Crystal, method for producing crystal, and method for inducing self-organization of silanol compound

Abstract

This crystal contains multiple molecules of a silanol compound represented by formula (1), and exhibits an interaction among the multiple molecules of the silanol compound via a hydrogen bond provided by at least one hydroxy group of the silanol compound.

Description

Crystals, method for producing crystals, and method for self-organizing silanol compounds

[0001] The present invention relates to a crystal, a method for producing a crystal, and a method for self-organizing a silanol compound.

[0002] By controlling and constructing materials at the atomic level, unprecedented physical properties can be realized, making it possible to create useful materials. For example, fullerenes, carbon nanotubes, and graphene are nanocarbon materials in which carbon is assembled in zero, one, or two dimensions, and each has unique physical properties.

[0003] SiO ２ Like carbon, SiO exists in inexhaustible quantities on Earth and is a material that has been used continuously up to the present day. ２ SiO ２ The method for obtaining the material is SiO ２ The basic unit of orthosilicic acid (Si(OH) ４ ) is thought to be an efficient method of assembling Si(OH) ４ It is known that Si(OH) can be synthesized and isolated by, for example, reacting a silicon compound having a benzyl protecting group that can be removed by hydrogenolysis in the presence of a Pd or Pt / C catalyst (see, for example, Non-Patent Document 1). ４ The dimer, cyclic trimer, and cyclic tetramer of these Si(OH) have been successfully synthesized and isolated. ４ Oligomers such as dimers, cyclic trimers, and cyclic tetramers of the above are also useful. ２ It is useful as a raw material for obtaining materials.

[0004]

[0005] Nature Communications, 2017, 8, 140.

[0006] SiO ２ SiO ２ To obtain the material, SiO ２ The basic unit of orthosilicic acid (Si(OH) ４As mentioned above, Si(OH) ４ and Si(OH) ４ Although the isolation of the dimer, cyclic trimer, and cyclic tetramer of SiO ２ To obtain the material, SiO ２ There is a need for raw materials that are suitable for more efficiently controlling and assembling the basic units of these.

[0007] The present invention has been made in view of the above circumstances, and is a method for manufacturing a silicon dioxide film by using SiO ２ The objective is to provide raw materials useful for obtaining materials.

[0008] As a result of extensive research to solve the above problems, the present inventors have found that a specific Si(OH) ４ The present inventors have found that the oligomers self-assemble in a controlled manner at the atomic level, and that the oligomers are obtained as regularly aligned crystals, thereby completing the present invention.

[0009] That is, this application provides the following invention: [1] A crystal containing a plurality of silanol compounds represented by the following formula (1), which have interaction between the silanol compounds via a hydrogen bond formed by at least one hydroxy group: [2] The crystal according to [1], wherein the silanol compound has a one-dimensional structure linearly aligned due to interactions via hydrogen bonds. [3] The crystal according to [1], wherein the silanol compound has a two-dimensional structure planarly aligned due to interactions via hydrogen bonds. [4] The crystal according to [1], wherein the silanol compound has a three-dimensional structure sterically aligned due to interactions via hydrogen bonds. [5] The crystal according to any one of [1] to [4], which contains at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements. [6] A method for producing the crystal according to any one of [1] to [5], comprising the steps of: preparing a solution containing the silanol compound; and, if necessary, further adding at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements to the solution, and recrystallizing the solution by a vapor diffusion method. [7] A method for producing a crystal according to any one of [1] to [5], comprising the steps of: preparing a solution containing the silanol compound; and, if necessary, further adding at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements to the solution, and recrystallizing the solution by a poor solvent method. [8] A method for producing a crystal according to any one of [1] to [5], comprising the steps of: preparing a solution containing the silanol compound; and, if necessary, further adding at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements to the solution, and recrystallizing the solution by concentrating the solution under reduced pressure. [9] A method for producing a crystal according to any one of [1] to [5], comprising the steps of: preparing a solution containing the silanol compound; and, if necessary, further adding at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements to the solution, and recrystallizing the solution by cooling the solution.

[10] A method for producing the crystal according to any one of [1] to [5], comprising the steps of: preparing a solution containing the silanol compound; and, if necessary, further adding at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements to the solution, and heating the solution to recrystallize.

[11] A method for producing a crystal (P) containing at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements, comprising the steps of: preparing a crystal (S) containing a plurality of silanol compounds represented by the following formula (1), which interact with each other via a hydrogen bond formed by at least one hydroxy group between the silanol compounds, and which contains at least one first substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements; and contacting the crystal (S) with at least one second substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements to replace at least a portion of the first substance contained in the crystal (S) with the second substance, thereby obtaining a crystal (P).

[12] The method according to

[11] , wherein the step of preparing the crystals (S) comprises: preparing a solution containing the silanol compound; and adding, if necessary, a substance selected from the group consisting of an organic compound, a transition metal complex, an inorganic substance, and a simple element to the solution, and recrystallizing the solution by a vapor diffusion method for the solution, a poor solvent method for the solution, concentrating the solution under reduced pressure, cooling the solution, or heating the solution.

[13] A method for self-organizing the silanol compound, comprising: forming an interaction through hydrogen bonding by a vapor diffusion method for a solution containing a silanol compound represented by the following formula (1), a poor solvent method for the solution, concentrating the solution under reduced pressure, cooling the solution, or heating the solution.

[0010] According to the present invention, Si(OH) ４ The oligomers can provide regularly ordered crystals.

[0011] 1 is a diagram illustrating plane 1 and plane 2 in a structure of alignment as viewed from a perspective view, schematically illustrating the crystal structure determined by single crystal X-ray crystal structure analysis of the crystal (one-dimensional (rod-like) structure) produced in Example 1. FIG. 2 is a diagram illustrating the crystal structure determined by single crystal X-ray crystal structure analysis of the crystal (two-dimensional (sheet-like) structure) produced in Example 2. FIG. 3 is a diagram illustrating the crystal structure determined by single crystal X-ray crystal structure analysis of the crystal (three-dimensional (nano-sponge-like) structure) produced in Example 3. FIG. 4 is a diagram illustrating the crystal structure determined by single crystal X-ray crystal structure analysis of the crystal (three-dimensional (nano-honeycomb-like) structure) produced in Example 4. FIG. 5 is a diagram illustrating the crystal structure determined by single crystal X-ray crystal structure analysis of the crystal (three-dimensional (nano-honeycomb-like) structure) produced in Example 5. FIG. 6 is a diagram illustrating the crystal structure determined by single crystal X-ray crystal structure analysis of the crystal (three-dimensional (nano-honeycomb-like) structure) produced in Example 6. Schematic diagram showing the crystal structure determined from single crystal X-ray crystal structure analysis of the crystal (one-dimensional (rod-like) structure) produced in Example 19. Schematic diagram showing the crystal structure determined from single crystal X-ray crystal structure analysis of the crystal (two-dimensional (sheet-like) structure) produced in Example 20. Schematic diagram showing the crystal structure determined from single crystal X-ray crystal structure analysis of the crystal (three-dimensional (nanohoneycomb) structure) produced in Example 21. Schematic diagram showing the crystal structure determined from single crystal X-ray crystal structure analysis of the crystal (three-dimensional (nanohoneycomb) structure) produced in Example 22.

[0012] Hereinafter, a mode for carrying out the present invention (hereinafter also referred to as "the present embodiment") will be described in detail. Note that the present invention is not limited to the present embodiment, and various modifications can be made within the scope of the gist of the present invention.

[0013] [Crystal] The crystal of this embodiment contains a silanol compound that is a dodecamer of orthosilicic acid (hereinafter simply referred to as "dodecamer") represented by the following formula (1). The number of compounds that constitute the crystal of this embodiment is plural. Furthermore, the crystal of this embodiment has interaction between the silanol compounds via a hydrogen bond formed by at least one hydroxy group.

[0014]

[0015] The multiple silanol compounds contained in the crystal of this embodiment interact with each other via hydrogen bonds formed by at least one hydroxy group in the silanol compound. In this embodiment, the interaction via hydrogen bonds refers to a non-covalent interaction formed between a hydrogen atom of a hydroxy group contained in any silanol compound molecule in the crystal and an unshared electron pair of an oxygen atom in a silanol compound of another molecule. The interaction via hydrogen bonds is preferably formed between the hydrogen and oxygen in the hydroxy groups of the silanol compounds. The crystals referred to herein are solids and include aggregates in which silanol compounds are regularly aligned through interactions via hydrogen bonds. The aggregates may be aligned in a chain or a ring shape, in which the silanol compounds are aligned. The presence of a crystal containing interactions via hydrogen bonds between silanol compounds can be confirmed by X-ray crystal structure analysis of the crystal.

[0016] The crystal of this embodiment contains a plurality of the above-described 12-mer silanol compound. In the crystal of this embodiment, the hydroxy group forming the hydrogen bond of the silanol compound may be any hydroxy group. That is, the hydroxy group forming the hydrogen bond of the silanol compound may be any of the 12 hydroxy groups of the 12-mer.

[0017] The number of hydroxy groups forming hydrogen bonds of the silanol compound may be one or more per molecule. However, from the viewpoint of forming crystals, when the silanol compounds are aligned to form a chain-like aggregate, the number of hydroxy groups forming hydrogen bonds of the silanol compound, excluding the terminal silanol compounds, is two or more per molecule. Furthermore, when the silanol compounds are aligned to form a cyclic aggregate, the number of hydroxy groups forming hydrogen bonds of the silanol compound is two or more per molecule.

[0018] When the crystal of this embodiment contains a dodecamer of a silanol compound and the silanol compounds form a chain-like assembly, the number of hydroxy groups forming hydrogen bonds per molecule, excluding the silanol compounds at the ends of the chain-like assembly, may be any of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12. When the crystal of this embodiment contains a dodecamer of a silanol compound and the silanol compounds are aligned to form a cyclic assembly, the number of hydroxy groups forming hydrogen bonds per molecule may be any of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12.

[0019] The dodecamer silanol compound contained in the crystal of this embodiment self-assembles to form regularly aligned aggregates. Examples of the format of the dodecamer silanol compound are shown below. However, in this specification, the structure of the dodecamer may be abbreviated as (1)' below by omitting one Si-O-Si bond and representing it as one side, and omitting the OH group, as shown below:

[0020]

[0021] The dodecamer silanol compound contained in the crystal of this embodiment has a clear hole in the center of the hexagonal prism, as shown in the structure above. The arrangement form is not particularly limited, but an example is a one-dimensional structure in which the silanol compounds are linearly arranged.

[0022] The one-dimensional structure of the dodecamer is not particularly limited, and examples thereof include the structures shown in Tables 1-1, 1-2, 2, and 3 below. The structures shown in these tables are intended to schematically represent the alignment of silanol compounds constituting the one-dimensional structure by showing the arrangement of the silanol compounds and / or the orientation of the cyclic silanol faces in the silanol compounds. The one-dimensional structure of this embodiment allows for the silanol compounds to be displaced from these schematically represented alignments, and / or for the cyclic silanol faces to be displaced from the alignment axis. In the structures shown in Tables 1-1, 1-2, 2, and 3 below, the type of hydrogen bonding is arbitrary as long as the hydrogen bonds are formed to enable the alignment. Therefore, in the structures shown in Tables 1-1, 1-2, 2, and 3 below, hydrogen bonds are omitted. In this specification, the type of hydrogen bonding refers to the number and positions of hydrogen bonds formed between silanol compounds. The number of aligned silanol compounds is not limited to the numbers shown in each table. For example, in Format 4 of Table 1-2, the hydrogen bond may be formed in the form of the following structures A and B, and even if there is only one structure, the number and positions of the hydrogen bonds formed are arbitrary.

[0023]

[0024] In this specification, The bond between the silanol compounds represented by the formula (I) is the following hydrogen bond: In addition to the hydrogen bond, this bond may also include a hydrogen bond due to an interaction with a hydroxy group of another silanol compound, and / or a hydrogen bond due to an interaction with a substance such as an organic compound, a transition metal complex, an inorganic substance, or an elemental substance. Also, a compound having two or more hydrogen-bonding functional groups (e.g., H ２ O), provided that in the above structures A and B, the bond refers to a single hydrogen bond.

[0025] Also, in the table, surface 1 refers to the alignment structure viewed from an oblique direction, as viewed from direction 1 (on the paper, from above) in Figure 1, and surface 2 refers to the alignment structure viewed from an oblique direction, as viewed from direction 2 (on the paper, from the front) in Figure 1.

[0026]

[0027]

[0028]

[0029] As described above, the crystal of this embodiment may include a ring-shaped assembly of silanol compounds aligned together. The number of silanol compounds forming the ring-shaped assembly may be any number. For example, a dodecamer silanol compound may form a ring from an assembly of six silanol compounds (Form 7). The crystal of this embodiment may also have a layered structure in which one-dimensional structures of ring-shaped assembly such as Form 7 are stacked together via plane 1.

[0030]

[0031] The hydrogen bond mode will be explained below using the alignment format shown in the table above as an example. Examples of hydrogen bond modes that form the linearly aligned one-dimensional structure include modes in which two hydroxy groups contained in one silanol compound interact with hydroxy groups of another silanol compound via the plane of the tetramer through hydrogen bonding. The two hydroxy groups that form the hydrogen bond may be two hydroxy groups on adjacent silicon atoms in one silanol compound, or may be two hydroxy groups on silicon atoms that are separated by one or more siloxane bonds (—O—Si—O— bonds). Here, "adjacent silicon atoms" refers to silicon atoms that are separated by one oxygen atom from a given silicon atom, and "silicon atoms that are separated by one or more siloxane bonds" refers to silicon atoms that are separated by two or more oxygen atoms and one or more silicon atoms from a given silicon atom. In other words, "adjacent silicon atoms" refers to silicon atoms located across a structure represented by the following formula (a) where n is 0, and "silicon atoms at least one siloxane bond away" refers to silicon atoms located across a structure represented by the following formula (a) where n is an integer of 1 or more, O-(Si-O) ｎ ...(a) (wherein n represents an integer of 0 or more.)

[0032] An example of a one-dimensional structure in which the above-mentioned assembly is formed by hydrogen bonding between two hydroxy groups on silicon atoms that are one or more siloxane bond apart is a one-dimensional structure formed by repeating a sequence of steps, as shown in Formula 1, in which a hydroxy group on the upper silicon atom of a certain dodecamer forms a hydrogen bond with a hydroxy group on the upper silicon atom of another dodecamer, and a hydroxy group on an upper silicon atom that is one siloxane bond away from the upper silicon atom of the certain dodecamer (i.e., positioned across the structure represented by formula (a) where n is 1) forms a hydrogen bond with a hydroxy group on the upper silicon atom of yet another dodecamer (see the structure below).

[0033]

[0034] Another example of a one-dimensional structure in which the above-mentioned assembly is formed by hydrogen bonding between two hydroxy groups on adjacent silicon atoms is a one-dimensional structure formed by repeating a sequence in which a hydroxy group on the upper silicon atom of a dodecamer forms a hydrogen bond with a hydroxy group on the lower silicon atom of another dodecamer, and a hydroxy group on the upper silicon atom adjacent to the upper silicon atom of the dodecamer forms a hydrogen bond with a hydroxy group on the lower silicon atom of yet another dodecamer, as shown in Formula 2 (see the structure below).

[0035]

[0036] The linearly aligned one-dimensional structure can be, for example, an assembly formed by the interaction of four hydroxy groups contained in one silanol compound with hydroxy groups of another silanol compound through hydrogen bonding. Specific examples of the one-dimensional structure include a structure in which, of the four hydroxy groups contained in one silanol compound, two hydroxy groups bonded to adjacent silicon atoms are hydrogen-bonded to two hydroxy groups bonded to adjacent silicon atoms of another silanol compound, and the remaining two hydroxy groups bonded to adjacent silicon atoms of the one silanol compound are hydrogen-bonded to two hydroxy groups bonded to adjacent silicon atoms of yet another silanol compound, and suitable examples of the one-dimensional structure include structures 1, 2, and 3 in Table 1-1.

[0037] Examples of one-dimensional structures include structures in which cyclic silanol surfaces are aligned so as to overlap each other, as shown in Formulas 3 and 6. Specific examples of one-dimensional structures include structures in which a cyclic silanol surface contained in one silanol compound interacts with a cyclic silanol surface of another silanol compound via hydrogen bonds (hereinafter also referred to as a rod-like structure), and examples include, but are not limited to, the following structure i. When the silanol compound is a dodecamer represented by formula (1), the cyclic silanol surface is preferably the surface of a 12-membered ring (hexamer (cyclohexasiloxane skeleton)).

[0038]

[0039] The structure i has a rod shape due to the alignment of the faces overlapping each other. Note that in the structure i, it is sufficient that the faces are aligned to overlap each other to form a hydrogen bond network; it is not necessary for all hydroxy groups to form hydrogen bonds.

[0040] Further, examples of rod-shaped structures include a structure in which, in the alignment of a dodecamer of a silanol compound, the faces of the eight-membered rings (tetramers (cyclotetrasiloxane skeletons)) of the dodecamer interact with each other via hydrogen bonds. Specific examples include the alignment form shown in Format 3. In the alignment form shown in Format 3, it is sufficient that a hydrogen bond network is formed so that the faces are aligned so as to overlap each other, and it is not necessary for all hydroxy groups to form hydrogen bonds.

[0041] In the one-dimensional structure described above, the number of hydrogen bonds formed between one hydroxy group bonded to one silicon atom contained in one silanol compound and the hydroxy group of another silanol compound is one. On the other hand, the number of hydrogen bonds that the hydroxy group can form may be two or more, and it may further form a hydrogen bond with the hydroxy group of another silanol compound. By forming a hydrogen bond with the hydroxy group of another silanol compound, the crystal becomes a two-dimensionally and three-dimensionally aligned structure. That is, the crystal of this embodiment may be a crystal having a two-dimensional structure in which the silanol compound is aligned in a plane due to interactions via hydrogen bonds, or a crystal having a three-dimensional structure in which the silanol compound is aligned three-dimensionally due to interactions via hydrogen bonds.

[0042] In the crystal having a two-dimensional structure of this embodiment, the bonding form of the hydrogen bonds is not particularly limited as long as the silanol compounds are aligned in a planar manner. Here, the planarly aligned structure in this specification can also be referred to as a structure in which multiple silanol compounds are regularly aligned in two directions, the X-axis direction and the Y-axis direction. Examples of crystals having a two-dimensional structure of this embodiment include structures in which the above-mentioned one-dimensional structure interacts with another one-dimensional structure via hydrogen bonds to form a planar arrangement. The two-dimensional structure of this embodiment also includes structures in which the ends of two-dimensionally aligned structures interact with each other via hydrogen bonds to form a ring. Preferred examples of crystals having a two-dimensional structure include structures in which one longitudinal side of the one-dimensional structure of the rod-like structure interacts with one longitudinal side of another one-dimensional structure via hydrogen bonds to form a planar arrangement. Specific examples include, but are not limited to, those represented by the following structure ii. Furthermore, other specific examples of crystals having a two-dimensional structure include, but are not limited to, crystals represented by the following structure iii. Note that in the following structures ii and iii, it is not necessary for all hydroxy groups to form hydrogen bonds.

[0043] structure ii

[0044] structure iii

[0045] The crystal having a three-dimensional structure of this embodiment is not particularly limited in the form of hydrogen bonds, as long as the silanol compounds are three-dimensionally aligned. Here, the three-dimensionally aligned structure in this specification can also be referred to as a structure in which multiple silanol compounds are regularly aligned in three directions: the X-axis direction, the Y-axis direction, and the Z-axis direction. Examples of the crystal having a three-dimensional structure of this embodiment include a structure in which the above-mentioned two-dimensional structure interacts with multiple other two-dimensional structures via hydrogen bonds to form a three-dimensional alignment. Furthermore, suitable examples of the crystal having a three-dimensional structure include, but are not limited to, the following structures iv to vii. structure iv structure v structure vi structure vii

[0046] As described below, the crystals of this embodiment can be prepared by recrystallization from a solution containing a silanol compound and, if necessary, an organic compound, and the resulting crystals may contain the organic compound. The substances contained in the crystals are not limited to the solvent used during production and / or the organic compound added, but may also be, for example, transition metal complexes, inorganic substances, or simple elements. The organic compounds, transition metal complexes, inorganic substances, and simple elements may be contained among clusters of silanol compounds aligned by interactions via hydrogen bonds, and if the crystals have a three-dimensional structure, they may be contained within the three-dimensional structure.

[0047] The organic compounds, transition metal complexes, inorganic substances, and elemental substances contained in the crystals are not particularly limited, but preferably have a molecular weight of 2 to 1000 g / mol. The substances contained in the crystals are not particularly limited, but examples thereof include hydrogen (hydrogen gas), nitrogen (nitrogen gas), helium, diethyl ether, diisopropyl ether, tert-butyl ethyl ether, furan, glycidyl methyl ether, allyl glycidyl ether, glycidyl isopropyl ether, glycidyl propargyl ether, butyl glycidyl ether, glycidyl phenyl ether, benzyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, 1,2-epoxybutanediol, glycidyl methyl ... methyl ether, glycidyl methyl ether, glycidyl methyl ether, glycidyl isopropyl ether, glycidyl propargyl ether, butyl glycidyl ether, glycidyl phenyl ether, benzyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, glycidyl methyl ether, glycidyl propargyl ether, glycidyl methyl ether, glycidyl methyl ether, glycidyl methyl ether, glycidyl methyl ether, glycidyl methyl ether, glycidyl methyl ether, glycidyl methyl ether, glycidyl methyl ether, glycidyl methyl ether, glycidyl methyl ether, glycidyl methyl ether, glycidyl methyl ether, glycidyl methyl benzene, 3,4-epoxy-1-butene, 1,2:3,4-diepoxybutane, 1,2:5,6-diepoxyhexane, 1,2:7,8-diepoxyoctane, tetramethylene glycol diglycidyl ether, 1,2-epoxycyclohexane, 1,2-epoxy-4-vinylcyclohexane, tetrahydrofuran (THF), tetrahydrothiophene, 1,3-dioxolane, ethylene carbonate, 1,4-dioxane, 1,3,5-trithiane, thiophene, selenophene, 2,5-dibromoselenophene , tellurophene, oxazole, isoxazole, isothiazole, pyrazole, imidazole, thiazole, 1H-1,2,3-triazole, 1,2,4-triazole, 1H-tetrazole, pyridine, pyrazine, triazine, benzoxazole, 1,2-benzisoxazole, 2,1-benzisoxazole, 1,2-benzisothiazol-3(2H)-one, indole, benzimidazole, 1,3-benzodioxole, benzothiazole, 2,1,3-benzothiadiazole, indole Indazole, 1,2,3-benzotriazole, pyrazolo[3,4-b]pyridine, methyl acetate, ethyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, allyl acrylate, allyl methacrylate, butyl acrylate, isobutyl acrylate, butyl methacrylate, isobutyl methacrylate, 2-methoxyethyl methacrylate, 1,4-phenylenediisocyanate, 1,4-phenylenediisothiocyanate, 1,5-diisocyanatonaphthalene, squaric acid (3,4-Dihydroxy-3-cyclobutene-1,2-dione), croconic acid (4,5-dihydroxy-4-cyclopentene-1,2,3-trione), dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, N,N-dimethylacetamide, N,N-dimethylformamide (DMF), N-methylacetamide, dimethyl sulfoxide, dimethylurea, tetramethylurea, aniline, pyridine, pyrazine, 4-dimethylaminopyridine, quinoline, quinoxaline, 1,5-naphthyridine, acridine, Phenazine, 1,4-anthrazoline, 1,5-anthrazoline, 1,6-anthrazoline, 1,10-phenanthroline, 2,2-bipyridyl, 3,3-bipyridyl, 4,4-bipyridyl, quinuclidine, 1,4-diazabicyclooctane, hexamethylenetetramine, cyclopentanone, cyclohexanone, 1,2-cyclohexanedione, 1,3-cyclohexanedione, 1,4-cyclohexanedione, 1,4-benzoquinone, tetrafluoro-1,4-benzoquinone, hydroquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, 2-methyl 1,4-naphthoquinone, anthraquinone, 1,4-anthraquinone, benzene, toluene, xylene, 1,2-bis(bromomethyl)benzene, 1,4-dibromo-2,5-dimethylbenzene, 1,4-dibromo-2,5-bis(bromomethyl)benzene, 1,2-dibromo-4,5-dimethylbenzene, 1,4-dibromo-2,5-dimethylbenzene, 1,4-bis(dimethylsilyl)benzene, 1,4-bis(trimethylsilyl)benzene, 1,4-bis(hydroxydimethylsilyl)benzene, styrene, 4-methylstyrene, 2,3,4 , 5,6-pentafluorostyrene, naphthalene, 2,3-dimethylnaphthalene, 2,6-dimethylnaphthalene, 2,7-dimethylnaphthalene, 2,6-dibromonaphthalene, 2,7-dibromonaphthalene, benzo[b]thiophene, 5-bromobenzo[b]thiophene, 6-bromobenzo[b]thiophene, anthracene, naphthacene, pentacene, 2,3-dimethylanthracene, 2-bromoanthracene, 2,6-dibromoanthracene, carbazole, 2-bromocarbazole, 3-bromocarbazole, 2,7-dibromocarbazole, 3,6-Dibromocarbazole, dibenzothiophene, 3-bromodibenzothiophene, 2,8-dibromodibenzothiophene, 3,7-dibromodibenzothiophene, 4,6-dibromodibenzothiophene, 2-iododibenzothiophene, 2,8-diiododibenzothiophene, 2,8-dimethyldibenzothiophene, benzo[1,2-b':4,5-b']dithiophene, 2,6-dibromobenzo[1,2-b':4,5-b']dithiophene, 2,8-dimethylanthra[2,3-b:6,7-b']dithiophene, phenanthro[1,2-b :8,7-b']dithiophene, thieno[3,2-b]thiophene, 3-bromothieno[3,2-b]thiophene, 2,5-dibromothieno[3,2-b]thiophene, 2,5-di(2-thienyl)thieno[3,2-b]thiophene, 3,6-dibromothieno[3,2-b]thiophene, thieno[2,3-b]thiophene, 2-bromothieno[2,3-b]thiophene, 2,5-dibromothieno[2,3-b]thiophene, 3,4-dibromothieno[2,3-b]thiophene, dithieno[3,2-b:2',3'-d]thiophene, 2,6-dibromothieno[3,2-b:2',3'-d]thiophene Modithieno[3,2-b:2',3'-d]thiophene, 3,5-dibromodithieno[3,2-b:2',3'-d]thiophene, biphenyl, p-terphenyl, 4-bromo-p-terphenyl, 4,4"-dibromo-p-terphenyl, 4-bromobiphenyl, 4,4'-dibromobiphenyl, p-quaterphenyl, 2,2'-bithiophene, 3,3'-dibromo-2,2'-bithiophene, 5,5'-dibromo-2,2'-bithiophene, 3,3',5,5'-dibromo-2,2'-bithiophene, 2,2'-bithiophene-5-carboxamide thiophene, 5-bromo-2,2'-bithiophene-5'-carboxaldehyde, 2,2'-bithiophene-5,5'-dicarboxaldehyde, terthiophene, 5,5"-dibromo-2,2':5',2"-terthiophene, 5"-bromo-2,2':5',2"-terthiophene-5-carboxaldehyde, 2,2':5',2"-terthiophene-5,5"-dicarboxaldehyde, α-quaterthiophene, α-quinchithiophene, α-sexithiophene, α-septithiophene, 1,4-cyclohexadiene, 1-methyl-1,4-Cyclohexadiene, azobenzene, 3,3'-dimethylazobenzene, trans-stilbene, trans-4-bromostilbene, 4,4'-dibromo-trans-stilbene, 4-methyl-trans-stilbene, 4,4'-dimethyl-trans-stilbene, 1,4-diethynylbenzene, diphenylacetylene, 1-ethynyl-4-(phenylethynyl)benzene, adamantane, 1,3-dimethyladamantane, 1-bromoadamantane, 2-bromoadamantane, 3-bromoadamantane, 1,3-dibromoadamantane , pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, tetracosane, acetonitrile, adiponitrile, fumaronitrile, tetracyanoethylene, 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3,5,5,5-heptamethyltrisiloxane, 1,1 , 1,3,5,5,5-heptamethyltrisiloxane, 1,1,1,3,3,5,5,5-octamethyltrisiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, decamethyltetrasiloxane, 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11-dodecamethylhexasiloxane, ferrocene, nickelocene, ruthenocene, chromocene, manganocene, cobaltocene, Smosene, vanadocene, acetylacetonate, bis(ethylene)rhodium, (2,4-pentanedionato)lithium, bis(2,4-pentanedionato)beryllium, bis(2,4-pentanedionato)magnesium, bis(2,4-pentanedionato)calcium, bis(2,4-pentanedionato)manganese, bis(2,4-pentanedionato)cobalt, bis(2,4-pentanedionato)nickel, bis(2,4-pentanedionato)copper, bis(2,4-pentanedionato)palladium, bis(2,4-pentanedionato)platinum, tris(2,4-pentanedionato)chromium, tris(2,4-pentanedionato)cobalt, tris(2,4-pentanedionato)gallium, tris(2,4-pentanedionato)indium, tris(2,4-pentanedionato)iridium, tris(2,4-pentanedionato)iron, tris(2,4-pentanedionato)lanthanum, bis(benzene)chromium, (benzene)tricarbonylchromium, cyclopentadienyldicarbonylcobalt, tris(cyclopentadienyl)gadolinium, tris(cyclopentadienyl)yttrium, cyclo Pentadienylindium, bis(cyclopentadienyl)magnesium, cyclopentadienylmanganese tricarbonyl, cycloheptatrienemolybdenum tricarbonyl, tris(cyclopentadienyl)neodynium, allylpalladium chloride (dimer), bis(cyclooctatetraene)iron, cyclohexadieneiron tricarbonyl, dicarbonylcyclopentadienyliodionite, cyclopentadienyliron dicarbonyl (dimer), tricarbonyl(cyclooctatetraene)iron, iron(II) acetate, (acetylacetonate)(1 ,5-cyclooctadiene)iridium, chloro(1,5-cyclooctadiene)iridium (dimer), chlorobis(ethylene)iridium (dimer), (cycloheptatrienyl)(cyclopentadienyl)titanium, bis(1,5-cyclooctadiene)nickel, bis(1,5-cyclooctadiene)platinum, (trimethyl)cyclopentadienylplatinum, tris(cyclopentadienyl)praseodymium, cyclopentadienylrhenium tricarbonyl, dicarbonyl(2,4-pentanedionato)rhodium, hydroxy(1,5-cyclopentadienyl) Examples of suitable rhodium compounds include chloro(1,5-cyclooctadiene)rhodium (dimer), acetylacetonato(norbornadiene)rhodium, chloro(1,5-cyclooctadiene)rhodium (dimer), rhodium acetate (dimer), chloro(norbornadiene)rhodium (dimer), dicarbonylcyclopentadienylruthenium (dimer), tris(cyclopentadienyl)samarium, cyclopentadienylthallium, dicarbonylbis(cyclopentadienyl)titanium, cyclopentadienylvanadium tetracarbonyl, bromine, iodine, sulfur, mercury, and water.

[0048] When the crystal of this embodiment contains an organic compound, a transition metal complex, an inorganic substance, or a substance of a single element, the organic compound, the transition metal complex, the inorganic substance, or the substance of a single element may be added to a solution containing a silanol compound used for recrystallization, as described below, or the organic compound, the transition metal complex, the inorganic substance, or the substance of a single element may be added to the obtained crystal.

[0049] When the crystal of this embodiment contains, for example, benzene, the benzene molecule can be encapsulated within the above structure v (nanohoneycomb (type 1) (structure of 12-membered ring (hexamer) planes)).

[0050] [Method for Producing Crystals] The crystals of this embodiment can be produced, for example, by preparing a solution containing a dodecamer silanol compound, optionally adding at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements to the solution, and recrystallizing the solution by a vapor diffusion method; optionally adding at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements to the solution, and recrystallizing the solution by a poor solvent method; optionally adding at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements to the solution, and recrystallizing the solution by concentrating it under reduced pressure; optionally adding at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements to the solution, and cooling the solution to recrystallize; or optionally adding at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements to the solution, and recrystallizing the solution by heating the solution. That is, one method for producing crystals of this embodiment includes the steps of preparing a solution containing the silanol compound; and, if necessary, further adding at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements to the solution, and recrystallizing the solution by a vapor diffusion method. Here, the vapor diffusion method refers to, for example, a method of adding a poor solvent to the solution by vapor diffusion. Also, one method for producing crystals of this embodiment includes the steps of preparing a solution containing the silanol compound; and, if necessary, further adding at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements to the solution, and recrystallizing the solution by a poor solvent method. Here, the poor solvent method refers, for example, to a method of adding a poor solvent to the solution all at once.One method for producing crystals of this embodiment includes the steps of: preparing a solution containing the silanol compound; and, if necessary, further adding at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements to the solution, and then concentrating the solution under reduced pressure to recrystallize the solution. Another method for producing crystals of this embodiment includes the steps of preparing a solution containing the silanol compound; and, if necessary, further adding at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements to the solution, and then cooling the solution to recrystallize the solution. Here, "cooling" refers to heating the solution once and then allowing it to stand, etc., to lower the temperature (e.g., to room temperature), or cooling the solution to, for example, -80°C to 25°C, preferably -30°C to 25°C. The temperature at which the solution is heated is preferably, for example, 30 to 180°C. Furthermore, one method for producing crystals according to this embodiment includes the steps of preparing a solution containing the silanol compound; and, if necessary, further adding at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements to the solution, and heating the solution to recrystallize it. The heating temperature is, for example, 30 to 180°C, preferably 60 to 120°C, and the heating time is, for example, preferably 0.5 to 24 hours. Heating under these conditions tends to precipitate crystals having the most stable crystal structure (Type 1). After heating, the crystals can be recovered after cooling. These methods can also be performed in combination.

[0051] In the above-described production method, an interaction between silanol compounds through hydrogen bonding can be generated by evaporating the solvent from a solution containing the silanol compound, by cooling the solution, or by heating the solution. One embodiment is a method for self-organizing the silanol compound, which includes a step of forming an interaction through hydrogen bonding by applying a vapor diffusion method to a solution containing a 12-mer silanol compound, by applying a poor solvent method to the solution, by concentrating the solution under reduced pressure, or by cooling the solution, for example, by cooling the solution and evaporating the solvent, or by heating the solution.

[0052] When the crystal of this embodiment contains a substance such as an organic compound, a transition metal complex, an inorganic substance, or a simple element, the crystal of this embodiment may be produced by impregnating the crystal obtained by recrystallization as described above with a substance or a solution thereof selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements. This method allows for the production of various crystals containing organic compounds, transition metal complexes, inorganic substances, and simple elements, starting from the crystal obtained by recrystallization. The crystal to be impregnated is not particularly limited as long as it is a crystal of this embodiment. Specifically, it may be any of the following: a crystal having a one-dimensional structure in which the silanol compound is linearly aligned through the interaction via the hydrogen bonds; a crystal having a two-dimensional structure in which the silanol compound is planarly aligned through the interaction via the hydrogen bonds; or a crystal having a three-dimensional structure in which the silanol compound is sterically aligned through the interaction via the hydrogen bonds.

[0053] In this specification, a crystal containing a raw material substance is referred to as a crystal (S), and a crystal containing a substance in which at least a portion of the substance contained in the crystal (S) has been substituted is referred to as a crystal (P).

[0054] By the above-described impregnation method, the substance in the crystal (S) is replaced with the substance to be impregnated to form the crystal (P). This replacement is thought to occur because the crystal (S) originally has a crystal structure formed by a first substance, such as an organic compound, a transition metal complex, an inorganic substance, or a simple element, and a silanol compound, and the second substance, such as an organic compound, a transition metal complex, an inorganic substance, or a simple element, is present in excess and / or has a higher affinity with the silanol compound, resulting in preferential formation of a crystal structure with the second substance.

[0055] One embodiment of the present invention is a method for producing a crystal (P) containing at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements. The method for producing the crystal (P) includes the steps of: preparing a crystal (S) containing a plurality of 12-mer silanol compounds represented by the following formula (1), which interact with each other via a hydrogen bond formed by at least one hydroxyl group between the silanol compounds, and containing at least one first substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements; contacting the crystal (S) with at least one second substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements, thereby substituting at least a portion of the first substance contained in the crystal (S) with the second substance, thereby obtaining a crystal (P).

[0056] Here, it is preferable that at least a part of the substance after substitution is a substance different from the substance before substitution.

[0057] That is, one embodiment of the present invention is a method for producing a crystal (P) containing a plurality of 12-mer silanol compounds represented by formula (1), the silanol compounds interacting with each other via a hydrogen bond formed by at least one hydroxy group, the silanol compounds having a linearly aligned one-dimensional structure, and at least one substance selected from the group consisting of an organic compound, a transition metal complex, an inorganic substance, and a simple element, the method comprising: preparing a crystal (S), the plurality of 12-mer silanol compounds represented by formula (1), the silanol compounds interacting with each other via a hydrogen bond formed by at least one hydroxy group, the silanol compounds having a linearly aligned one-dimensional structure, and the silanol compounds comprising at least one first substance selected from the group consisting of an organic compound, a transition metal complex, an inorganic substance, and a simple element; and contacting the crystal (S) with at least one second substance selected from the group consisting of an organic compound, a transition metal complex, an inorganic substance, and a simple element, thereby substituting at least a portion of the first substance contained in the crystal (S) with the second substance, thereby obtaining a crystal (P).

[0058] One of the present embodiments is a method for producing a crystal (P) containing a plurality of 12-mer silanol compounds represented by formula (1), the silanol compounds interacting with each other via a hydrogen bond formed by at least one hydroxy group, the silanol compounds having a two-dimensional structure in which the silanol compounds are aligned in a plane, and at least one substance selected from the group consisting of an organic compound, a transition metal complex, an inorganic substance, and a simple element, the method comprising: preparing a crystal (S), the plurality of 12-mer silanol compounds represented by formula (1), the silanol compounds interacting with each other via a hydrogen bond formed by at least one hydroxy group, the silanol compounds having a two-dimensional structure in which the silanol compounds are aligned in a plane, and the crystal (S) containing at least one first substance selected from the group consisting of an organic compound, a transition metal complex, an inorganic substance, and a simple element; and contacting the crystal (S) with at least one second substance selected from the group consisting of an organic compound, a transition metal complex, an inorganic substance, and a simple element, thereby substituting at least a portion of the first substance contained in the crystal (S) with the second substance, thereby obtaining a crystal (P).

[0059] In particular, when the crystal of this embodiment has a three-dimensional structure as described above and contains an organic compound, a transition metal complex, an inorganic substance, or a simple element within the three-dimensional structure (the crystal in this case is also referred to as a "substance-containing three-dimensional structure crystal"). A preferred method is to impregnate the crystal produced by the recrystallization method with a substance or a solution thereof selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements. When producing a substance-containing three-dimensional structure crystal using the production method including the recrystallization step described above, it may be difficult to include certain substances within the three-dimensional structure. On the other hand, the method of impregnating a substance can easily replace the organic compound, transition metal complex, inorganic substance, or simple element originally contained in the raw material substance-containing three-dimensional structure crystal with the impregnated substance. As a result, a three-dimensional structure crystal containing a substance that is difficult to include within the three-dimensional structure can be produced.

[0060] Therefore, one embodiment of the present invention is a method for producing a crystal (P) having a three-dimensional structure and containing at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements. The method for producing the crystal (P) includes the steps of: preparing a crystal (S) containing a plurality of 12-mer silanol compounds represented by formula (1), which have an interaction via a hydrogen bond between at least one hydroxy group between the silanol compounds, and which have a three-dimensional structure in which the silanol compounds are sterically aligned due to the interaction via the hydrogen bond, and which contains at least one first substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements; contacting the crystal (S) with at least one second substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements, thereby replacing at least a portion of the first substance contained in the crystal (S) with the second substance, thereby obtaining a crystal (P).

[0061] Here, the substitution step in this embodiment may be performed two or more times. For example, when two substitution steps are performed, the first substance is substituted with the second substance in the first substitution step, and the second substance is substituted with the third substance in the second substitution step.

[0062] The crystal (S) may be prepared, for example, by the above-described crystal production method, specifically, by a production method including the steps of: preparing a solution containing the dodecamer compound represented by formula (1); and, if necessary, adding at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements to the solution, and recrystallizing the solution by a vapor diffusion method, a poor solvent method, concentrating the solution under reduced pressure, cooling the solution, or heating the solution. The crystal (S) is preferably prepared by a production method including the steps of: preparing a solution containing the dodecamer compound represented by formula (1); and adding the first substance to the solution, and recrystallizing the solution by a vapor diffusion method, a poor solvent method, concentrating the solution under reduced pressure, cooling the solution, or heating the solution.

[0063] The crystals (S) may be crystals obtained by a production method including a recrystallization step as they are, or may be crystals that have been washed with a solvent to remove silanol compounds that have not been arranged in the recrystallization step and / or reagents used in the production of the dodecamer silanol compound described below. The solvent is not particularly limited, but examples include water, acetonitrile, diethyl ether, diisopropyl ether, tert-butyl ethyl ether, furan, tetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 1,4-dioxane, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N-methylacetamide, dimethyl sulfoxide, tetramethylurea, tetraethylurea, ethyl acetate, acetone, 2-butanone, benzene, toluene, cyclohexane, and hexane. These solvents may be used alone or in combination of two or more. When a polar solvent such as water, tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dimethylacetamide, or dimethylurea is used as the solvent, it is preferable to appropriately adjust the amount used to suppress dissolution of the crystals. Furthermore, in order to suppress dissolution of the crystals while maintaining cleaning power, the above polar solvents may be blended with other solvents in any ratio. Specifically, washing can be performed by contacting the crystals obtained by a production method including a recrystallization step with a solvent and then separating the liquid from the crystals.

[0064] The organic compound, transition metal complex, inorganic substance, and elemental substance to be brought into contact with the crystal (S) may be liquid or solid. When the organic compound, transition metal complex, inorganic substance, and elemental substance are solid, it is preferable to bring them into contact with the crystal (S) using a solution in which the solid is dissolved in a solvent. In addition, it is preferable to use a solvent that is bulkier than the pore size of the nanohoneycomb structure of the three-dimensional crystal. By using the bulky solvent, substitution from the substance contained in the crystal (S) tends to occur easily.

[0065] [Method for Producing a Dodecamer Silanol Compound] The dodecamer silanol compound can be produced by organic synthesis techniques. Specifically, it can be produced as follows.

[0066] The dodecamer silanol compound can be produced, for example, by a production method including a proton exchange step (hereinafter sometimes abbreviated as "proton exchange step") in which a silicate having a structure represented by the following formula (1)' (hereinafter sometimes abbreviated as "silicate") is reacted with an acidic compound to obtain a solution containing the silanol compound represented by the following formula (1). The silicate having the structure represented by the following formula (1') may be produced by an organic synthesis method or is available as a commercially available product.

[0067] (1)' (In formula (1)', Q ＋ represents a cation.) (1)

[0068] Furthermore, it is preferable that the method for producing a dodecamer silanol compound further comprises a step of adding a poor solvent to the solution obtained in the proton exchange step to precipitate the silanol compound represented by formula (1), and isolating the silanol compound represented by formula (1) as a powder (hereinafter, this step may be abbreviated as an "isolation step").

[0069] The silicate, acidic compound, and other reaction conditions in the proton exchange step will be described in detail below.

[0070] (Proton Exchange Step) The specific type of silicate used in the proton exchange step, the specific type of acidic compound, the amount of acidic compound used, the type of reaction medium (solvent or dispersion medium), reaction conditions, etc. are not particularly limited and can be appropriately selected depending on the purpose.

[0071] The acidic compound used in the proton exchange step is preferably an acidic compound having an acid dissociation constant pKa in dimethyl sulfoxide (DMSO) (hereinafter sometimes abbreviated as "pKa(DMSO)") of -1 to 20.

[0072] Proton exchange with an acidic compound having a pKa(DMSO) of -1 to 20 tends to enable efficient production of a silanol compound. When the pKa(DMSO) is -1 to 20, the cation (Q ＋ ) and the protons of the acidic compound (H ＋ ) exchange proceeds efficiently, and side reactions are suppressed. Therefore, the silanol compound itself can be synthesized with high yield. Furthermore, the method for producing a silanol compound according to this embodiment is a production method that is very suitable for industrial use because the reaction proceeds quickly under mild conditions. Note that the smaller the pKa(DMSO), the faster the proton exchange step tends to proceed.

[0073] Furthermore, pKa (DMSO) refers to a known value calculated from the concentrations of each component in the acid dissociation equilibrium of an acidic compound in DMSO at 25° C. Specifically, it is a value obtained by converting the value Ka calculated by the following formula into a common logarithm:

[0074]

[0075] In the proton exchange step, a silicate having a structure represented by the following formula (1)' is reacted with an acidic compound. (In formula (1)', Q ＋ represents a cation.) In formula (1)′, Q ＋ The cation is not particularly limited, but for example, a lithium ion (Li ＋ ), sodium ions (Na ＋ ), potassium ions (K ＋ ), alkali metal ions such as magnesium ions (Mg ２＋ ), and calcium ions (Ca ２＋ ), alkaline earth metal ions such as iron (III) ions (Fe ３＋ ), copper (II) ions (Cu ２＋ ), and zinc ions (Zn ２＋ ), transition metal ions such as ammonium ions (NH ４ ＋ ), tetramethylammonium ion (NMe ４ ＋ ), ethyltrimethylammonium ion (NEtMe ３＋ ), diethyldimethylammonium ion (NEt ２ Me ２ ＋ ), triethylmethylammonium ion (NEtMe ＋ ), tetraethylammonium ion (NEt ４ ＋ ), tetrapropylammonium ion (NPr ４ ＋ ), and tetrabutylammonium ion (NBu ４ ＋ Among these, sodium ions (Na ＋ ), potassium ions (K ＋ ), tetramethylammonium ion (NMe ４ ＋ ), tetraethylammonium ion (NEt ４ ＋ ), and ethyltrimethylammonium ion (NEtMe ３ ＋ ) is particularly preferred.

[0076] In the proton exchange step, the silicate to be reacted with the acidic compound is not particularly limited, but may be, for example, a cage potassium silicate dodecamer (Q ), in which two α-cyclodextrins (αCD) are coordinated above and below, as shown in the following formula described in Angew. Chem. Int. Ed. Engl. 1997, 36, 743: １２ K １２ ) hydrate (dodecapotassium-2,4,6,8,10,12,14,16,18,20,22,24,25,26,27,28,29,30-octadecaoxa-1,3,5,7,9,11,13,15,17,19,21,23-dodecasilaheptacyclo[13.9.1.1 ３，１３ .1 ５，１１ .1 ７，２１ .1 ９，１９ .1 １７，２３ ]triacontane-1,3,5,7,9,11,13,15,17,19,21,23-dodecaquis(olate) bis(α-dextrin) hydrate (hereinafter referred to as "Q １２ K １２ ・2αCD・nH２ It may be abbreviated as ".O".)) Such a Q １２ K １２ ・2αCD・nH ２ O is not particularly limited, and can be prepared by referring to the descriptions in, for example, Angew. Chem. Int. Ed. Engl. 1997, 36, 743. and Crystals 2018, 8, 457.

[0077] The acidic compound is preferably an acidic compound having a pKa(DMSO) of −1 to 20. The pKa(DMSO) of the acidic compound is preferably 0 or more, more preferably 1 or more, even more preferably 2 or more, and is preferably 16 or less, more preferably 14 or less, even more preferably 8 or less. When the pKa(DMSO) of the acidic compound is within the above range, the silanol compound can be produced efficiently.

[0078] Specific examples of the acidic compound are not particularly limited, but include inorganic acids such as nitric acid (pKa(DMSO) is 1.4), sulfuric acid (pKa1(DMSO) is 1.4, pKa2(DMSO) is 14.7), hydrochloric acid (pKa(DMSO) is 2.1), and phosphoric acid (pKa1(DMSO) is 1.83, pKa2(DMSO) is 6.43, pKa3(DMSO) is 11.46), and organic acids which are at least one selected from the group consisting of acetic acid and compounds having structures represented by the following formulas (b-1) to (b-5). (In formulas (b-1) to (b-5), each X independently represents an oxygen atom, a sulfur atom, or an amino group (—NR ３ -) to R １ represents a hydrogen atom or a hydrocarbon group having 1 to 14 carbon atoms, R ２ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 14 carbon atoms.

[0079] When a proton exchange reaction using an organic acid is carried out in a reaction medium such as N,N-dimethylacetamide (hereinafter also referred to as "DMAc") or methanol (hereinafter also referred to as "MeOH"), which will be described later, the resulting ammonium salt or alkali metal salt dissolves in the reaction medium. For this reason, it is preferable to separate the by-product ammonium salt or alkali metal salt by column purification or the like. On the other hand, when a proton exchange reaction using an inorganic acid is carried out in a reaction medium such as tetrahydrofuran (hereinafter also referred to as "THF"), which will be described later, the resulting ammonium salt or alkali metal salt, α-dextrin, and chemical species derived from α-dextrin are difficult to dissolve in the reaction medium. For this reason, the ammonium salt or alkali metal salt can be separated by a simple separation means such as filter filtration, and a silanol compound solution is obtained as a filtrate. For this reason, the acidic compound is preferably an inorganic acid.

[0080] Among inorganic acids, nitric acid, sulfuric acid, hydrochloric acid, and phosphoric acid are preferred, nitric acid or hydrochloric acid is more preferred, and hydrochloric acid is particularly preferred. Hydrochloric acid is inexpensive and tends to result in a high yield.

[0081] The wavy lines in the above formulas (b-2) to (b-5) indicate that the end of the wavy line is an arbitrary structure. For example, the acidic compound may contain a functional group that is not involved in the reaction. Therefore, for example, the acidic compound having the structure represented by the above formula (b-4) may be a compound that contains a hydrocarbon group such as a methyl group at the end of the oxygen atom corresponding to X, such as dimethyl malonate represented by the following formula. Furthermore, for example, the acidic compound having the structure represented by the above formula (b-4) may be a compound in which the hydrocarbon group at the end of the oxygen atom corresponding to X is bonded to form a cyclic structure, such as Meldrum's acid represented by the following formula:

[0082]

[0083] The structures represented by the above formulas (b-1) to (b-5) are so-called β-dicarbonyl structures, and it is known that the hydrogen of the methylene group sandwiched between two carbonyl groups, i.e., the α-hydrogen, functions as an acid site. By having the structures represented by the above formulas (b-1) to (b-5), the acidic compound exhibits an appropriate acid dissociation constant, and the electrons of the anion generated by proton dissociation are delocalized within the structure. For example, an acidic compound having the structure represented by the above formula (b-2) dissociates protons as represented by the following formula. Therefore, it is believed that the acidic compounds having the structures represented by the above formulas (b-1) to (b-5) have reduced anion basicity and nucleophilicity, thereby effectively suppressing side reactions.

[0084]

[0085] X is an amino group (-NR ３ X is preferably an oxygen atom. １ When R is a hydrocarbon group, the number of carbon atoms is preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less. １ is not particularly limited, and examples thereof include a hydrogen atom, a methyl group (-Me), an ethyl group (-Et), an n-propyl group (-nPr), an i-propyl group (-iPr), an n-butyl group (-nBu), and a phenyl group (-Ph), but is preferably a hydrogen atom.

[0086] R ２ When R is a hydrocarbon group, the number of carbon atoms is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. ２ Examples of the alkyl group include a hydrogen atom, a methyl group (-Me), an ethyl group (-Et), an n-propyl group (-nPr), an i-propyl group (-iPr), and an n-butyl group (-nBu), and a hydrogen atom is preferred.

[0087] The acidic compound represented by the formula (b-4) is not particularly limited, but examples thereof include the acidic compound represented by the following formula (b-4-1): The acidic compound represented by the formula (b-5) includes the acidic compound represented by the following formula (b-5-1):

[0088] (In formulas (b-4-1) and (b-5-1), R １ represents a hydrogen atom or a hydrocarbon group having 1 to 14 carbon atoms, R ４ represents a divalent hydrocarbon group having 1 to 14 carbon atoms.

[0089] R ４ is not particularly limited, but examples thereof include a methylene group (—CH ２ -), ethylene group (-CH ２ CH ２ -), n-propylene group (-CH ２ CH ２ CH ２ -), dimethylmethylene group (-C(CH ３ ) ２ -), and i-propylene group (-CH(CH ３ ) CH ２ -) are listed.

[0090] Specific examples of the acidic compound include, but are not limited to, acetic acid (pKa(DMSO) is 12.6), benzoic acid (pKa(DMSO) is 11.1), Meldrum's acid (pKa(DMSO) is 7.3), Meldrum's acid derivatives, dimedone (pKa(DMSO) is 11.2), dimedone derivatives, acetylacetone (pKa(DMSO) is 13.3), and acetylacetone derivatives (see the formula below).

[0091]

[0092] The acidic compound may be a low molecular weight compound such as Meldrum's acid, or an organic solid material such as a resin, or an inorganic solid material such as silica or carbon, to which a compound represented by one of the formulas (b-2) to (b-5) has been introduced. When the acidic compound is a solid, it can be packed into a column and used like an ion exchange resin. This allows for highly efficient production of silanol compounds. A common solid acid (e.g., Amberlyst or Amberlite) may also be used as the acidic compound.

[0093] In particular, the acidic compound is preferably a resin having at least one structure selected from the group consisting of the above formulas (b-2) to (b-5), and is preferably one that can be regenerated as an acidic compound by exposing the resin to an acidic aqueous solution such as hydrochloric acid after the proton exchange step.

[0094] The amount of the acidic compound used in the proton exchange step, in terms of the amount of substance, relative to the silicate is usually at least 1 time, preferably at least 1.5 times, more preferably at least 2.0 times, and usually at most 50 times, preferably at most 20 times, more preferably at most 5 times. When the amount of the acidic compound used is within the above range, the silanol compound can be produced efficiently.

[0095] The reaction in the proton exchange step is preferably carried out in a liquid (reaction medium). Such a reaction medium is not particularly limited, but examples thereof include tetrahydrofuran (THF), tetrahydropyran, dioxane, diethyl ether (Et ２ether-based liquids such as dimethyl ether, diisopropyl ether, diphenyl ether, methyl ethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; alcohol-based liquids such as methanol, ethanol, n-propanol, and i-propanol; amide-based liquids such as formamide, N,N-dimethylformamide (DMF), acetamide, N-methylacetamide, N,N-dimethylacetamide (DMAc), urea, and tetramethylurea; ester-based liquids such as ethyl acetate, n-amyl acetate, and ethyl lactate; halogen-based liquids such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, and hexachloroethane; acetonitrile, acetone, methyl ethyl ketone, phenyl methyl ketone, dimethyl sulfoxide (DMSO), and water. The reaction medium is not limited to one type, and two or more types may be combined.

[0096] The amount of reaction medium used in the proton exchange step is preferably an amount that results in a silicate content of 0.005 to 0.04 mol / L. This is because this silicate content allows for efficient production of a silanol compound. The reaction temperature in the proton exchange step is usually -80°C or higher, preferably 0°C or higher, more preferably 20°C or higher, and usually 200°C or lower, preferably 70°C or lower, more preferably 40°C or lower. The reaction time in the proton exchange step is usually 48 hours or shorter, preferably 24 hours or shorter, more preferably 8 hours or shorter, and particularly preferably 1 hour or shorter. Within the above range, a silanol compound can be efficiently produced.

[0097] (Isolation Step) The method for producing a silanol compound of this embodiment preferably includes a step of adding a poor solvent to the solution of the silanol compound represented by formula (1) obtained in the proton exchange step, precipitating the silanol compound represented by formula (1), and isolating the silanol compound represented by formula (1) as a powder. By including such a step, the method for producing a silanol compound of this embodiment does not cause dehydration condensation even in the absence of a crystallization solvent, and the silanol compound represented by formula (1) can be extremely simply isolated as a single powder.

[0098] The poor solvent for precipitating the silanol compound represented by the above formula (1) is not particularly limited, but examples thereof include hexane, benzene, toluene, dibutyl ether, diisopropyl ether, diethyl ether, dichloromethane, chloroform, and ethyl acetate. Among these, hexane, benzene, diisopropyl ether, and ethyl acetate are preferred, and diethyl ether and ethyl acetate are particularly preferred. In addition, in the isolation step, the silicate to be reacted with the acidic compound may be a precursor (e.g., Q １２ K １２ ・2αCD・nH ２ When using a silanol compound represented by formula (1), it is preferable to use a solvent that dissolves the ligand and its decomposition products (e.g., αCD and αCD decomposition products) as a poor solvent for precipitating the silanol compound represented by formula (1). The boiling point of the poor solvent for precipitating the silanol compound represented by formula (1) is usually 0°C or higher, preferably 10°C or higher, and more preferably 30°C or higher, and usually 300°C or lower, preferably 200°C or lower, and more preferably 150°C or lower.

[0099] In addition, the solution obtained in the proton exchange step is preferably filtered to remove salts produced by the reaction, and the filtrate is then concentrated to obtain a concentrate. By using such a concentrate, the silanol compound represented by formula (1) can be precipitated more efficiently.

[0100] In the isolation step, the time for precipitating the silanol compound represented by formula (1) is not particularly limited and can be selected appropriately, and is usually 24 hours or less, preferably 12 hours or less, more preferably 6 hours or less, and usually 0.25 hours or more, preferably 0.5 hours or more, more preferably 1 hour or more. When precipitating the silanol compound, stirring the mixture makes the precipitated particles more uniform and makes it easier to powder them in the drying step.

[0101] The method for isolating the silanol compound represented by formula (1) as a powder is not particularly limited, but may be, for example, filtration. Furthermore, it is preferable to dry the powder of the silanol compound represented by formula (1) obtained by such an isolation method. The drying temperature, drying pressure, drying time, etc. are not particularly limited and can be appropriately selected depending on the purpose.

[0102] When producing the crystal of this embodiment, the desired one-dimensional, two-dimensional, or three-dimensional structure can be obtained by controlling the formation of hydrogen bonds during the recrystallization process. Methods for controlling the formation of hydrogen bonds include, for example, selecting the type of solvent in which the silanol compound is dissolved, controlling the temperature during recrystallization, controlling the degree of vacuum during solvent removal, and adding a substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements, preferably an organic compound, in addition to the solvent. Among these control methods, the method of selecting the type of solvent in which the silanol compound is dissolved is preferred. In particular, by using a solvent with low hydrogen bonding ability with the silanol compound as the solvent, the formation of hydrogen bonds between the silanol compound and the solvent molecules is suppressed, and the formation of hydrogen bonds between the silanol compounds is controlled so as to be promoted. The solvent may be appropriately selected from diethyl ether, diisopropyl ether, tert-butyl ethyl ether, furan, tetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 1,4-dioxane, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N-methylacetamide, dimethyl sulfoxide, tetramethylurea, tetraethylurea, water, etc. These may be used alone or in combination of two or more. Furthermore, by using a mixed solvent of two or more types and changing the mixing ratio of the two types, the degree of hydrogen bond formation between the silanol compound and the solvent molecules can be adjusted, and a desired one-dimensional structure, two-dimensional structure, or three-dimensional structure can be produced.

[0103] Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples.

[0104] Synthesis Example 1 Dodecapotassium-2,4,6,8,10,12,14,16,18,20,22,24,25,26,27,28,29,30-octadecaoxa-1,3,5,7,9,11,13,15,17,19,21,23-dodecasilaheptacyclo[13.9.1.1 ３，１３ .1 ５，１１ .1 ７，２１ .1 ９，１９ .1 １７，２３ ]triacontane-1,3,5,7,9,11,13,15,17,19,21,23-dodecaquis(olate) bis(α-dextrin) hydrate (hereinafter referred to as "Q １２ K １２ ・2αCD・nH ２ It may be abbreviated as "O".) Q １２ K １２ ・2αCD・59.1H ２ 41.572 g (9.674 mmol) of HCl was suspended in 480 mL of THF, to which 24.051 mL (288.0 mmol) of hydrochloric acid was added and stirred for 15 minutes to obtain a suspension. This suspension was filtered to obtain a filtrate. 450 mL of ethyl acetate was added to the obtained filtrate, and the mixture was stirred for 60 minutes to cause reprecipitation (precipitation of solids). This suspension was filtered to separate the solids. After collecting the solids, they were dried under reduced pressure to obtain a compound having the composition formula Si １２ O ３０ H １２ (a compound represented by the following formula (1), ３，１３ .1 ５，１１ .1 ７，２１ .1 ９，１９ .1 １７，２３ ]triacontane-1,3,5,7,9,11,13,15,17,19,21,23-dodecaol (CAS No. 126347-25-9 (hereinafter referred to as "Q １２ H１２ )) was isolated as a colorless solid (powder) in a yield of 66% (6.116 g). [Example 1] Q １２ H １２ One-dimensional (rod-shaped) crystals (DMF-containing composition) of Q １２ H １２ 0.100 g of this compound was dissolved in 2.0 mL of N,N-dimethylformamide (DMF), and the solution was recrystallized at room temperature by the vapor diffusion method, which is a method of adding diethyl ether, a poor solvent, to the solution. １２ H １２ 0.131 g of a colorless solid (columnar crystal) containing 58.6% by mass of １ H-NMR (DMSO-d ６ ): 7.08ppm, ２９ Si-NMR (DMSO-d ６ ): -101.3 ppm). Furthermore, single crystal X-ray crystal structure analysis revealed that the obtained crystals consisted of one molecule of Q １２ H １２ and 8 molecules of DMF are assembled into a crystal structure, Q １２ H １２ It was revealed that the molecules are stabilized by hydrogen bonds, forming a one-dimensional (rod-like) structure (a one-dimensional rod-like structure formed by eight-membered ring (tetramer) planes). The crystal structure determined by single-crystal X-ray crystal structure analysis is shown in Figure 2.

[0105] [Example 2] Q １２ H １２ Two-dimensional (sheet-like) crystals (DMAc, THF-containing composition) of Q prepared by a method in accordance with Synthesis Example 1 １２ H １２ 0.030 g of Q was mixed with 4.0 mL of THF and 0.06 mL of N,N-dimethylacetamide (DMAc), and recrystallized at room temperature by the so-called anti-solvent method, in which THF, a poor solvent, was added to the solution all at once. １２ H １２ 0.039 g of a colorless solid (plate crystal) was isolated, which was a composition containing 64.2% by mass of １ H-NMR (DMSO-d ６): 7.07ppm, ２９ Si-NMR (DMSO-d ６ ): -101.2 ppm). Furthermore, single crystal X-ray crystal structure analysis revealed that the obtained crystals consisted of one molecule of Q １２ H １２ It is a crystal structure composed of two molecules of DMAc and four molecules of THF. １２ H １２ It was revealed that the molecules have a two-dimensional (sheet-like) structure stabilized by hydrogen bonds. The crystal structure determined by single-crystal X-ray crystal structure analysis is shown in Figure 3.

[0106] [Example 3] Q １２ H １２ Three-dimensional (nano-sponge-like) crystals of (THF, water-containing composition) Q prepared by a method in accordance with Synthesis Example 1 １２ H １２ 0.102 g of Q4 was dissolved in 10.0 mL of THF and 0.15 mL of water, and then the solution was allowed to stand at room temperature for recrystallization by adding THF, a poor solvent, all at once, a so-called poor solvent method. １２ H １２ 0.109 g of a colorless solid (columnar crystal) was isolated, which was a composition containing 71.9% by mass of １ H-NMR (DMSO-d ６ ): 7.07ppm, ２９ Si-NMR (DMSO-d ６ ): -101.2 ppm). Furthermore, single crystal X-ray crystal structure analysis revealed that the obtained crystals consisted of one molecule of Q １２ H １２ The crystal structure is composed of three molecules of THF and six molecules of water. １２ H １２ It was revealed that the molecules have a three-dimensional (nano-sponge-like) structure stabilized by hydrogen bonds. The crystal structure determined by single-crystal X-ray crystal structure analysis is shown in Figure 4.

[0107] [Example 4] Q １２ H １２ Three-dimensional (nano-honeycomb) crystals (dioxane-containing composition) of Q prepared by a method in accordance with Synthesis Example 1 １２ H １２0.208 g of Q was dissolved in 6.0 mL of 1,4-dioxane and 0.20 mL of water to obtain a solution. This solution was heated at 100°C and maintained for 6 hours to recrystallize, thereby obtaining Q １２ H １２ 0.173 g of a colorless solid (columnar crystal) was isolated, which was a composition containing 81.4% by mass of １ H-NMR (DMSO-d ６ ): 7.07ppm, ２９ Si-NMR (DMSO-d ６ ): -101.2 ppm). Furthermore, single crystal X-ray crystal structure analysis revealed that the obtained crystals consisted of one molecule of Q １２ H １２ and one molecule of 1,4-dioxane. Q １２ H １２ It was revealed that the molecules are stabilized by hydrogen bonds to form a three-dimensional (nano-honeycomb) structure (Type 1 (12-membered ring (hexamer) plane-to-plane structure)). The crystal structure determined by single-crystal X-ray crystal structure analysis is shown in Figure 5.

[0108] [Example 5] Q １２ H １２ Three-dimensional (nano-honeycomb) crystals (dioxane-containing composition) of Q prepared by a method in accordance with Synthesis Example 1 １２ H １２ 0.100 g of Q was dissolved in 6.0 mL of 1,4-dioxane and 0.10 mL of water to obtain a solution. This solution was concentrated under reduced pressure (35 torr) at 25°C and recrystallized to obtain Q １２ H １２ 0.081 g of a colorless solid (plate crystal) was isolated, which was a composition containing 59.7% by mass of １ H-NMR (DMSO-d ６ ): 7.07ppm, ２９ Si-NMR (DMSO-d ６ ): -101.2 ppm). Furthermore, single crystal X-ray crystal structure analysis revealed that the obtained crystals consisted of one molecule of Q １２ H １２ and 5.5 molecules of 1,4-dioxane are assembled into a crystal structure, Q １２ H １２It was revealed that the molecules are stabilized by hydrogen bonds to form a three-dimensional (nano-honeycomb) structure (type 2 (a structure in which the planes of the eight-membered ring (tetramer) are shifted by half every two molecules)). The crystal structure determined by single-crystal X-ray crystal structure analysis is shown in Figure 6.

[0109] [Example 6] Q １２ H １２ Three-dimensional (nano-honeycomb) crystals (diethylene glycol dimethyl ether-containing composition) of Q １２ H １２ 0.010 g of Q was added to 2.0 mL of diethylene glycol dimethyl ether, and the solution was heated at 60°C. After that, the solution was allowed to stand at room temperature and cooled to cause recrystallization. １２ H １２ 0.008 g of a colorless solid (plate crystal) was isolated, which was a composition containing 75.5% by mass of １ H-NMR (DMSO-d ６ ): 7.07ppm, ２９ Si-NMR (DMSO-d ６ ): -101.2 ppm). Furthermore, single crystal X-ray crystal structure analysis revealed that the obtained crystals consisted of one molecule of Q １２ H １２ and two molecules of diethylene glycol dimethyl ether are assembled into a crystal structure, Q １２ H １２ It was revealed that the molecules are stabilized by hydrogen bonds, forming a three-dimensional (nano-honeycomb) structure (type 3 (8-membered ring (tetramer) planes) structure). The crystal structure determined by single-crystal X-ray crystal structure analysis is shown in Figure 7.

[0110] [Example 7] Q １２ H １２ Three-dimensional (nano-honeycomb) crystals (benzene-containing composition) of Q １２ H １２ 0.205 g of Q was dissolved in 6.0 mL of 1,4-dioxane and 0.20 mL of water to obtain a solution. This solution was heated at 100°C and maintained for 6 hours to recrystallize, thereby obtaining Q １２ H １２A colorless solid (columnar crystals) containing 81.4% by mass of Q was isolated. This colorless solid was washed five times with 3.0 mL of acetonitrile, and then 10 mL of acetonitrile was added and the solid was allowed to stand at room temperature for 24 hours. The liquid (acetonitrile) was removed, and the solid was washed five times with 3.0 mL of benzene, and then 10 mL of benzene was added and the solid was allowed to stand at room temperature for 24 hours. By removing the liquid (benzene), Q １２ H １２ 0.167 g of a colorless solid (columnar crystal) containing 84.4% by mass of １ H-NMR (DMSO-d ６ ): 7.07ppm, ２９ Si-NMR (DMSO-d ６ ): -101.2 ppm). Furthermore, single crystal X-ray crystal structure analysis revealed that the obtained crystals consisted of one molecule of Q １２ H １２ and one molecule of benzene. １２ H １２ It was revealed that the molecules have a three-dimensional (nanohoneycomb-like) structure (Type 1 (12-membered ring (hexamer) plane-to-plane structure)) stabilized by hydrogen bonds.

[0111] [Example 8] Q １２ H １２ Three-dimensional (nano-honeycomb) crystals (naphthalene-containing composition) prepared by a method conforming to Synthesis Example 1. １２ H １２ 0.202 g of Q was dissolved in 5.0 mL of 1,4-dioxane and 0.20 mL of water to obtain a solution. This solution was heated at 100°C and maintained for 6 hours to recrystallize, thereby obtaining Q １２ H １２ A colorless solid (columnar crystals) containing 81.4% by mass of the compound was isolated. This colorless solid was washed five times with 3.0 mL of acetonitrile, and then 10 mL of acetonitrile was added and the mixture was left standing at room temperature for 24 hours. The liquid (acetonitrile) was removed, and a solution containing 5.0 mL of 1,3,5-triisopropylbenzene and 0.515 g (4.000 mmol) of naphthalene was added, followed by leaving the mixture standing at 60°C for 44 hours. By removing the liquid (naphthalene / 1,3,5-triisopropylbenzene solution), Q １２ H １２0.147 g of a colorless solid (columnar crystal) was isolated, which was a composition containing 90.3% by mass of １ H-NMR (DMSO-d ６ ): 7.07ppm, ２９ Si-NMR (DMSO-d ６ ): -101.2 ppm). Furthermore, single crystal X-ray crystal structure analysis revealed that the obtained crystals consisted of one molecule of Q １２ H １２ and 0.59 molecules of naphthalene and 0.33 molecules of acetonitrile are assembled into a crystal structure, Q １２ H １２ It was revealed that the molecules have a three-dimensional (nanohoneycomb-like) structure (Type 1 (12-membered ring (hexamer) plane-to-plane structure)) stabilized by hydrogen bonds.

[0112] [Example 9] Q １２ H １２ Three-dimensional (nano-honeycomb) crystals (anthracene-containing composition) prepared by a method conforming to Synthesis Example 1. １２ H １２ 0.210 g of Q was dissolved in 5.0 mL of 1,4-dioxane and 0.20 mL of water to obtain a solution. This solution was heated at 100°C and maintained for 6 hours to recrystallize, thereby obtaining Q １２ H １２ A colorless solid (columnar crystals) containing 81.4% by mass of the compound was isolated. This colorless solid was washed five times with 3.0 mL of acetonitrile, and then 10 mL of acetonitrile was added and the mixture was left standing at room temperature for 24 hours. The liquid (acetonitrile) was removed, and a solution containing 20.0 mL of 1,3,5-triisopropylbenzene and 0.180 g (1.010 mmol) of anthracene was added, followed by leaving the mixture standing at 60°C for 44 hours. By removing the liquid (anthracene / 1,3,5-triisopropylbenzene solution), Q １２ H １２ 0.156 g of a colorless solid (columnar crystal) containing 85.7% by mass of １ H-NMR (DMSO-d ６ ): 7.07ppm, ２９ Si-NMR (DMSO-d ６): -101.2 ppm). Furthermore, single crystal X-ray crystal structure analysis revealed that the obtained crystals consisted of one molecule of Q １２ H １２ and a crystal structure consisting of 0.70 molecules of anthracene and 0.31 molecules of acetonitrile, and Q １２ H １２ It was revealed that the molecules have a three-dimensional (nanohoneycomb-like) structure (Type 1 (12-membered ring (hexamer) plane-to-plane structure)) stabilized by hydrogen bonds.

[0113] [Example 10] Q １２ H １２ Three-dimensional (nano-honeycomb) crystals (biphenyl-containing composition) of Q １２ H １２ 0.211 g of Q was dissolved in 6.0 mL of 1,4-dioxane and 0.20 mL of water to obtain a solution. This solution was heated at 100°C and maintained for 6 hours to recrystallize, thereby obtaining Q １２ H １２ A colorless solid (columnar crystals) containing 81.4% by mass of the compound was isolated. This colorless solid was washed five times with 3.0 mL of acetonitrile, and then 10 mL of acetonitrile was added and the mixture was allowed to stand at room temperature for 24 hours. The liquid (acetonitrile) was removed, and a solution containing 5.0 mL of 1,3,5-triisopropylbenzene and 0.255 g (1.650 mmol) of biphenyl was added, followed by allowing the mixture to stand at 25°C under reduced pressure (100 hPa) for 48 hours. By removing the liquid (biphenyl / 1,3,5-triisopropylbenzene solution), Q １２ H １２ 0.171 g of a colorless solid (columnar crystal) was isolated, which was a composition containing 88.6% by mass of １ H-NMR (DMSO-d ６ ): 7.07ppm, ２９ Si-NMR (DMSO-d ６ ): -101.2 ppm). Furthermore, single crystal X-ray crystal structure analysis revealed that the obtained crystals consisted of one molecule of Q １２ H １２ and 0.65 molecules of biphenyl and 0.15 molecules of acetonitrile are assembled into a crystal structure, Q １２ H １２It was revealed that the molecules have a three-dimensional (nanohoneycomb-like) structure (Type 1 (12-membered ring (hexamer) plane-to-plane structure)) stabilized by hydrogen bonds.

[0114] [Example 11] Q １２ H １２ Three-dimensional (nano-honeycomb) crystals (p-terphenyl-containing composition) of Q １２ H １２ 0.208 g of Q was dissolved in 6.0 mL of 1,4-dioxane and 0.20 mL of water to obtain a solution. This solution was heated at 100°C and maintained for 6 hours to recrystallize, thereby obtaining Q １２ H １２ A colorless solid (columnar crystals) containing 81.4% by mass of the compound was isolated. This colorless solid was washed five times with 3.0 mL of acetonitrile, and then 10 mL of acetonitrile was added and the mixture was left to stand at room temperature for 24 hours. The liquid (acetonitrile) was removed, and a solution containing 5.0 mL of 1,3,5-triisopropylbenzene and 0.234 g (1.016 mmol) of p-terphenyl was added, followed by standing at 65°C under reduced pressure (100 torr) for 48 hours. By removing the liquid (p-terphenyl / 1,3,5-triisopropylbenzene solution), Q １２ H １２ 0.176 g of a colorless solid (columnar crystal) was isolated, which was a composition containing 86.7% by mass of １ H-NMR (DMSO-d ６ ): 7.07ppm, ２９ Si-NMR (DMSO-d ６ ): -101.2 ppm). Furthermore, single crystal X-ray crystal structure analysis revealed that the obtained crystals consisted of one molecule of Q １２ H １２ and 0.54 molecules of p-terphenyl and 0.06 molecules of acetonitrile are assembled into a crystal structure, Q １２ H １２ It was revealed that the molecules have a three-dimensional (nanohoneycomb-like) structure (Type 1 (12-membered ring (hexamer) plane-to-plane structure)) stabilized by hydrogen bonds.

[0115] [Example 12] Q １２ H １２Three-dimensional (nano-honeycomb) crystals (1,4-benzoquinone-containing composition) prepared by a method in accordance with Synthesis Example 1. １２ H １２ 0.203 g of Q was dissolved in 6.0 mL of 1,4-dioxane and 0.20 mL of water to obtain a solution. This solution was heated at 100°C and maintained for 6 hours to recrystallize, thereby obtaining Q １２ H １２ A colorless solid (columnar crystals) containing 81.4% by mass of the compound was isolated. This colorless solid was washed five times with 3.0 mL of acetonitrile, after which 10 mL of acetonitrile was added and the mixture was allowed to stand at room temperature for 24 hours. The liquid (acetonitrile) was removed, and a solution containing 8.0 mL of 1,3,5-triisopropylbenzene and 0.112 g (1.034 mmol) of 1,4-benzoquinone was added, followed by allowing the mixture to stand at room temperature under reduced pressure (100 hPa) for 70 hours. By removing the liquid (1,4-benzoquinone / 1,3,5-triisopropylbenzene solution), Q １２ H １２ 0.159 g of a yellow solid (columnar crystal) was isolated, which was a composition containing 88.2% by mass of １ H-NMR (DMSO-d ６ ): 7.07ppm, ２９ Si-NMR (DMSO-d ６ ): -101.2 ppm). Furthermore, single crystal X-ray crystal structure analysis revealed that the obtained crystals consisted of one molecule of Q １２ H １２ and a crystal structure consisting of 0.96 molecules of 1,4-benzoquinone and 0.17 molecules of acetonitrile, and Q １２ H １２ It was revealed that the molecules have a three-dimensional (nanohoneycomb-like) structure (Type 1 (12-membered ring (hexamer) plane-to-plane structure)) stabilized by hydrogen bonds.

[0116] [Example 13] Q １２ H １２ Three-dimensional (nano-honeycomb) crystals (thiophene-containing composition) prepared by a method in accordance with Synthesis Example 1 １２ H １２0.211 g of Q was dissolved in 6.0 mL of 1,4-dioxane and 0.20 mL of water to obtain a solution. This solution was heated at 100°C and maintained for 6 hours to recrystallize, thereby obtaining Q １２ H １２ A colorless solid (columnar crystals) containing 81.4% by mass of Q was isolated. This colorless solid was washed five times with 3.0 mL of acetonitrile, and then 10 mL of acetonitrile was added and the solid was allowed to stand at room temperature for 24 hours. The liquid (acetonitrile) was removed, and the solid was washed five times with 3.0 mL of thiophene, and then 10 mL of thiophene was added and the solid was allowed to stand at room temperature for 24 hours. By removing the liquid (thiophene), Q １２ H １２ 0.200 g of a colorless solid (columnar crystal) containing 74.2% by mass of １ H-NMR (DMSO-d ６ ): 7.07ppm, ２９ Si-NMR (DMSO-d ６ ): -101.2 ppm). Furthermore, single crystal X-ray crystal structure analysis revealed that the obtained crystals consisted of one molecule of Q １２ H １２ and one molecule of thiophene. １２ H １２ It was revealed that the molecules have a three-dimensional (nanohoneycomb-like) structure (Type 1 (12-membered ring (hexamer) plane-to-plane structure)) stabilized by hydrogen bonds.

[0117] [Example 14] Q １２ H １２ Three-dimensional (nano-honeycomb) crystals (dibromoterthiophene-containing composition) of Q １２ H １２ 0.103 g of Q was dissolved in 10.0 mL of 1,4-dioxane and 0.10 mL of water to obtain a solution. This solution was heated at 100°C and maintained for 6 hours to recrystallize, thereby obtaining Q １２ H １２A colorless solid (columnar crystals) containing 81.4% by mass of the compound was isolated. This colorless solid was washed five times with 3.0 mL of acetonitrile, and then 10 mL of acetonitrile was added and the mixture was allowed to stand at room temperature for 24 hours. The liquid (acetonitrile) was removed, and a solution containing 12.0 mL of 1,3,5-triisopropylbenzene and 0.051 g (0.126 mmol) of dibromoterthiophene was added, followed by allowing the mixture to stand at 60°C for 100 hours. By removing the liquid (dibromoterthiophene / 1,3,5-triisopropylbenzene solution), Q １２ H １２ 0.083 g of a deep green solid (columnar crystal) containing 79.4% by mass of １ H-NMR (DMSO-d ６ ): 7.07ppm, ２９ Si-NMR (DMSO-d ６ ): -101.2 ppm). Furthermore, single crystal X-ray crystal structure analysis revealed that the obtained crystals consisted of one molecule of Q １２ H １２ and 0.50 molecules of dibromoterthiophene and 0.29 molecules of acetonitrile are assembled into a crystal structure, Q １２ H １２ It was revealed that the molecules have a three-dimensional (nanohoneycomb-like) structure (Type 1 (12-membered ring (hexamer) plane-to-plane structure)) stabilized by hydrogen bonds.

[0118] [Example 15] Q １２ H １２ Three-dimensional (nano-honeycomb) crystals (dodecane-containing composition) of Q １２ H １２ 0.206 g of Q was dissolved in 6.0 mL of 1,4-dioxane and 0.20 mL of water to obtain a solution. This solution was heated at 100°C and maintained for 6 hours to recrystallize, thereby obtaining Q １２ H １２A colorless solid (columnar crystals) was isolated, which was a composition containing 81.4 mass% of Q. This colorless solid was washed five times with 3.0 mL of acetonitrile, after which 10 mL of acetonitrile was added and the mixture was left standing at room temperature for 24 hours. The liquid (acetonitrile) was removed, and the solid was washed five times with 3.0 mL of benzene, after which 10 mL of benzene was added and the mixture was left standing at room temperature for 24 hours. The liquid (benzene) was removed, and the solid was washed five times with 3.0 mL of dodecane, after which 10 mL of dodecane was added and the mixture was left standing at room temperature for 24 hours. By removing the liquid (dodecane), Q １２ H １２ 0.169 g of a colorless solid (columnar crystal) was isolated, which was a composition containing 85.9% by mass of １ H-NMR (DMF-d ７ ): 7.40ppm, ２９ Si-NMR (DMF-d ７ ): -100.5 ppm). Furthermore, single crystal X-ray crystal structure analysis revealed that the obtained crystals consisted of one molecule of Q １２ H １２ and 0.80 molecules of dodecane are assembled into a crystal structure, and Q １２ H １２ It was revealed that the molecules have a three-dimensional (nanohoneycomb-like) structure (Type 1 (12-membered ring (hexamer) plane-to-plane structure)) stabilized by hydrogen bonds.

[0119] [Example 16] Q １２ H １２ Three-dimensional (nano-honeycomb) crystals (ferrocene-containing composition) of Q １２ H １２ 0.102 g of Q was dissolved in 10.0 mL of 1,4-dioxane and 0.10 mL of water to obtain a solution. This solution was heated at 100°C and maintained for 6 hours to recrystallize, thereby obtaining Q １２ H １２A colorless solid (columnar crystals) containing 81.4% by mass of Q was isolated. This colorless solid was washed five times with 3.0 mL of acetonitrile, and then 10 mL of acetonitrile was added and the mixture was allowed to stand at room temperature for 24 hours. The liquid (acetonitrile) was removed, and a solution containing 6.0 mL of 1,3,5-triisopropylbenzene and 0.380 g (2.042 mmol) of ferrocene was added, followed by heating and allowing to stand under reduced pressure (50°C, 75 torr) for 147 hours. By removing the liquid (ferrocene / 1,3,5-triisopropylbenzene solution), Q １２ H １２ 0.086 g of a black solid (columnar crystal) was isolated, which was a composition containing 89.7% by mass of １ H-NMR (DMSO-d ６ ): 7.07ppm, ２９ Si-NMR (DMSO-d ６ ): -101.2 ppm). Furthermore, single crystal X-ray crystal structure analysis revealed that the obtained crystals consisted of one molecule of Q １２ H １２ and 0.36 molecules of ferrocene and 0.70 molecules of acetonitrile are assembled into a crystal structure, Q １２ H １２ It was revealed that the molecules have a three-dimensional (nanohoneycomb-like) structure (Type 1 (12-membered ring (hexamer) plane-to-plane structure)) stabilized by hydrogen bonds.

[0120] [Example 17] Q １２ H １２ Three-dimensional (nano-honeycomb) crystals (cobalt complex-containing composition) of Q １２ H １２ 0.206 g of Q was dissolved in 5.0 mL of 1,4-dioxane and 0.20 mL of water to obtain a solution. This solution was heated at 100°C and maintained for 6 hours to recrystallize, thereby obtaining Q １２ H １２A colorless solid (columnar crystals) was isolated, which was a composition containing 81.4 mass% of the above. This colorless solid was washed five times with 3.0 mL of acetonitrile, and then 10 mL of acetonitrile was added and the mixture was allowed to stand at room temperature for 24 hours. The liquid (acetonitrile) was removed, and 2.0 mL of 1,3,5-triisopropylbenzene and cyclopentadienyldicarbonylcobalt (CoCp(CO) ２ A solution containing 0.180 g (1.000 mmol) of cyclopentadienyldicarbonylcobalt / 1,3,5-triisopropylbenzene was added, and the mixture was allowed to stand at room temperature for 48 hours. １２ H １２ 0.181 g of a brown solid (columnar crystal) was isolated, which was a composition containing 80.2% by mass of １ H-NMR (DMSO-d ６ ): 7.07ppm, ２９ Si-NMR (DMSO-d ６ ): -101.2 ppm). Furthermore, single crystal X-ray crystal structure analysis revealed that the obtained crystals consisted of one molecule of Q １２ H １２ and 0.97 molecules of cyclopentadienyldicarbonylcobalt and 0.75 molecules of acetonitrile, and Q １２ H １２ It was revealed that the molecules have a three-dimensional (nanohoneycomb-like) structure (Type 1 (12-membered ring (hexamer) plane-to-plane structure)) stabilized by hydrogen bonds.

[0121] [Example 18] Q １２ H １２ Three-dimensional (nano-honeycomb) crystals (iodine-containing composition) prepared by a method conforming to Synthesis Example 1, １２ H １２ 0.212 g of Q was dissolved in 10.0 mL of 1,4-dioxane and 0.20 mL of water to obtain a solution. This solution was heated at 100°C and maintained for 6 hours to recrystallize, thereby obtaining Q １２ H １２A colorless solid (columnar crystals) was isolated, which was a composition containing 81.4% by mass of the compound. This colorless solid was washed five times with 3.0 mL of acetonitrile, and then 10 mL of acetonitrile was added and the mixture was allowed to stand at room temperature for 24 hours. The liquid (acetonitrile) was removed, and 15.0 mL of 1,3,5-triisopropylbenzene and iodine (I ２ A solution containing 0.257 g (1.012 mmol) of iodine was added, and the mixture was allowed to stand at room temperature for 51 hours. １２ H １２ 0.192 g of a red solid (columnar crystal) was isolated, which was a composition containing 62.0% by mass of １ H-NMR (DMSO-d ６ ): 7.07ppm, ２９ Si-NMR (DMSO-d ６ ): -101.2 ppm). Furthermore, single crystal X-ray crystal structure analysis revealed that the obtained crystals consisted of one molecule of Q １２ H １２ and two iodine molecules are assembled into a crystal structure, Q １２ H １２ It was revealed that the molecules have a three-dimensional (nanohoneycomb-like) structure (Type 1 (12-membered ring (hexamer) plane-to-plane structure)) stabilized by hydrogen bonds.

[0122] [Example 19] Q １２ H １２ One-dimensional (rod-shaped) crystals (phenazine-containing composition) of Q １２ H １２ 0.100 g of Q was dissolved in 20 mL of THF, and the solution was filtered. 0.5 mL of a THF solution containing 0.25 mol % of phenazine was added to the resulting filtrate, and the mixture was left to stand at room temperature under reduced pressure (130 hPa) until the solvent disappeared. １２ H １２ A yellow solid (needle-shaped crystal) was isolated, which was a composition containing 43.4% by mass of . Furthermore, single crystal X-ray crystal structure analysis revealed that the obtained crystal contained one molecule of Q. １２ H １２ and six phenazine molecules are assembled into a crystal structure, Q １２ H １２It was revealed that the molecules are stabilized by hydrogen bonds, forming a one-dimensional (rod-like) structure (a one-dimensional rod-like structure formed by planes of 12-membered rings (hexamers)). The crystal structure determined by single-crystal X-ray crystal structure analysis is shown in Figure 8.

[0123] [Example 20] Q １２ H １２ Two-dimensional (sheet-like) crystals (2,2-bipyridyl-containing composition) of Q prepared by a method conforming to Synthesis Example 1 １２ H １２ 0.100 g of Q was dissolved in 20 mL of THF, and the solution was filtered. 0.05 mL of 2,2-bipyridyl was added to the obtained filtrate, and the mixture was left to stand at room temperature under reduced pressure (100 hPa) until the solvent disappeared. １２ H １２ A colorless solid (amorphous crystal) containing 45.1% by mass of the compound was isolated. Single crystal X-ray crystal structure analysis revealed that the obtained crystal contained one molecule of Q １２ H １２ The crystal structure is composed of six molecules of 2,2-bipyridyl and one molecule of THF. １２ H １２ It was revealed that the molecules have a two-dimensional (sheet-like) structure stabilized by hydrogen bonds. The crystal structure determined by single-crystal X-ray crystal structure analysis is shown in Figure 9.

[0124] [Example 21] Q １２ H １２ Three-dimensional (nano-honeycomb) crystals (pyridine-containing composition) of Q prepared by a method conforming to Synthesis Example 1 １２ H １２ 0.100 g of Q was dissolved in 20 mL of THF, and the solution was filtered. 0.05 mL of pyridine was added to the obtained filtrate, and the mixture was concentrated at room temperature under reduced pressure (100 hPa) until the remaining solution volume was 1 mL. １２ H １２ A colorless solid (rectangular plate-like crystal) containing 62.3% by mass of the compound was isolated. Single crystal X-ray crystal structure analysis revealed that the obtained crystal contained one molecule of Q １２ H １２ The crystal structure is composed of four molecules of pyridine and two molecules of THF.１２ H １２ It was revealed that the molecules have a three-dimensional structure stabilized by hydrogen bonds. The crystal structure determined by single-crystal X-ray crystal structure analysis is shown in Figure 10.

[0125] [Example 22] Q １２ H １２ Three-dimensional (nano-honeycomb) crystals (phenazine-containing composition) of Q prepared by a method conforming to Synthesis Example 1 １２ H １２ 0.100 g of the compound was dissolved in 20 mL of THF, and the solution was filtered. 0.5 mL of a THF solution containing 0.25 mol % of phenazine was added to the resulting filtrate, and the mixture was left to stand at room temperature under reduced pressure (300 hPa) for 15 hours. After that, the mixture was concentrated at 130 hPa until the remaining solution volume was 1 mL. １２ H １２ A yellow solid (rectangular plate-like crystal) containing 62.2% by mass of the compound was isolated. Single crystal X-ray crystal structure analysis revealed that the obtained crystal contained one molecule of Q １２ H １２ Q is a crystal structure formed by assembling two molecules of phenazine and two molecules of THF. １２ H １２ It was revealed that the molecules have a three-dimensional structure stabilized by hydrogen bonds. The crystal structure determined by single-crystal X-ray crystal structure analysis is shown in Figure 11.

[0126] This application is based on a Japanese patent application (Patent Application No. 2023-151414) filed on September 19, 2023, the contents of which are incorporated herein by reference.

[0127] By heating the crystal of the present invention or contacting it with an acid and / or a base, etc., it is possible to obtain a material having a regular microstructure. In particular, by combining it with other organic compounds, transition metal complexes, inorganic substances, elemental substances, etc., it is possible to create a material with a finely controlled structure having unprecedented physical properties. Furthermore, the crystal of the present invention can be used, for example, for drug delivery applications, etc. ２ It has industrial applicability as a raw material for obtaining materials.

Claims

1. A crystal comprising a plurality of silanol compounds represented by the following formula (1), which have interaction between the silanol compounds via a hydrogen bond formed by at least one hydroxyl group.

2. The crystal according to claim 1, wherein the silanol compound has a one-dimensional structure linearly aligned by interactions via the hydrogen bonds.

3. The crystal according to claim 1, wherein the silanol compound has a two-dimensional structure in which the silanol compound is aligned in a plane due to interactions via hydrogen bonds.

4. The crystal according to claim 1, wherein the silanol compound has a three-dimensional structure in which the silanol compound is spatially ordered due to interactions via the hydrogen bonds.

5. The crystal according to claim 1, comprising at least one substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements.

6. A method for producing the crystal according to any one of claims 1 to 5, comprising the steps of: preparing a solution containing the silanol compound; and adding at least one substance selected from the group consisting of an organic compound, a transition metal complex, an inorganic substance, and a simple element to the solution as necessary, and recrystallizing the solution by a vapor diffusion method.

7. A method for producing the crystal according to any one of claims 1 to 5, comprising: a step of preparing a solution containing the silanol compound; and a step of adding at least one substance selected from the group consisting of an organic compound, a transition metal complex, an inorganic substance, and a simple element to the solution as necessary, and recrystallizing the solution by a poor solvent method.

8. A method for producing the crystal according to any one of claims 1 to 5, comprising: a step of preparing a solution containing the silanol compound; and a step of adding at least one substance selected from the group consisting of an organic compound, a transition metal complex, an inorganic substance, and a simple element to the solution as necessary, and concentrating the solution under reduced pressure to recrystallize the solution.

9. A method for producing the crystal according to any one of claims 1 to 5, comprising: a step of preparing a solution containing the silanol compound; and a step of adding at least one substance selected from the group consisting of an organic compound, a transition metal complex, an inorganic substance, and a simple element to the solution as necessary, and cooling the solution to recrystallize.

10. A method for producing the crystal according to any one of claims 1 to 5, comprising: a step of preparing a solution containing the silanol compound; and a step of adding at least one substance selected from the group consisting of an organic compound, a transition metal complex, an inorganic substance, and a simple element to the solution as necessary, and heating the solution to recrystallize.

11. A method for producing a crystal (P) containing at least one substance selected from the group consisting of an organic compound, a transition metal complex, an inorganic substance, and a simple element, comprising the steps of: preparing a crystal (S) containing a plurality of silanol compounds represented by the following formula (1), which have an interaction between the silanol compounds via a hydrogen bond formed by at least one hydroxyl group, and which contains at least one first substance selected from the group consisting of an organic compound, a transition metal complex, an inorganic substance, and a simple element; contacting the crystal (S) with at least one second substance selected from the group consisting of an organic compound, a transition metal complex, an inorganic substance, and a simple element, to obtain a crystal (P) by replacing at least a portion of the first substance contained in the crystal (S) with the second substance.

12. The method according to claim 11, wherein the step of preparing the crystals (S) comprises: preparing a solution containing the silanol compound; and adding a substance selected from the group consisting of an organic compound, a transition metal complex, an inorganic substance, and a simple element to the solution as necessary, and recrystallizing the solution by a vapor diffusion method, a poor solvent method, concentrating the solution under reduced pressure, cooling the solution, or heating the solution.

13. A method for self-organizing a silanol compound represented by the following formula (1), comprising a step of forming an interaction through hydrogen bonds by a vapor diffusion method for a solution containing the silanol compound, or by a poor solvent method for the solution, or by concentrating the solution under reduced pressure, or by cooling the solution, or by heating the solution:

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