.4(BPDC.sup.2).sub.4.Math.Y.sub.2p, (Zn.sup.2+).sub.5(TPHAP.sup.).sub.4(BPDC.sup.2).sub.4.Math.Y.sub.2p, and (Cd.sup.2+).sub.5(TPHAP.sup.).sub.4(BPDC.sup.2).sub.4.Math.Y.sub.2p. Y is a cation present as a counter ion. Specific examples of cations include Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+, Mg.sup.2+, Ca.sup.2+, Sr.sup.2+, tetra-n-butylammonium (TBA.sup.+), and dimethylammonium (DMA+). The same applies to suitable Y in (IV), (VI), and (VII) described below.
[0092] 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. Further, a solvent may be coordinated. Preferred examples of the unit structure include (Mn.sup.2+).sub.2(TPHAP.sup.).sub.1(DHC.sup.2).sub.2.Math.Y.sub.p, (Fe.sup.2+).sub.2(TPHAP.sup.).sub.1(DHC.sup.2).sub.2.Math.Y.sub.p, (Co.sup.2+).sub.2(TPHAP.sup.).sub.1(DHC.sup.2).sub.2.Math.Y.sub.p, (Ni.sup.2+).sub.2(TPHAP.sup.).sub.1(DHC.sup.2).sub.2.Math.Y.sub.p, (Cu.sup.2+).sub.2(TPHAP.sup.).sub.1(DHC.sup.2).sub.2.Math.Y.sub.p, (Zn.sup.2+).sub.2(TPHAP.sup.).sub.1(DHC.sup.2).sub.2.Math.Y.sub.p, and (Cd.sup.2+).sub.2(TPHAP.sup.).sub.1(DHC.sup.2).sub.2.Math.Y.sub.p. DHC.sup.2 represents the anion of 2,5-dihydroxyterephthalic acid. In addition, Y is a cation that exists as a counter ion.
[0093] 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. Further, a solvent may be coordinated. Preferred examples of the unit structure include (Mn.sup.2+).sub.2(TPHAP.sup.)(TCBM.sup.3), (Fe.sup.2+).sub.2(TPHAP.sup.)(TCBM.sup.3), (Co.sup.2+).sub.2(TPHAP.sup.)(TCBM.sup.3), (Ni.sup.2+).sub.2(TPHAP.sup.)(TCBM.sup.3), (Cu.sup.2+).sub.2(TPHAP.sup.)(TCBM.sup.3), (Zn.sup.2+).sub.2(TPHAP.sup.)(TCBM.sup.3), and (Cd.sup.2+).sub.2(TPHAP.sup.)(TCBM.sup.3). TCBM.sup.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.
[0094] The PCN represented by formula (VI) has a crystal structure having a unit structure of three metals, two first ligand ions, and one second ligand. Further, Y is a counter ion. However, the charge of the metal and the second ligand is balanced in formula (VI), which thus may also include compounds that do not include a first ligand. From a macroscopic viewpoint, it is known that the composition taking into account defects is [(M.sup.2+).sub.3(L1a.sup.).sub.(4+2x)/3(L2b.sup.3).sub.2].Math.Y.sub.(4+2x)/3 (0<x<1). Further, a solvent may be coordinated. Suitable examples of the unit structure include [(Mn.sup.2+).sub.3(TPHAP.sup.).sub.2(BTCA.sup.3).sub.2]Y.sub.2p, [(Mn.sup.2+).sub.3(TPHAP.sup.).sub.2(BTCA.sup.3).sub.2].Math.Y.sub.2p, [(Fe.sup.2+).sub.3(TPHAP.sup.).sub.2(BTCA.sup.3).sub.2].Math.Y.sub.2p, [(Co.sup.2+).sub.3(TPHAP.sup.).sub.2(BTCA.sup.3).sub.2].Math.Y.sub.2p, (Ni.sup.2+).sub.3(TPHAP.sup.).sub.2(BTCA.sup.3).sub.2].Math.Y.sub.2p, [(Cu.sup.2+).sub.3(TPHAP.sup.).sub.2(BTCA.sup.3).sub.2].Math.Y.sub.2p, [(Zn.sup.2+).sub.3(TPHAP.sup.).sub.2(BTCA.sup.3).sub.2].Math.Y.sub.2p, and [(Cd.sup.2+).sub.3(TPHAP.sup.).sub.2(BTCA.sup.3).sub.2].Math.Y.sub.2p. BTCA.sup.3 is the anion of [1,1-biphenyl]-3,4,5-tricarboxylic acid.
[0095] The PCN represented by formula (VII) has a crystal structure having a unit structure of two metals, two first ligand ions, three second ligand ions, and six tertiary ligand ions. Y is a counter ion. In addition, a solvent may be coordinated. Suitable examples of the unit structure include (Mn.sup.2+).sub.8(HTCHAP.sup.3).sub.2(TDC.sup.2).sub.3(TAZ.sup.).sub.6.Math.Y.sub.2p, (Fe.sup.2+).sub.8(HTCHAP.sup.3).sub.2(TDC.sup.2).sub.3(TAZ.sup.).sub.6.Math.Y.sub.2p, (Ni.sup.2+).sub.8(HTCHAP.sup.3).sub.2(TDC.sup.2).sub.3(TAZ.sup.).sub.6.Math.Y.sub.2p, (Co.sup.2+).sub.8(HTCHAP.sup.3).sub.2(TDC.sup.2).sub.3(TAZ.sup.).sup.6.Math.Y.sub.2p, (Zn.sup.2+).sub.8(HTCHAP.sup.3).sub.2(TDC.sup.2).sub.3(TAZ.sup.).sub.6.Math.Y.sub.2p, and (Cd.sup.2+).sub.8(HTCHAP.sup.3).sub.2(TDC.sup.2).sub.3(TAZ.sup.).sub.6.Math.Y.sub.2p. TDB.sup.2 is the anion of 2,5-(thiophenediyl)dibenzoic acid, and TDC.sup.2 is the anion of 2,5-thiophenedicarboxylic acid, and TAZ.sup. is the anion of 1,2,3-triazole. In addition, HTCHAP.sup.3 is the first ligand ion of the above formula (2).
[0096] The PCN represented by formula (VIII) has a crystal structure having a unit structure of six metals (including five divalent metal ions and one trivalent metal ion), three first ligand ions, and five second ligand ions. In addition, a solvent may be coordinated. Suitable examples of the unit structure include (Co.sup.2+).sub.5(Co.sup.3+).sub.1(TPHAP.sup.).sub.3(FDCA.sup.2).sub.5, (Mn.sup.2+).sub.5(Mn.sup.3+).sub.1(TPHAP.sup.).sub.3(FDCA.sup.2).sub.5, and (Fe.sup.2+).sub.5(Fe.sup.3+).sub.1(TPHAP.sup.).sub.3(FDCA.sup.2).sub.5. FDCA.sup.2 is the anion of 2,5-furandicarboxylic acid.
[0097] The shape of the pores in PCN varies depending on the raw material molecules used. The size of the pore opening can be easily adjusted depending on the type of ligand and metal. For the analysis of medium-sized molecules, a PCN with as large an opening size as possible is preferable.
[0098] Solvent molecules such as DMF may be coordinated to the metal. The bond between the solvent molecules incorporated into the unit crystal and the metal is preferably weaker than the coordinate bond between the metal and the first ligand, and between the metal and the second ligand, or between the second ligand and the third ligand. Incorporating solvent molecules into the crystal structure units of the PCN is expected to exhibit the effect of reducing structural fluctuations when analyzing guest molecules to improve the accuracy of the analysis. In addition, it is possible to replace the solvent depending on the guest molecules being incorporated, and it is expected to increase the number of subjects to be analyzed. Further, these solvent molecules inside the pores can be confirmed through analysis.
[0099] The present PCN is suitable as a crystal for analyzing the crystal structure of high molecular weight guest molecules, such as pharmaceuticals and peptides. In addition, forming the crystal having an organic solvent as a ligand allows the position of the guest molecule relative to the solvent molecule to be analyzed. Further, making the bond between this organic solvent and the metal weaker than the coordinate bonds between the first ligand and the metal, and the coordinate bonds between the second ligand, or the second ligand and the third ligand, and the metal, thereby allowing the freedom of replacement with other solvent molecules to be increased. Therefore, it is possible to adjust the environmental field of the pores of the PCN depending on the guest molecule. These effects are expected to improve the accuracy of crystal structure analysis.
[0100] Further, the present PCN can provide various PCNs with new structures 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 below, it is possible to change the structure of the PCN obtained by the synthetic method in the same combination. For this reason, for example, multiple test tubes including different types of PCN and a solvent are provided, a guest molecule is added thereto, and a PCN that is compatible with the guest molecule can be easily screened. As a result, it is expected to easily analyze the structures of medium-sized molecules, which have been particularly difficult to analyze until now.
[0101] The examples of use for analysis are described above, but it is also suitable for applications in substance purification processes and as a reaction field in closed spaces. In addition, the surface area is significantly larger than that of zeolites, and thus the application to an adsorbent or purification purposes is expected. Further, the application to sensing organic substances, i.e. a chemical sensor material is possible. In addition, the application to drug delivery systems that release adsorbed guest molecules in response to external stimuli such as UV light is expected.
(Production Method)
[0102] Then, an example of a method for producing the PCN will be described. However, the method for producing the PCN according to the present disclosure is not limited to the following method.
[0103] First, a metal or metal compound, ligands (first ligand/second ligand, or first ligand/second ligand/tertiary ligand), and a solvent are placed in a container and heated, and synthesis can be performed using the solvothermal method. This allows the PCN having pores to be produced through a self-organizing one-step reaction. After synthesis of the PCN, crystals can be obtained by thorough washing. Instead of the solvothermal method, the PCN may be synthesized by the solution diffusion method, electrochemical synthesis method, microwave irradiation method, mechanochemical synthesis method, or ultrasonic synthesis method. Various PCNs can be synthesized by changing the solvent and the concentration thereof, the molar ratio between metal and ligand, temperature, and metal ion.
[0104] The molar ratio between the first ligand and the metal used is 1:1 to 1:10, preferably 1:1 to 1:5, and more preferably 1:1 to 1:3. The molar ratio between the second ligand (the second and third ligands, if the third ligand is used) and the metal is 1:1 to 1:7, preferably 1:1 to 1:5, and more preferably 1:1 to 1:3.
[0105] The organic solvent to be used is not particularly limited as long as it 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 isopropyl alcohol; and ketones such as acetone and methyl ethyl ketone. The solvent may be used singly or in combination of two or more.
[0106] Among these, amide-based reaction solvents are preferred as the reaction solvent, because of allowing the porous coordination network of the present disclosure to be synthesized in higher yield, and DMF, DMA, NMP, and the like are particularly suitable.
[0107] The precipitated PCN can be collected by filtration. The structure of the PCN can be confirmed by elemental analysis, IR, UV absorption spectroscopy, visible light absorption spectroscopy, single crystal X-ray structure analysis, and the like.
(Method of Preparing Sample for Crystal Structure Analysis)
[0108] Then, a method for preparing a sample for crystal structure analysis according to the present embodiment will be described. The preparation of the sample for crystal structure analysis involves incorporating a compound to be analyzed (guest molecule) into the pores of the PCN to provide a sample for structural analysis of the compound.
[0109] First, a sample in which the compound to be analyzed is dissolved in a solvent is provided, and the PCN is dispersed in the sample. The sample is prepared by, for example, a step of incorporating the compound to be analyzed into the pores of the PCN and removing the solvent.
[0110] A method for bringing a mixture including a compound to be analyzed into contact with the PCN and incorporating molecules of the compound to be analyzed into the pores of the PCN can be performed by a known method.
[0111] The compound to be analyzed is not particularly limited, as long as it is of a size that can enter the pores of the PCN. The application is possible to a wide variety of compounds, including low molecular weight compounds, medium-sized molecule compounds such as pharmaceuticals, and chiral compounds. For example, molecules having a molecular weight of about 50 to 7000 can be analyzed. Suitable is a compound having a molecular weight of preferably 5000 or less, more preferably 480 to 4000, and particularly preferably 500 to 3000.
[0112] The method for contacting the PCN with the compound to be analyzed is not particularly limited. For example, for a method for preparing a solution of the compound to be analyzed and bringing the PCN to be brought into contact with this solution, or in a case where the compound to be analyzed is a liquid or gas, the molecules of the compound to be analyzed can be incorporated in the pores of the PCN by directly contacting the PCN with the compound to be analyzed. Among these, the method of preparing a solution of the compound to be analyzed and contacting the PCN with this solution is preferable because it is easier to obtain a better quality sample for crystal structure analysis.
[0113] In addition, when using a solution including the compound to be analyzed or when the compound to be analyzed is liquid, the contact operation can be performed by a method for immersing the single crystal in a solution including the compound to be analyzed, by a method for packing the single crystal into a capillary and then passing a solution including the compound to be analyzed through the capillary, or the like.
[0114] The solvent of the solution including the compound to be analyzed may be any solvent that does not dissolve the single crystal used and 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 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. The solvent can be used singly or in combination of two or more.
[0115] The contact time between the compound to be analyzed and the PCN is not particularly limited, but is typically from a few minutes to a few months. Depending on the compound, the contact time can be shortened or lengthened as appropriate. The contact temperature is not particularly limited, and can be in the range of, for example, 30 to 200 C. It is preferable to perform the contact at a temperature at which the compound to be analyzed can be easily handled.
[0116] A sample for crystal structure analysis has molecules of the compound to be analyzed incorporated into the pores of the PCN. Due to the size of the pore opening, the compound to be analyzed is regularly disposed within the pores. Being regularly disposed in this case means that the molecules of the compound to be analyzed are incorporated into the pores to an extent that the structure thereof can be determined by crystal structure analysis.
[0117] The sample for crystal structure analysis may be only capable of determining the molecular structure of the compound to be analyzed, and it is not necessary for the molecules of the compound to be analyzed to be incorporated into all of the pores of the PCN. The molecular structure of the compound to be analyzed is determined by performing crystal structure analysis of the compound to be analyzed using the sample for crystal structure analysis. Structural analysis can utilize X-ray diffraction, neutron diffraction, and the like. Performing crystal structure analysis using a sample for crystal structure analysis obtained by the method for preparing a sample for crystal structure analysis can determine the molecular structure of the compound to be analyzed. The present disclosure allows crystal structure analysis by using a sample for crystal structure analysis obtained by the above-described method for preparing a sample for crystal structure analysis.
EXAMPLES
[0118] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to the following examples.
[Physical Property Evaluation]
(Solvent Stability)
[0119] A drop of a solvent including a PCN was placed into a glass vial. Subsequently, approximately 2 cm.sup.3 of the solvent to be tested for stability was added, and the supernatant was then immediately removed by decantation. This operation was performed a total of three times, after which the solvent was added and the mixture was allowed to stand at room temperature. After leaving the mixture to stand for several days, an optical microscope was used to check whether the crystalline shape of the PCN had changed.
(Single Crystal X-Ray Structure Analysis)
[0120] The PCN that underwent guest inclusion was subjected to single crystal X-ray diffraction measurement using Varimax Saturn, manufactured by Rigaku Corporation, or Synergy-R/DWTI APEX II, manufactured by Rigaku Corporation, or a synchrotron KEK-BL5A.
Example 1
[0121] 5 mg (0.03 mmol) of terephthalic acid (H.sub.2BDC), 6.4 mg (0.01 mmol) of tetra-n-butylammonium 2,5,8-tri(4-pyridyl)1,3,4,6,7,9-hexaazaphenalenyl (TBA.sup.+TPHAP.sup.), and 6.6 mg (0.03 mmol) of cobalt bromide were heated with 2 cm.sup.3 of DMF in a vial at 80 C. for 24 hours to provide a square reddish purple PCN single crystal (PCNI-1).
[0122] The resulting reddish purple single crystal PCNI-1 was identified by X-ray structural analysis, and was confirmed to be a PCN having a unit structure represented by (Co.sup.2+).sub.4(TPHAP.sup.).sub.2(BDC.sup.2).sub.3.
[0123] The results of X-ray structural analysis of PCNI-1 are shown in Table 1,
TABLE-US-00001 TABLE 1 Name PCNI-1 Temperature/K 173.15 Crystal system Monoclinic Space group P2.sub.1/c a/ 14.0080 (7) b/ 17.6494 (7) c/ 28.6715 (11) / 90 / 103.259 (4) / 90 Volume/.sup.3 6899.6 (5) Z 4 Crystal size/mm.sup.3 0.115 0.043 0.025 Radiation Mo K ( = 0.71073) Independent reflections 15916 [R.sub.int = 0.3285, R.sub.sigma = 0.3239] Goodness-of-fit on F.sup.2 1.199
[0124] PCNI-1 is formed based on a cobalt dinuclear cluster including three TPHAP-derived pyridinyl groups, three BDC-derived carboxylic acids, and two DMFs, as shown in
Example 2
[0125] 5 mg (0.03 mmol) of terephthalic acid (H.sub.2BDC), 6.4 mg (0.01 mmol) of tetra-n-butylammonium 2,5,8-tri(4-pyridyl)1,3,4,6,7,9-hexaazaphenalenyl (TBA.sup.+TPHAP.sup.), and 6.6 mg (0.03 mmol) of cobalt bromide were heated with 2 cm.sup.3 of DMF at 90 C. in an autoclave for 24 hours to provide hexagonal reddish purple PCNI-2 single crystals.
[0126] The resulting reddish purple single crystal PCNI-2 was identified by X-ray structural analysis and confirmed to be a PCN having a unit structure represented by (Co.sup.2+).sub.4(TPHAP.sup.).sub.2(BDC.sup.2).sub.3.
[0127] The results of X-ray structural analysis of PCNI-2 are shown in Table 2,
TABLE-US-00002 TABLE 2 Name PCNI-2 Temperature/K 173.15 Crystal system monoclinic Space group P2/c a/ 30.7062 (10) b/ 20.5493 (5) c/ 22.6908 (9) / 90 / 93.221 (3) / 90 Volume/.sup.3 14295.1 (8) Z 4 Crystal size/mm.sup.3 0.223 0.135 0.094 Radiation Mo K ( = 0.71073) Independent reflections 33005 [R.sub.int = 0.2634, R.sub.sigma = 0.2216] Goodness-of-fit on F.sup.2 1.601 Final R indexes R.sub.1 = 0.2612, wR.sub.2 = 0.5676 [I >= 2 (I)]
[0128] In PCNI-2, a unit structure is formed based on a cobalt dinuclear cluster formed by the coordination of three TPHAP-derived pyridinyl groups, three BDC-derived carboxyl groups, and two solvents, as shown in
Example 3
[0129] 65 mg (0.3 mmol) of 2,6-naphthalenedicarboxylic acid (H.sub.2NDC), 128 mg (0.2 mmol) of tetra-n-butylammonium 2,5,8-tri(4-pyridyl)1,3,4,6,7,9-hexaazaphenalenyl (TBA.sup.+TPHAP.sup.), and 87.5 mg (0.4 mmol) of cobalt bromide were heated in a mixed solvent of 30 cm.sup.3 of dehydrated DMF and 15 cm.sup.3 of dehydrated acetonitrile (MeCN) at 100 C. in a pressure vessel for 72 hours to provide reddish purple single crystals of PCNI-3.
[0130] The resulting reddish purple single crystal PCNI-3 was identified by X-ray structural analysis and confirmed to be a PCN having a structural unit represented by (Co.sup.2+).sub.4(TPHAP.sup.).sub.2(NDC.sup.2).sub.3.
[0131] The results of X-ray structural analysis of PCNI-3 are shown in Table 3,
TABLE-US-00003 TABLE 3 Name PCNI-3 Temperature/K 95 Crystal system Orthorhombic Space group Pbca a/ 29.216 (6) b/ 20.741 (8) c/ 36.290 (5) / 90 / 90 / 90 Volume/.sup.3 21991 (10) Z 8 Crystal size/mm.sup.3 0.259 0.241 0.143 Radiation 0.75 (KEK BL-5A) Independent reflections 41733 [R.sub.int = 0.0465, R.sub.sigma = 0.0219] Goodness-of-fit on F.sup.2 1.395 Final R indexes R.sub.1 = 0.1091, wR.sub.2 = 0.3335 [I >= 2 (I)]
[0132] PCNI-3 has a structure including a cobalt dinuclear cluster obtained by the coordination of three TPHAP-derived pyridinyl groups, three NDC-derived carboxyl groups, and two DMFs, as shown in
Example 4
[0133] 6.5 mg (0.03 mmol) of 2,6-naphthalenedicarboxylic acid (H.sub.2NDC), 6.4 mg (0.01 mmol) of tetra-n-butylammonium 2,5,8-tri(4-pyridyl)1,3,4,6,7,9-hexaazaphenalenyl (TBA.sup.+TPHAP.sup.), and 6.6 mg (0.03 mmol) of cobalt bromide were heated with a mixed solvent of 2 cm.sup.3 of DMF and 0.1 cm.sup.3 of methanol (MeOH) in a vial at 80 C. for 24 hours to provide square orange PCN single crystals (PCNI-4).
[0134] The resulting reddish purple single crystal PCNI-4 was identified by X-ray structural analysis and confirmed to be a PCN having a structural unit represented by (Co.sup.2+).sub.4(TPHAP.sup.).sub.2(NDC.sup.2).sub.3.
[0135] The results of X-ray structural analysis of PCNI-4 are shown in Table 4,
TABLE-US-00004 TABLE 4 Name PCNI-4 Temperature/K 173.15 Crystal system Monoclinic Space group P2.sub.1/n a/ 16.6632 (11) b/ 19.1759 (10) c/ 33.2438 (9) / 90 / 88.187 (4) / 90 Volume/.sup.3 10617.1 (9) Z 4 Crystal size/mm.sup.3 0.126 0.079 0.036 Radiation Mo K ( = 0.71073) Independent reflections 24460 [R.sub.int = 0.1908, R.sub.sigma = 0.1798] Goodness-of-fit on F.sup.2 1.483 Final R indexes R.sub.1 = 0.1895, wR.sub.2 = 0.4687 [I >= 2 (I)]
[0136] PCNI-4 has a unit structure in which three TPHAP-derived pyridyl groups and three NDC-derived carboxyl groups are formed from a cobalt dinuclear cluster, as shown in
Example 5
[0137] 4.3 mg (0.03 mmol) of trans,trans-muconic acid (H.sub.2MA), 6.4 mg (0.01 mmol) of tetra-n-butylammonium 2,5,8-tri(4-pyridyl)1,3,4,6,7,9-hexaazaphenalenyl (TBA.sup.+TPHAP.sup.), and 6.6 mg (0.03 mmol) of cobalt bromide were heated with 2 cm.sup.3 of DMF in a vial at 80 C. for 24 hours to provide tetrahedral orange PCN single crystals (PCNII-1).
[0138] The resulting orange single crystal PCNII-1 was identified by X-ray structural analysis and confirmed to be a PCN having a structural unit represented by (Co.sup.2+).sub.11(TPHAP.sup.).sub.6(MA.sup.2).sub.8.
[0139] The results of the X-ray structural analysis of PCNII-1 are shown in Table 5,
TABLE-US-00005 TABLE 5 Name PCNII-1 Temperature/K 95.15 Crystal system Triclinic Space group P-1 a/ 19.5272(6) b/ 19.8546(6) c/ 19.9971(5) / 109.146(3) / 104.885(3) / 108.800(3) Volume/.sup.3 6338.0(4) Z 2 Crystal size/mm.sup.3 0.035 0.052 0.127 Radiation CuK ( = 1.54184) Independent reflections 26117 [R.sub.int = 0.1666, R.sub.sigma = 0.0978] Goodness-of-fit on F.sup.2 1.077 Final R indexes R.sub.1 = 0.1130, wR.sub.2 = 0.3013 [I >= 2 (I)]
[0140] As shown in
Example 6
[0141] 7.3 mg (0.03 mmol) of 4,4-biphenyldicarboxylic acid (H.sub.2BPDC), 6.4 mg (0.01 mmol) of tetra-n-butylammonium 2,5,8-tri(4-pyridyl)1,3,4,6,7,9-hexaazaphenalenyl (TBA.sup.+TPHAP.sup.), and 6.6 mg (0.03 mmol) of cobalt bromide were heated with a mixed solvent of 2 cm.sup.3 of DMF and 0.1 cm.sup.3 of methanol (MeOH) in a vial at 80 C. for 24 hours to provide square reddish purple PCN single crystals (PCNIII-1).
[0142] The resulting orange single crystal PCNIII-1 was identified by X-ray structural analysis and confirmed to be a PCN having a unit structure represented by [(Co.sup.2+).sub.5(TPHAP.sup.).sub.4(BPDC.sup.2).sub.4](TBA.sup.+).sub.2.
[0143] The results of X-ray structural analysis of PCNIII-1 are shown in Table 6,
TABLE-US-00006 TABLE 6 Name PCNIII-1 Temperature/K 173.15 Crystal system Monoclinic Space group P2.sub.1/n a/ 19.9901(12) b/ 31.4742(16) c/ 26.6899(18) / 90 / 108.513(7) / 90 Volume/.sup.3 15923.6(18) Z 4 Crystal size/mm.sup.3 0.024 0.051 0.168 Radiation Mo K ( = 0.71073) Independent reflections 36746 [R.sub.int = 0.4673, R.sub.sigma = 0.4628] Goodness-of-fit on F.sup.2 1.139 Final R indexes R.sub.1 = 0.1973, wR.sub.2 = 0.4539 [I >= 2 (I)]
[0144] As shown in
Example 7
[0145] 5.9 mg (0.03 mmol) of 2,5-dihydroxyterephthalic acid (H.sub.2DHC), 6.4 mg (0.01 mmol) of tetra-n-butylammonium 2,5,8-tri(4-pyridyl)1,3,4,6,7,9-hexaazaphenalenyl (TBA.sup.+TPHAP.sup.), and 6.6 mg (0.03 mmol) of cobalt bromide were heated with 2 cm.sup.3 of DMF in a vial at 80 C. for 18 hours to provide square orange PCN single crystals (PCNIV-1).
[0146] The resulting orange single crystal PCNIV-1 was identified by X-ray structural analysis and confirmed to be a PCN having a composition represented by [(Co.sup.2+).sub.2(TPHAP.sup.).sub.1(DHC.sup.2).sub.2].Math.TBA.sup.+.
[0147] The results of the X-ray structural analysis of PCNIV-1 are shown in Table 7,
TABLE-US-00007 TABLE 7 Name PCNIV-1 Temperature/K 173.15 Crystal system monoclinic Space group P2.sub.1/m a/ 14.7620(14) b/ 30.938(2) c/ 18.7627(16) / 90 / 92.924(9) / 90 Volume/.sup.3 8558.0(13) Z 4 Crystal size/mm.sup.3 0.260 0.251 0.037 Radiation Mo K ( = 0.71073) Independent reflections 20131 [R.sub.int = 0.2971, R.sub.sigma = 0.2442] Goodness-of-fit on F.sup.2 1.773 Final R indexes R.sub.1 = 0.3044, wR.sub.2 = 0.6383 [I >= 2 (I)]
[0148] PCNIV-1 includes two types of cobalt dinuclear clusters as shown in
Example 8
[0149] 71.8 mg (0.1 mmol) of 5,5-bis(4-carboxyphenyl)-2,2,4,4,6,6-hexamethylene-[1,1: 3,1:3,1quaterphenyl]-4,4-dicarboxylic acid (H.sub.4TCBM), 64 mg (0.1 mmol) of tetra-n-butylammonium 2,5,8-tri(4-pyridyl)1,3,4,6,7,9-hex aazaphenalenyl (TBA.sup.+TPHAP.sup.), and 43.7 mg (0.2 mmol) of cobalt bromide were heated with 20 cm.sup.3 of dehydrated DMF at 100 C. in a pressure vessel for 72 hours to provide reddish purple single crystals of PCNV-1.
[0150] The resulting PCNV-1 was identified by single crystal X-ray diffraction and confirmed to be a PCN having a unit structure represented by (Co.sup.2+).sub.2(TPHAP.sup.)(TCBM.sup.3).
[0151] The results of X-ray structural analysis of PCNV-1 are shown in Table 8,
TABLE-US-00008 TABLE 8 Name PCNV-1 Temperature/K 95 Crystal system Monoclinic Space group P2.sub.1/n a/ 18.203(4) b/ 32.801(6) c/ 23.671(2) / 90 / 93.188(9) / 90 Volume/.sup.3 14112(4) Z 4 Crystal size/mm.sup.3 0.477 0.181 0.027 Radiation 0.75 (KEK BL-5A) Independent reflections 48027 [R.sub.int = 0.0353, R.sub.sigma = 0.0224] Goodness-of-fit on F.sup.2 1.925 Final R indexes R.sub.1 = 0.1552, wR.sub.2 = 0.4646 [I >= 2 (I)]
[0152] It was confirmed that PCNV-1 has a unit structure formed from a cobalt dinuclear cluster including four TPHAP-derived pyridine sites, four TCBM-derived carboxyl groups, and two DMFs, as shown in
Example 9
[0153] 8.6 mg (0.03 mmol) of [1,1-biphenyl]-3,4,5-tricarboxylic acid (H.sub.3BTCA), 6.6 mg (0.03 mmol) of tetra-n-butylammonium 2,5,8-tri(4-pyridyl)1,3,4,6,7,9-hexaazaphenalenyl (TBA.sup.+TPHAP.sup.), and 8.6 mg (0.03 mmol) of cobalt bromide were heated with 2 cm.sup.3 of dehydrated DMF in a vial at 100 C. for 72 hours to provide reddish purple single crystals of PCNVI-1.
[0154] The resulting PCNVI-1 was identified by single crystal X-ray diffraction and confirmed to be a PCN having a unit structure represented by [(Co.sup.2+).sub.3(TPHAP.sup.).sub.(4+2x)/3(BTCA.sup.3).sub.2].Math.Y.sub.(4+2x)/3 (where m is any integer). However, 0<x1. It was confirmed that the unit structure is [(Co.sup.2+).sub.3(TPHAP.sup.).sub.2(BTCA.sup.3).sub.2].Math.TBA.sup.+.sub.2.
[0155] The results of the X-ray structural analysis of PCNVI-1 are shown in Table 9,
TABLE-US-00009 TABLE 9 NAME PCNVI-1 Temperature/K 123.15 Crystal system Trigonal Space group R-3c a/ 31.1843(6) b/ 31.1843(6) c/ 62.2037(18) / 90 / 90 / 120 Volume/3 52386(3) Z 36 Radiation MoK.sub. ( = 0.71073) Independent reflections 16048 [R.sub.int = 0.0579, R.sub.sigma = 0.0482] Goodness-of-fit on F2 1.569 Final R indexes R1 = 0.1652, wR2 = 0.4540 [I >= 2 (I)]
[0156] PCNVI-1 has a unit structure, the structure formed by a cobalt dinuclear cluster formed from four TPHAP-derived pyridine sites and four BTCA-derived carboxy groups, as well as a cobalt mononuclear cluster formed from two TPHAP-derived pyridyl groups, two BTCA-derived carboxy groups, and one molecule of water, as shown in
Example 10
[0157] 8.9 mg (16.7 mol) of 2,5,8-tri(4-carboxybenzyl)-1,3,4,6,7,9-hexaazaphenalene (H.sub.4TCHAP), 4.3 mg (24.4 mol) of 2,5-thiophenedicarboxylic acid (H.sub.2TDC), 3.6 mg (52.1 mol) of 1H-1,2,3-triazole (HTAZ), and 26.6 mg (83.33 mol) of zinc iodide (II) were placed in a pressure vessel, 2 cm.sup.3 of dehydrated DMF and 0.030 cm.sup.3 of acetic acid were added thereto, and the mixture was heated at 120 C. for 40 hours to provide colorless crystals of PCNVII-1.
[0158] The resulting PCNVII-1 was identified by single crystal X-ray diffraction and confirmed to be a PCN with a unit structure represented by [(Zn.sup.2+).sub.8(HTCHAP.sup.3).sub.2(TDC.sup.2).sub.3(TAZ.sup.).sub.6].Math.(Y.sup.+).sub.2. Immediately after synthesis, the cation Y.sup.+ is a dimethylammonium ion (DMA.sup.+) generated by decomposition of the solvent N,N-dimethylformamide.
[0159] The results of the X-ray structural analysis of PCNVII-1 are shown in Table 10,
TABLE-US-00010 TABLE 10 Empirical formula PCNVII-1 Temperature/K 123.15 Crystal system monoclinic Space group C2/m a/ 47.9530(4) b/ 30.0035(6) c/ 24.7272(2) / 90 / 120.5970(10) / 90 Volume/.sup.3 30623.1(8) Z 8 Crystal size/mm.sup.3 0.131 0.131 0.02 Radiation CuK ( = 1.54178) Independent reflections 32034 [R.sub.int = 0.0548, R.sub.sigma = 0.0395] Goodness-of-fit on F.sup.2 1.315 Final R indexes R.sub.1 = 0.1060, wR.sub.2 = 0.3266 [I >= 2 (I)]
[0160] The PCN of Example 10 had pores as shown in
[0161] The PCNs synthesized in Examples 1 to 10 were stable in DMF for more than one week. Others that showed notable stability are shown below. When the solvent stability of PCNI-3 in Example 3 was evaluated, it was found to be 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 was stable for about five days in ethyl acetate, and for more than one month in other organic solvents. When the solvent stability of PCNV-1 in Example 8 was evaluated, PCNV-1 was stable in methanol, ethyl acetate, acetone, hexane, heptane, kerosene, and cyclohexane for at least 5 days or more. In particular, it was confirmed that single crystals remained in solvents other than methanol after one month or more. When the solvent stability of PCNVII-1 in Example 10 was evaluated, it was confirmed that PCNVII-1 was stable in acetone and heptane and maintained single crystallinity in these solvents for one week or more.
[0162] An example of guest inclusion structure analysis using the synthesized PCN is described below.
Example 11
[0163] The PCNI-3 obtained in Example 3 was used to analyze the crystal structure of the guest molecule spironolactone (C.sub.24H.sub.32O.sub.4S, 416.57 g/mol). First, PCNI-3 was washed with ethyl acetate three times and solvent-exchanged for one day. Then, immediately before the inclusion of spironolactone, ethyl acetate was replaced with heptane as the solvent. 2 mg of spironolactone was dissolved in a mixed solvent of 1 cm.sup.3 of heptane and 0.1 cm.sup.3 of acetone, several PCNI-3 crystals were added to this mixed solvent, the mixture was left at 40 C. for 3 days and then spironolactone was included in PCNI-3, and single crystal X-ray diffraction was measured. The measurement results are shown in Table 11 and
TABLE-US-00011 TABLE 11 Name inclusion of Spironolactone PCNI-3 Temperature/K 95 Crystal system monoclinic Space group P2.sub.1 a/ 32.060(4) b/ 19.739(4) c/ 35.105(5) / 90 / 96.336(2) / 90 Volume/.sup.3 22080(6) Z 2 Crystal size/mm.sup.3 0.146 0.139 0.021 Radiation 0.75 (KEK BL-5A) Independent reflections 163418 [R.sub.int = 0.0772, R.sub.sigma = 0.0862] Data/restraints/parameters 163418/3/2765 Goodness-of-fit on F.sup.2 1.532 Final R indexes R.sub.1 = 0.1680, wR.sub.2 = 0.4379 [I >= 2 (I)] Flack parameter 0.107(4)
Example 12
[0164] The PCNI-3 obtained in Example 3 was used to analyze the crystal structure of the guest molecule betamethasone (C.sub.22H.sub.29FO.sub.5, 392.46 g/mol). First, PCNI-3 was washed three times with ethyl acetate and solvent-exchanged for one day. Then, immediately before the inclusion of betamethasone, ethyl acetate was exchanged for toluene as the solvent. 2 mg of betamethasone was dissolved in 1 cm.sup.3 of toluene, several PCNI-3 crystals were added to this solution, the mixture was left to stand at 40 C. for three days and then betamethasone was included in PCNI-3, and single crystal X-ray diffraction was measured. The measurement results are shown in Table 12 and
TABLE-US-00012 TABLE 12 Name inclusion of betamethasone PCNI-3 Temperature/K 95 Crystal system orthorhombic Space group P2.sub.12.sub.12.sub.1 a/ 16.361(4) b/ 34.981(10) c/ 38.823(15) / 90 / 90 / 90 Volume/.sup.3 22219(12) Z 4 Crystal size/mm.sup.3 0.098 0.186 0.031 Radiation 0.75 (KEK BL-5A) 2 range for data 1.654 to 71.382 collection/ Index ranges 25 h 25, 52 k 52, 59 l 60 Reflections collected 489415 Independent reflections 84720 [R.sub.int = 0.0960, R.sub.sigma = 0.0677] Data/restraints/parameters 84720/877/2035 Goodness-of-fit on F.sup.2 1.052 Final R indexes R.sub.1 = 0.1232, wR.sub.2 = 0.3128 [I >= 2 (I)] Final R indexes [all data] R.sub.1 = 0.2304, wR.sub.2 = 0.3868 Largest diff. peak/hole/e .sup.3 1.34/0.98 Flack parameter 0.023(5)
Example 13
[0165] The PCNV-1 obtained in Example 8 was used to analyze the crystal structure of the guest molecule griseofulvin (C.sub.17H.sub.17ClO.sub.6, 352.77 g/mol). First, PCNV-1 was washed three times with ethyl acetate and solvent-exchanged for one day. Then, immediately before the inclusion of griseofulvin, ethyl acetate was replaced with hexane as the solvent. 2 mg of griseofulvin was added to 1 cm.sup.3 of n-heptane, several PCNV-1 crystals were added to this solution, the mixture was allowed to stand at 40 C. for three days and then griseofulvin was included in PCNV-1, and single crystal X-ray diffraction was measured. The measurement results are shown in Table 13 and
TABLE-US-00013 TABLE 13 Empirical formula inclusion of griseofulvin PCNV-1 Temperature/K 95 Crystal system monoclinic Space group P2.sub.1 a/ 18.298(2) b/ 34.540(10) c/ 24.327(5) / 90 / 95.913(6) / 90 Volume/.sup.3 15293(5) Z 2 Crystal size/mm.sup.3 0.267 0.271 0.053 Radiation 0.75 (KEK BL-5A) Independent reflections 104174 [R.sub.int = 0.0332, R.sub.sigma = 0.0341] Goodness-of-fit on F.sup.2 1.569 Final R indexes R.sub.1 = 0.1424, wR.sub.2 = 0.4122 [I >= 2 (I)] Flack parameter 0.320(4)
Example 14
[0166] The PCNVII-1 obtained in Example 10 was used to analyze the crystal structure of the guest molecule betamethasone (C.sub.22H.sub.29FO.sub.5, 392.46 g/mol). First, PCNVII-1 was washed three times with DMF, then the solvent was replaced with acetone and left at room temperature for three days. Then, several PCNVII-1 crystals were added to a solution in which betamethasone was dissolved to saturation amount in 1 cm.sup.3 of heptane, and betamethasone was included. After three days at 40 C., structure analysis was performed by single crystal X-ray structure analysis (KEK BL-5A). The measurement results are shown in Table 14 and
TABLE-US-00014 TABLE 14 Name inclusion of betamethasone PCNVII-1 Temperature/K 95 Crystal system Monoclinic Space group C2 a/ 46.524(11) b/ 31.572(5) c/ 24.832(7) / 90 / 119.635(14) / 90 Volume/.sup.3 31703(14) Z 4 Radiation 0.75 (KEK BL-5A) Independent reflections 103642 [R.sub.int = 0.0840, R.sub.sigma = 0.0776] Goodness-of-fit on F.sup.2 0.945 Final R indexes R.sub.1 = 0.1174, wR.sub.2 = 0.2977 [I >= 2 (I)] Flack parameter 0.204(8)
Example 15
[0167] The PCNVII-1 obtained in Example 10 was used to analyze the crystal structure of the guest molecule ivermectin (C.sub.48H.sub.74O.sub.14, 875.11 g/mol). First, PCNVII-1 was washed three times with DMF, then the solvent was replaced with acetone and left at room temperature for three days. Then, several PCNVII-1 crystals were added to a solution in which ivermectin had been dissolved to a saturation amount in a mixture of 0.1 cm.sup.3 of acetone and 1 cm.sup.3 of heptane, and ivermectin was included. After three days at room temperature, single crystal X-ray structure analysis was performed. The measurement results are shown in Table 15 and
TABLE-US-00015 TABLE 15 Name inclusion of ivermectin PCNVII-1 Temperature/K 95 Crystal system Monoclinic Space group C2 a/ 47.340(9) b/ 30.700(3) c/ 24.975(4) / 90 / 121.568(4) / 90 Volume/.sup.3 30926(8) Z 4 Crystal size/mm.sup.3 0.18 0.08 0.02 Radiation 0.75 (KEK BL-5A) Independent reflections 102425 [R.sub.int = 0.0630, R.sub.sigma = 0.0573] Goodness-of-fit on F.sup.2 1.107 Final R indexes R.sub.1 = 0.1207, wR.sub.2 = 0.3281 [I >= 2 (I)] Flack parameter 0.096(5)
[0168] As shown in
Example 16
[0169] 5.2 mg (0.03 mmol) of 2,5-thiophenedicarboxylic acid (H.sub.2TDCA), 6.4 mg (0.01 mmol) of 2,5,8-tri(4-pyridyl)1,3,4,6,7,9-hexaazaphenalenyl (4TPHAP.sup.), and 6.6 mg (0.03 mmol) of cobalt bromide were heated in a mixed solution of 2 mL of DMF and 100 L of acetic acid at 100 C. in a vial for 72 hours to provide square reddish purple PCN single crystals (PCNI-5, TDCA-PCN).
[0170] The resulting reddish purple PCN single crystal, PCNI-5, was identified by X-ray structure analysis and confirmed to be a PCN having a unit structure represented by (Co.sup.2+).sub.4(TPHAP.sup.).sub.2(TDCA.sup.2).sub.3. The results of the X-ray structure analysis of PCNI-5 are shown in Table 16,
TABLE-US-00016 TABLE 16 Name PCNI-5 Temperature/K 173.15 Crystal system Monoclinic Space group P2.sub.1/n a/ 9.6843(3) b/ 41.3785(12) c/ 18.0270(5) / 90 / 104.853(3) / 90 Volume/.sup.3 6982.4(4) Z 1 Crystal size/mm.sup.3 0.075 0.045 0.0225 Radiation Mo K ( = 0.71073) Independent reflections 14138 [Rint = 0.0815, Rsigma = 0.0608] Goodness-of-fit on F.sup.2 1.295 Final R indexes R1 = 0.1270, wR2 = 0.3409 [I >= 2 (I)]
[0171] PCNI-5 is formed based on a cobalt dinuclear cluster including three TPHAP-derived pyridyl groups, three BDC-derived carboxylic acids, and two DMFs, as shown in
Example 17
[0172] The PCNI-5 obtained in Example 16 was used to analyze the crystal structure of the guest molecule 5-methyl-2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile (ROY). First, PCNI-5 was washed three times with ethyl acetate and solvent-exchanged for one day. Then, immediately before the inclusion of ROY, ethyl acetate was replaced with heptane as the solvent. 1 mg of ROY was dissolved in 1 cm.sup.3 of heptane, several particles of PCNI-5 were added to this solution, the mixture was allowed to stand at 40 C. for three days and then ROY was included in PCNI-5, and single crystal X-ray diffraction was measured. The measurement results are shown in Table 17 and
TABLE-US-00017 TABLE 17 Name inclusion of ROY PCNI-5 Temperature/K 95 Crystal system Monoclinic Space group P2.sub.1/n a/ 19.113(4) b/ 41.470(3) c/ 19.362(3) / 90 / 111.355(10) / 90 Volume/.sup.3 14293(4) Z 1 Crystal size/mm.sup.3 0.075 0.045 0.0225 Radiation 0.75 (KEK BL-5A) 2 range for data 2.072 to 71.166 collection/ Index ranges 25 h 26, 61 k 60, 29 l 29 Reflections collected 157495 Independent reflections 46366 [Rint = 0.0545, Rsigma = 0.0491] Data/restraints/parameters 46366/0/1853 Goodness-of-fit on F.sup.2 1.265 Final R indexes R1 = 0.1034, wR2 = 0.3152 [I >= 2 (I)] Final R indexes [all data] R1 = 0.1408, wR2 = 0.3476 Largest diff. peak/ 2.57/3.48 hole/e .sup.3
Example 18
[0173] 4.7 mg (0.03 mmol) of 2,5-furandicarboxylic acid (H.sub.2FDCA), 6.4 mg (0.01 mmol) of 2,5,8-tri(4-pyridyl)1,3,4,6,7,9-hexaazaphenalenyl (4TPHAP.sup.), and 6.6 mg (0.03 mmol) of cobalt bromide were heated in a mixed solution of 2 mL of DMF and 100 L of acetic acid in a vial at 100 C. for 72 hours to provide square reddish purple PCN single crystals (PCNVIII-1, FDCA-PCN).
[0174] The resulting reddish purple PCN single crystal, PCNVIII-1, was identified by X-ray structure analysis and confirmed to be a PCN having a unit structure represented by (Co.sup.2+).sub.5(Co.sup.3+).sub.1(TPHAP.sup.).sub.3(FDCA.sup.2).sub.5. The results of the X-ray structure analysis of PCN-18 are shown in Table 18,
TABLE-US-00018 TABLE 18 Name PCNVIII-1 Temperature/K 173.15 Crystal system Monoclinic Space group Cm a/ 21.0227(9) b/ 61.8945(14) c/ 9.2701(4) / 90 / 120.985(6) / 90 Volume/.sup.3 10340.9(9) Z 1 Crystal size/mm.sup.3 0.199 0.209 0.0596 Radiation Mo K ( = 0.71073) Independent reflections 17529 [Rint = 0.0503, Rsigma = 0.0738] Goodness-of-fit on F.sup.2 1.010 Final R indexes R1 = 0.0669, wR2 = 0.1899 [I >= 2 (I)]
[0175] PCNVIII-1 according to Example 18 had pores as shown in FIG. 30, with a maximum opening size of 7.710.1 . The porosity was 49.7% (6092.8 .sup.3).
Example 19
[0176] The PCNV-1 obtained in Example 8 was used to analyze the crystal structure of the guest molecule monensin sodium (C.sub.36H.sub.61NaO.sub.11, 682.86 g/mol). First, PCNV-1 was washed three times with ethyl acetate and solvent-exchanged for one day. Then, immediately before the inclusion of monensin sodium, ethyl acetate was replaced with heptane as the solvent. 1 mg of monensin sodium was added to 1 cm.sup.3 of heptane, several PCNV-1 crystals were added to this solution, the mixture was left to stand at 40 C. for three days and then monensin sodium was included in PCNV-1, and single crystal X-ray diffraction was measured.
[0177] The measurement results are shown in Table 19 and
TABLE-US-00019 TABLE 19 Empirical formula inclusion of monensin sodium PCNV-1 Temperature/K 95 Crystal system monoclinic Space group P2.sub.1 a/ 18.222(2) b/ 32.244(6) c/ 23.684(3) / 90 / 92.966(13) / 90 Volume/.sup.3 15457(4) Z 2 Crystal size/mm.sup.3 0.133 0.175 0.057 Radiation 0.75 (KEK BL-5A) Independent reflections 101660 [R.sub.int = 0.0388, R.sub.sigma = 0.0273] Goodness-of-fit on F.sup.2 1.144 Final R indexes R.sub.1 = 0.11.39, wR.sub.2 = 0.3435 [I >= 2 (I)] Flack parameter 0.054(4)
INDUSTRIAL APPLICABILITY
[0178] The present PCN can be used as a crystal for analyzing the crystal structure of high molecular weight guest molecules such as pharmaceuticals and peptides. In particular, it is expected that the structure of medium-sized molecules, which have been difficult to analyze until now, can be easily analyzed. Further, the present PCN can be used in substance purification processes, as a reaction field in closed spaces, as an adsorbent, and as a chemical sensor material.
[0179] This application claims priority based on Japanese Patent Application No. 2022-140327, filed on Sep. 2, 2022, the disclosure of which is incorporated herein in its entirety.