Compound and compound production method

Abstract

Provided is a compound having a pore structure in which one or more types of silanol compound selected from the group consisting of an octamer represented by formula (1), a decamer represented by formula (2), and a dodecamer represented by formula (3) are regularly arranged by being bonded to each other by dehydration condensation.

Description

Compounds and methods for producing compounds

[0001] The present invention relates to compounds and methods for making the compounds.

[0002] Conventional inorganic porous compounds include silica gel, activated carbon, and zeolite, each of which has been widely used industrially to take advantage of its unique properties. Zeolite, a microporous crystalline aluminosilicate, possesses molecular sieving, ion exchange, catalytic, and adsorption properties due to its unique structure. Its applications are diverse, including deodorization, water quality improvement, soil modification, and intestinal regulation in livestock. Zeolites are classified into natural, artificial, and synthetic zeolites. Natural zeolites are inexpensive because they are natural minerals formed by volcanic activity, but they have poor quality stability and absorption / adsorption capacity. Artificial zeolites are relatively inexpensive because they are made from waste materials such as incineration ash, making it difficult to achieve stable quality and uniform pore size. On the other hand, synthetic zeolites are produced using controlled industrial raw materials, resulting in homogeneous and stable quality.

[0003] Examples of synthetic zeolites include LTA-type zeolite represented by the following formula (i), FAU-type zeolite represented by the following formula (ii), and CHA-type zeolite represented by the following formula (iii).

[0004] Common methods for synthesizing synthetic zeolites include, for example, hydrothermal synthesis (e.g., 130-180°C, 1 day) in an autoclave using raw materials such as amorphous silica, alumina, or tetraethoxysilane (TEOS) in an aqueous solution together with a mineralizer or structure-directing agent such as sodium hydroxide, potassium hydroxide, or a quaternary ammonium salt. Methods for synthesizing zeolites by heating raw silicates and dehydrating and condensing them have also been proposed. Specifically, Non-Patent Document 1 proposes a method for synthesizing zeolites by heating rod-shaped silicates and dehydrating and condensing them. Non-Patent Documents 2 and 3 propose methods for synthesizing zeolites by heating layered silicates and dehydrating and condensing them.

[0005] Jian Li et al., "Supplementary Materials for A 3D extra-large-pore zeolite enabled by 1D-to-3D topotactic condensation of a chain silicate," Science, American Association for the Advancement of Science (AAAS), 2023, vol. 379, pp. 283-287; Jihong Yu et al., "Synthesis of new zeolite structures," Chemical Society Reviews, Royal Society of Chemistry, 2015, vol. 44, pp. 7112-7127; Michael E. Leonowicz et al., "MCM-22: A Molecular Sieve with Two Independent Multidimensional Channel Systems," Science, American Association for the Advancement of Science (AAAS), 1994, vol. 264, pp. 1910-1913

[0006] However, in the conventional general synthesis method of zeolite by hydrothermal synthesis, crystallization proceeds through repeated condensation and cleavage under hydrothermal conditions, resulting in a complex crystallization mechanism and making it difficult to control the crystal structure at the molecular level.Furthermore, the synthesis methods of zeolite by dehydration condensation described in Non-Patent Documents 1 to 3 require the use of specific precursors and specific structure-directing agents, which limits the range of possible synthesis.

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a compound having a regularly arranged pore structure while controlling the crystal structure at the molecular level, and to provide a novel compound having a regularly arranged pore structure.

[0008] As a result of intensive research to solve the above problems, the inventors discovered that a compound having a regularly arranged pore structure can be obtained by controlling the crystal structure at the molecular level using a specific method, and also discovered a novel compound having a specific pore structure, which led to the completion of the present invention.

[0009] That is, this application provides the following invention: [1] A compound having a pore structure in which at least one silanol compound selected from the group consisting of an octamer represented by the following formula (1), a decamer represented by the following formula (2), and a dodecamer represented by the following formula (3) is bonded to itself by dehydration condensation to form a regularly arranged pore (excluding LTA zeolite derived from the octamer represented by the following formula (1), and FAU zeolite and CHA zeolite derived from the dodecamer represented by the following formula (3)). [2] The compound according to [1], wherein the pore structure is a linearly aligned one-dimensional structure. [3] The compound according to [1], wherein the pore structure is a planarly aligned two-dimensional structure. [4] The compound according to [1], wherein the pore structure is a planarly aligned two-dimensional structure formed by covalent bonding of a plurality of linearly aligned one-dimensional structures. [5] The compound according to [1], wherein the pore structure is a sterically aligned three-dimensional structure. [6] The compound according to [1], wherein the pore structure is a sterically aligned three-dimensional structure formed by covalent bonding of a plurality of planarly aligned two-dimensional structures. [7] The compound according to any one of [1] to [6], wherein the pore structure is a structure in which hydrogen-bonding moieties in a hydrogen-bonding inorganic structure are converted into covalent bonds by dehydration condensation, and the hydrogen-bonding inorganic structure contains a plurality of the silanol compounds and is a crystal having interaction between the silanol compounds via hydrogen bonding through at least one hydroxy group between the silanol compounds. [8] The compound according to [1], wherein the pore structure is a linearly aligned one-dimensional structure in which two hydroxy groups contained in one silanol compound in the silanol compound are each bonded by dehydration condensation with a hydroxy group of another silanol compound, and the two hydroxy groups bonded by dehydration condensation are two hydroxy groups on adjacent silicon atoms in one silanol compound, or two hydroxy groups on silicon atoms separated by one or more siloxane bonds (—O—Si—O— bonds). [9] The compound according to [1], wherein the pore structure is a linearly aligned one-dimensional structure in which, of four hydroxy groups contained in one silanol compound in the silanol compound, two hydroxy groups bonded to adjacent silicon atoms are each bonded by dehydration condensation with two hydroxy groups bonded to adjacent silicon atoms of another silanol compound, and the remaining two hydroxy groups bonded to adjacent silicon atoms in the one silanol compound are further bonded by dehydration condensation with two hydroxy groups bonded to adjacent silicon atoms of another silanol compound, respectively.

[10] The compound according to [1], wherein the pore structure is a one-dimensional structure in which a surface of a cyclic silanol contained in one silanol compound in the silanol compound is linearly aligned by being bonded via a covalent bond to a surface of a cyclic silanol contained in another silanol compound.

[11] The compound according to

[10] , wherein the surface of the cyclic silanol is a surface of an 8-membered ring when the silanol compound is an octamer represented by formula (1), a surface of an 8- or 10-membered ring when the silanol compound is a decamer represented by formula (2), or a surface of an 8- or 12-membered ring when the silanol compound is a dodecamer represented by formula (3).

[12] The pore structure is a two-dimensional structure in which a plurality of one-dimensional structures are bonded to each other via covalent bonds and aligned in a plane, and the one-dimensional structure is a one-dimensional structure in which two hydroxy groups contained in one silanol compound are bonded to hydroxy groups of another silanol compound by dehydration condensation and aligned linearly, and the two hydroxy groups bonded by dehydration condensation are two hydroxy groups on adjacent silicon atoms in one silanol compound, or two hydroxy groups on silicon atoms separated by one siloxane bond (—O—Si—O— bond) or more, The compound according to [1], wherein two of the four hydroxy groups contained in one silanol compound that are bonded to adjacent silicon atoms are bonded to two hydroxy groups that are bonded to adjacent silicon atoms of another silanol compound by dehydration condensation, and the remaining two hydroxy groups that are bonded to adjacent silicon atoms of the one silanol compound are further bonded to two hydroxy groups that are bonded to adjacent silicon atoms of another silanol compound by dehydration condensation, thereby forming a linearly aligned one-dimensional structure.

[13] The pore structure is a two-dimensional structure in which ends of one-dimensional structures are bonded to each other via a covalent bond and aligned in a ring, and the one-dimensional structure is a one-dimensional structure in which two hydroxy groups contained in one silanol compound are linearly aligned by being bonded to hydroxy groups of another silanol compound by dehydration condensation, and the two hydroxy groups bonded by dehydration condensation are two hydroxy groups on adjacent silicon atoms in one silanol compound, or two hydroxy groups on silicon atoms separated by one siloxane bond (—O—Si—O— bond) or more, or The compound according to [1], wherein two of the four hydroxy groups contained in one silanol compound in the silanol compound that are bonded to adjacent silicon atoms are bonded to two hydroxy groups that are bonded to adjacent silicon atoms in another silanol compound by dehydration condensation, and the remaining two hydroxy groups that are bonded to adjacent silicon atoms in the one silanol compound are further bonded to two hydroxy groups that are bonded to adjacent silicon atoms in another silanol compound by dehydration condensation, thereby forming a linearly aligned one-dimensional structure.

[14] The compound according to [1], wherein the pore structure is a two-dimensional structure in which one longitudinal side of a plurality of one-dimensional structures is bonded to each other via a covalent bond and aligned in a plane, and the one-dimensional structure is a one-dimensional structure in which a plane of a cyclic silanol contained in one silanol compound in the silanol compound is bonded to a plane of a cyclic silanol of another silanol compound by a covalent bond and aligned in a linear manner.

[15] The pore structure is a three-dimensional structure in which a plurality of two-dimensional structures are bonded together via covalent bonds and sterically aligned, the two-dimensional structure is a two-dimensional structure in which a plurality of one-dimensional structures are bonded together via covalent bonds and aligned in a plane, the one-dimensional structure is a one-dimensional structure in which two hydroxy groups contained in one silanol compound in the silanol compound are bonded to hydroxy groups of another silanol compound by dehydration condensation and aligned linearly, and the two hydroxy groups bonded by dehydration condensation are two hydroxy groups on adjacent silicon atoms in one silanol compound, or two hydroxy groups on silicon atoms separated by one siloxane bond (—O—Si—O— bond) or more, or The compound according to [1], wherein two of the four hydroxy groups contained in one silanol compound that are bonded to adjacent silicon atoms are bonded to two hydroxy groups that are bonded to adjacent silicon atoms of another silanol compound by dehydration condensation, and the remaining two hydroxy groups that are bonded to adjacent silicon atoms of the one silanol compound are further bonded to two hydroxy groups that are bonded to adjacent silicon atoms of another silanol compound by dehydration condensation, thereby forming a linearly aligned one-dimensional structure.

[16] The pore structure is a three-dimensional structure in which a plurality of two-dimensional structures are bonded together via covalent bonds and sterically aligned, the two-dimensional structure being a two-dimensional structure in which ends of one-dimensional structures are bonded together via covalent bonds and aligned in a ring, the one-dimensional structure being a one-dimensional structure in which two hydroxy groups contained in one silanol compound are bonded to hydroxy groups of another silanol compound by dehydration condensation and aligned linearly, and the two hydroxy groups bonded by dehydration condensation are two hydroxy groups on adjacent silicon atoms in one silanol compound, or two hydroxy groups on silicon atoms separated by one siloxane bond (—O—Si—O— bond) or more, or The compound according to [1], wherein two of the four hydroxy groups contained in one silanol compound in the silanol compound that are bonded to adjacent silicon atoms are bonded to two hydroxy groups that are bonded to adjacent silicon atoms in another silanol compound by dehydration condensation, and the remaining two hydroxy groups that are bonded to adjacent silicon atoms in the one silanol compound are further bonded to two hydroxy groups that are bonded to adjacent silicon atoms in another silanol compound by dehydration condensation, thereby forming a linearly aligned one-dimensional structure.

[17] The compound according to [1], wherein the pore structure is a three-dimensional structure in which a plurality of two-dimensional structures are bonded to each other via covalent bonds and are sterically aligned, the two-dimensional structure is a two-dimensional structure in which one longitudinal side of a plurality of one-dimensional structures is bonded to each other via covalent bonds and is aligned in a plane, and the one-dimensional structure is a one-dimensional structure in which a plane of a cyclic silanol contained in one silanol compound in the silanol compound is bonded to a plane of a cyclic silanol of another silanol compound by covalent bonds and is aligned in a linear manner.

[18] The compound according to [2], wherein the one-dimensional structure is at least one structure selected from the group consisting of the following formulas (1-1) to (1-3): (In structural formulas (1-1) to (1-3), one Si—O—Si bond is omitted and represented by one side.)

[19] The compound according to [3], wherein the two-dimensional structure is at least one structure selected from the group consisting of the following formulas (2-1) and (2-2): (In structural formulas (2-1) to (2-2), one Si—O—Si bond is omitted and represented by one side.)

[20] The compound according to [5], wherein the three-dimensional structure is at least one structure selected from the group consisting of the following formulas (3-1) to (3-3): (In structural formulas (3-1) to (3-3), one Si—O—Si bond is omitted and represented by one side.)

[21] The compound according to any one of [1] to

[20] , comprising at least one substance selected from the group consisting of an organic compound, a transition metal complex, an inorganic substance, and a simple element.

[22] A method for producing a compound, comprising: a step of preparing a crystal (Z) containing a plurality of at least one silanol compound selected from the group consisting of an octamer represented by the following formula (1), a decamer represented by the following formula (2), and a dodecamer represented by the following formula (3), wherein the silanol compounds interact with each other via a hydrogen bond formed by at least one hydroxy group; a step of using the crystal (Z) to obtain an intermediate in which some of the silanol compounds are bonded together by dehydration condensation; and a step of heating the intermediate at 200 to 900° C. to obtain a compound having a regularly arranged pore structure in which the silanol compounds are bonded together by dehydration condensation.

[23] The step of obtaining an intermediate is a step of heating the crystal (Z) at 80 to 250°C in the presence of an additive and a solvent to obtain an intermediate in which some of the silanol compounds are bonded to each other by dehydration condensation, and in the step of obtaining an intermediate, the additive is an alkylammonium salt NR ４ ＋ X － (Wherein R is CH ３ , C ２ H ５ , C ３ H ７ , or C ４ H ９and X=Cl, Br, or CH ３ COO), tertiary amines and amidines, and the solvent is an alcohol R'OH (wherein R' is CH ３ , C ２ H ５ , C ３ H ７ , C ４ H ９ , C ５ H １１ , (CH ３ ) ２ CH, or (CH ３ ) ３ C.), organic acid R″COOH (wherein R″ is H, CH ３ , C ２ H ５ , C ３ H ７ , or C ４ H ９ ), and ester R １ COOR ２ (In the formula, R １ and R ２ are each independently CH ３ , C ２ H ５ , C ３ H ７ , C ４ H ９ , or C ６ H ５

[24] A method for producing the compound according to

[22] , wherein the crystal (Z) is at least one selected from the group consisting of:

[0023] (wherein the crystal (Z) is at least one selected from the group consisting of:

[0024] (wherein the crystal (Z) is at least one selected from the group consisting of:

[0025] (wherein the crystal (Z) is at least one selected from the group consisting of:

[0026] (wherein the crystal (Z) is at least one selected from the group consisting of:

[0027] (wherein the crystal (Z) is at least one selected from the group consisting of:

[0028] (wherein the crystal (Z) is at least one selected from the group consisting of: [0029 ...

[0010] According to the present invention, it is possible to provide a novel compound having a regularly arranged pore structure while controlling the crystal structure at the molecular level.

[0011] FIG. 1 is a diagram illustrating plane 1 and plane 2 in a schematic diagram of an aligned structure viewed from an oblique direction. FIG. 2 is a diagram illustrating a crystal structure determined by single-crystal X-ray crystal structure analysis of a crystal (three-dimensional (nanohoneycomb) structure) produced in Synthesis Example 1. FIG. 3 is a diagram illustrating a crystal structure determined by single-crystal X-ray crystal structure analysis of a crystal (three-dimensional (nanohoneycomb) structure) produced in Synthesis Example 3. FIG. 4 is a measurement result of powder X-ray crystal structure analysis of an intermediate produced in Example 1. ２９ 1 shows the results of Si-MAS-NMR measurement. 2 shows the results of powder X-ray crystal structure analysis of the intermediate produced in Example 2. ２９ 1 shows the results of Si-MAS-NMR measurement. 2 shows the results of powder X-ray crystal structure analysis of the crystals produced in Example 2. ２９ 1 shows the results of Si-MAS-NMR measurement. 2 shows the results of single crystal X-ray crystal structure analysis of the crystal produced in Example 2.

[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] [Method for Producing Compound] The method for producing a compound of this embodiment includes the steps of: preparing a crystal (Z) containing a plurality of at least one silanol compounds selected from the group consisting of an octamer represented by formula (1) below, a decamer represented by formula (2) below, and a dodecamer represented by formula (3) below, wherein the silanol compounds interact with each other via a hydrogen bond formed by at least one hydroxy group; using the crystal (Z) to obtain an intermediate in which some of the silanol compounds are bonded together by dehydration condensation; and heating the intermediate at 200 to 900°C to obtain a compound having a regularly arranged pore structure in which the silanol compounds are bonded together by dehydration condensation.

[0014] The method for producing a compound according to the present embodiment has such characteristics, and thus can produce a compound having a regularly arranged pore structure while controlling the crystal structure at the molecular level.

[0015] In the method for producing a compound of this embodiment, the step of obtaining the intermediate is a step of heating the crystal (Z) at 80 to 250°C in the presence of an additive and a solvent to obtain an intermediate in which some of the silanol compounds are bonded to each other by dehydration condensation, and in the step of obtaining the intermediate, the additive is an alkylammonium salt NR ４ ＋ X － (Wherein R is CH ３ , C ２ H ５ , C ３ H ７ , or C ４ H ９ and X=Cl, Br, or CH ３ COO), tertiary amines and amidines, and the solvent is an alcohol R'OH (wherein R' is CH ３ , C ２ H５ , C ３ H ７ , C ４ H ９ , C ５ H １１ , (CH ３ ) ２ CH, or (CH ３ ) ３ C.), organic acid R″COOH (wherein R″ is H, CH ３ , C ２ H ５ , C ３ H ７ , or C ４ H ９ ), and ester R １ COOR ２ (In the formula, R １ and R ２ are each independently CH ３ , C ２ H ５ , C ３ H ７ , C ４ H ９ , or C ６ H ５ It is preferable that the compound is at least one selected from the group consisting of:

[0016] Furthermore, in the method for producing a compound of this embodiment, the step of obtaining the intermediate may be a step of freeze-drying the crystals (Z) to obtain an intermediate in which some of the silanol compounds are bonded to each other by dehydration condensation.

[0017] [Crystal (Z)] The crystal (Z) (hereinafter also simply referred to as "crystal (Z)") used in the production method of this embodiment contains a plurality of at least one silanol compound selected from the group consisting of an octamer represented by formula (1) (hereinafter also simply referred to as "octamer"), a decamer represented by formula (2) (hereinafter also simply referred to as "decamer"), and a dodecamer represented by formula (3) (hereinafter also simply referred to as "dodecamer"). The number of compounds constituting the crystal (Z) is plural. Furthermore, the crystal (Z) has interaction between the silanol compounds via a hydrogen bond formed by at least one hydroxy group.

[0018]

[0019] The multiple silanol compounds contained in the crystal (Z) 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 crystal (Z) in this specification is solid and includes an assembly in which silanol compounds are regularly aligned through interactions via hydrogen bonds. The assembly may be in the form of a chain or a ring in which the silanol compounds are aligned. The fact that the crystal includes interactions via hydrogen bonds between silanol compounds can be confirmed by performing X-ray crystal structure analysis of the crystal.

[0020] The crystal (Z) used in the production method of this embodiment contains a plurality of at least one silanol compound selected from the group consisting of the octamer, decamer, and dodecamer. Suitable examples of the crystal (Z) include crystal (I) containing a plurality of octamer silanol compounds, crystal (II) containing a plurality of decamer silanol compounds, and crystal (III) containing a plurality of dodecamer silanol compounds. Furthermore, the crystal (Z) may contain a plurality of at least two silanol compounds selected from the group consisting of octamer silanol compounds, decamer silanol compounds, and dodecamer silanol compounds. Furthermore, the crystal (Z) may be a mixture of at least two types of crystals, for example, a mixture of at least two types selected from the group consisting of the crystal (I), crystal (II), and crystal (III).

[0021] In the crystal (Z), the hydroxy group forming the hydrogen bond of the silanol compound may be any hydroxy group, i.e., the hydroxy group forming the hydrogen bond of the silanol compound may be any of the eight hydroxy groups of the octamer, any of the ten hydroxy groups of the decamer, or any of the twelve hydroxy groups of the dodecamer.

[0022] 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.

[0023] When the crystal (Z) contains an octameric silanol compound and the silanol compounds form a chain-like assembly, the number of hydroxy groups forming hydrogen bonds may be any of 2, 3, 4, 5, 6, 7, or 8 per molecule, excluding the silanol compounds at the ends of the chain-like assembly. When the crystal (Z) contains an octameric silanol compound and the silanol compounds are aligned to form a cyclic assembly, the number of hydroxy groups forming hydrogen bonds may be any of 2, 3, 4, 5, 6, 7, or 8 per molecule. When the crystal (Z) contains a decameric silanol compound and the silanol compounds form a chain-like assembly, the number of hydroxy groups forming hydrogen bonds may be any of 2, 3, 4, 5, 6, 7, 8, 9, or 10 per molecule, excluding the silanol compounds at the ends of the chain-like assembly. Furthermore, when the crystal (Z) contains a decameric 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, or 10. When the crystal (Z) contains a dodecamer silanol compound and the silanol compounds form a chain-like 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, or 12, excluding the silanol compounds at the ends of the chain-like assembly. Furthermore, when the crystal (Z) contains a dodecamer of a silanol compound and the silanol compounds are aligned to form a cyclic assembly, the number of hydroxy groups that form hydrogen bonds may be any of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12 per molecule.

[0024] The octameric, decamer, and dodecamer silanol compounds contained in crystal (Z) self-assemble to form regularly aligned aggregates. Hereinafter, examples of the formats of the octameric, decamer, and dodecamer silanol compounds will be given. However, in this specification, in the octameric, decamer, and dodecamer structures, one Si—O—Si bond is omitted to represent one side, and OH groups are omitted, so that the structures of formulas (1), (2), and (3) are abbreviated as (1)′, (2)′, and (3)′, respectively, as follows:

[0025]

[0026] The octamer, decamer, and dodecamer silanol compounds contained in crystal (Z) have clear vacancies in the center of the square prism, pentagonal prism, and hexagonal prism, respectively, as shown in the above structures.

[0027] The type of alignment is not particularly limited, but an example is a one-dimensional structure in which silanol compounds are linearly aligned.

[0028] The one-dimensional structures of the octamer, decamer, and dodecamer are not particularly limited, and examples thereof include the structures shown in Tables 1-1, 1-2, and 2 to 9 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 in 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, and 2 to 9 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, and 2 to 9 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.

[0029]

[0030] 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.

[0031] 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.

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040] As described above, the crystal (Z) may include a group in which silanol compounds are aligned to form a ring. In this case, the number of silanol compounds forming the ring group is arbitrary. In the case of a decameric silanol compound, for example, a group of 10 compounds (Formula 17) as shown in Table 8 can form a ring, and in the case of a dodecameric silanol compound, for example, a group of 6 compounds (Formula 18) as shown in Table 9 can form a ring. In addition, the crystal (Z) may have a layered structure in which one-dimensional structures of ring groups such as Form 17 and Form 18 are stacked together via plane 1.

[0041]

[0042] 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.)

[0043] When the above-mentioned assembly is formed by hydrogen bonding between two hydroxy groups on adjacent silicon atoms, suitable examples of the one-dimensional structure include Forms 7 and 8 in Table 3 above, and Form 12 in Table 5. The bonding modes of hydrogen bonds in Form 7 in Table 3 above and Form 12 in Table 5 above are represented by, for example, the following i-1 and i-2, respectively.

[0044] (In the above structure, the dashed lines represent hydrogen bonds.)

[0045] An 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 of steps, as shown in Format 8 in Table 3, in which a hydroxy group on the upper silicon atom of one octamer forms a hydrogen bond with a hydroxy group on the lower silicon atom of another octamer, and a hydroxy group on the upper silicon atom adjacent to the upper silicon atom of the above-mentioned octamer forms a hydrogen bond with a hydroxy group on the lower silicon atom of yet another octamer (see the structure below).

[0046]

[0047] Similarly, an 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 certain decamer forms a hydrogen bond with a hydroxy group on the lower silicon atom of another decamer, and a hydroxy group on the lower silicon atom adjacent to the upper silicon atom of the certain decamer forms a hydrogen bond with a hydroxy group on the upper silicon atom of yet another decamer (see the structure below), as shown in Format 15 in Table 7 above.

[0048]

[0049] When the above assembly is formed by hydrogen bonding between two hydroxy groups on silicon atoms separated by one or more siloxane bonds, suitable one-dimensional structures include Format 10 in Table 4 and Format 14 in Table 6. The bonding modes of hydrogen bonds in Format 10 in Table 4 and Format 14 in Table 6 are represented by, for example, the following ii-1 and ii-2, respectively.

[0050] (In the above structure, the dashed lines represent hydrogen bonds.)

[0051] Another 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 Format 1 in Table 1 above, 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).

[0052]

[0053] Similarly, 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 Format 9 in Table 3, in which a hydroxy group on the upper silicon atom of a certain octamer forms a hydrogen bond with a hydroxy group on the upper silicon atom of another octamer, and a hydroxy group on an upper silicon atom that is one siloxane bond away from the upper silicon atom of the certain octamer (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 octamer (see the structure below).

[0054]

[0055] Similarly, 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 Format 11 in Table 5, in which a hydroxy group on the upper silicon atom of a certain decamer forms a hydrogen bond with a hydroxy group on the upper silicon atom of another decamer, and a hydroxy group on an upper silicon atom that is one siloxane bond away from the upper silicon atom of the certain decamer (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 decamer (see the structure below).

[0056]

[0057] Similarly, examples of one-dimensional structures in which the above-mentioned clusters are formed by hydrogen bonds between two hydroxy groups on silicon atoms that are one or more siloxane bond apart include, as shown in Format 13 in Table 5, a one-dimensional structure in which a hydroxy group on the upper silicon atom of a certain decamer forms a hydrogen bond with a hydroxy group on the lower silicon atom of another decamer, and a hydroxy group on a lower silicon atom that is one or two siloxane bonds away from the upper silicon atom of the certain decamer (i.e., positioned across the structure represented by Formula (a) where n is 1 or 2) forms a hydrogen bond with a hydroxy group on the upper silicon atom of yet another decamer, and such a structure is repeated (see the structure below).

[0058]

[0059] 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).

[0060]

[0061] Examples of the linearly aligned one-dimensional structure include an assembly formed by hydrogen bonding between four hydroxy groups contained in one silanol compound and hydroxy groups contained in another silanol compound. Specific examples of one-dimensional structures 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 in another silanol compound, and the remaining two hydroxy groups bonded to adjacent silicon atoms in the one silanol compound are hydrogen-bonded to two hydroxy groups bonded to adjacent silicon atoms in yet another silanol compound. Suitable examples of such structures include Formats 1, 2, and 3 in Table 1-1. Suitable examples of such structures include Formats 7, 8, and 9 in Table 3 and Formats 11, 12, 13, and 14 in Table 5. The hydrogen bonding modes of Format 9 in Table 3 and Format 12 in Table 5 are, for example, represented by the following formulas iii-1 and iii-2, but are not limited thereto. The structures represented by iii-1 and iii-2 are also called ladder structures.

[0062] (In the above structure, the dashed lines represent hydrogen bonds.)

[0063] 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, 6, and 16. Specific examples of one-dimensional structures include structures in which the surface of a cyclic silanol contained in one silanol compound interacts with the surface of a cyclic silanol of another silanol compound via hydrogen bonds (hereinafter also referred to as a rod-like structure). Specific examples, for example, when the silanol compound is a dodecamer represented by formula (3), include, but are not limited to, the following structure i. Furthermore, the surface of the cyclic silanol is preferably the surface of an 8-membered ring when the silanol compound is an octamer represented by formula (1), preferably the surface of a 10-membered ring when the silanol compound is a decamer represented by formula (2), and preferably the surface of a 12-membered ring (hexamer (cyclohexasiloxane skeleton)) when the silanol compound is a dodecamer represented by formula (3).

[0064] structure i

[0065] Other examples of the rod-like structure include, but are not limited to, the structure represented by iv-1 below when the silanol compound is an octamer represented by formula (1), and the structure represented by iv-2 below when the silanol compound is a decamer represented by formula (2).

[0066] (In the above structure, the dashed line represents the structure containing the hydrogen bond shown below; is an abbreviation for a bond containing

[0067] The above structures i, iv-1, and iv-2 are arranged so that their faces overlap each other to form a rod shape. Note that in the above structures i, iv-1, and iv-2, it is sufficient that the faces are arranged so that their faces overlap each other to form a hydrogen bond network, and it is not necessary for all hydroxy groups to form hydrogen bonds.

[0068] Further, examples of the rod-shaped structure include a structure in which, in the arrangement of a decameric silanol compound, faces of the cyclotetrasiloxane skeleton of the decameric silanol compound interact with each other via hydrogen bonds, and a structure in which, in the arrangement of a dodecamer silanol compound, faces of the 8-membered rings (tetramers (cyclotetrasiloxane skeletons)) of the dodecamer interact with each other via hydrogen bonds. Specific examples include the arrangement forms shown in Form 3 and Form 12. In the arrangement forms shown in Form 3 and Form 12, it is sufficient that a hydrogen-bonded network is formed so that the faces are aligned so as to overlap each other; it is not necessary for all hydroxy groups to form hydrogen bonds.

[0069] Examples of one-dimensional structures, including the one-dimensional structures described above, are shown in Tables 10 and 11 below. However, the one-dimensional structures are not limited to these. For example, in Tables 10 and 11 below, the number of hydrogen bonds in one molecule is an even number, but the number of hydrogen bonds in one molecule may be an odd number. For example, as exemplified above, the number of hydrogen bonds in one molecule can be an odd number by forming one hydrogen bond with another silanol compound and then forming two hydrogen bonds with yet another silanol compound.

[0070]

[0071]

[0072] 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 (Z) may be a crystal having a two-dimensional structure in which the silanol compounds are aligned in a plane due to interactions via hydrogen bonds, or a crystal having a three-dimensional structure in which the silanol compounds are aligned three-dimensionally due to interactions via hydrogen bonds.

[0073] In crystals having a two-dimensional structure, 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 include a structure in which multiple one-dimensional structures as described above interact with each other via hydrogen bonds and are aligned in a planar manner. The two-dimensional structure in this embodiment also includes structures in which the ends of the planarly aligned structures interact with each other via hydrogen bonds to form a ring. Preferred examples of crystals having a two-dimensional structure include structures formed in a planar manner by the interaction of one longitudinal side of multiple one-dimensional rod-shaped structures described above via hydrogen bonds. 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.

[0074] structure ii

[0075] structure iii

[0076] Further, other specific examples of crystals having a two-dimensional structure include, but are not limited to, crystals represented by the following structure iv.

[0077] Structure iv (In the above structure, the dashed line represents the structure containing the hydrogen bond shown below; is an abbreviation for a bond containing

[0078] One of the two-dimensional structures is formed in a planar manner by the interaction of one longitudinal side of a plurality of one-dimensional structures via hydrogen bonds, as shown in structure iv. Here, the hydrogen bonding pattern between the one-dimensional structures is, for example, represented schematically as follows: Note that the hydrogen bonding pattern shown below is an example, and the network structure formed by hydrogen bonds (direction of hydrogen bonds) is not limited.

[0079]

[0080] The hydrogen bond type of a crystal having a three-dimensional structure is not particularly limited 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 a plurality of silanol compounds are regularly aligned in three directions: the X-axis direction, the Y-axis direction, and the Z-axis direction. Examples of crystals having a three-dimensional structure include structures in which the above-mentioned two-dimensional structures interact with each other via hydrogen bonds and are three-dimensionally aligned. Furthermore, examples of crystals having a three-dimensional structure include, but are not limited to, the following structures v to viii. structure v structure vi structure vii structure viii

[0081] Furthermore, a suitable example of a crystal having a three-dimensional structure is a structure formed three-dimensionally by two adjacent longitudinal sides of the one-dimensional structure of the rod-shaped structure interacting with one longitudinal side of a different one-dimensional structure via hydrogen bonds, specifically as represented by ix below (hereinafter also referred to as nanohoneycomb structure), but is not limited to these.

[0082] Structure ix (in the above structure, the dashed line represents the structure containing the hydrogen bond shown below; is an abbreviation for a bond containing

[0083] The crystal (Z) can be prepared, for example, by recrystallization from a solution containing a silanol compound and, if necessary, an organic compound, as described below, and the resulting crystal may contain the organic compound. The substance contained in the crystal (Z) is not limited to the solvent used during production and / or the organic compound added, but may also be, for example, a transition metal complex, an inorganic substance, or a simple element. The organic compound, transition metal complex, inorganic substance, or simple element may be contained among an assembly of silanol compounds aligned by interactions via hydrogen bonds, and if the crystal has a three-dimensional structure, may be contained within the three-dimensional structure.

[0084] The organic compounds, transition metal complexes, inorganic substances, and simple elements that may be contained in the crystal (Z) are not particularly limited, but preferably have a molecular weight of 2 to 1000 g / mol. The substances that may be contained in the crystal (Z) 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, and glycidyl methacrylate. , 1,2-epoxybutane, 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, indazole, 1,2,3-benzotriazole, piazolo[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-phenylene diisocyanate, 1,4-phenylene diisothiocyanate, 1,5-dicysocyanatonaphthalene, 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, 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-di Methylbenzene, 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-dibromodithieno[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-quat phenyl, 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-carboxaldehyde, 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 carboxylic aldehyde, 2,2':5',2"-terthiophene-5,5"-dicarboxaldehyde, α-quaterthiophene, α-quinquithiophene, 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, osmocene, 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-pentane 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, cyclopentadienylindium, bis(cyclopentadienyl)magnesium, cyclopentadienylmanganese tricarbonyl, cycloheptatriene molybdenum tricarbonyl, tris(cyclopentadienyl)neodymium Nitrium, allylpalladium chloride (dimer), bis(cyclooctatetraene)iron, cyclohexadieneiron tricarbonyl, dicarbonylcyclopentadienyliodoniron, cyclopentadienyliron dicarbonyl (dimer), tricarbonyl(cyclooctatetraene)iron, iron(II) acetate, (acetylacetonato)(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-cyclooctadiene)rhodium (dimer), acetylacetonate(norbornane) Examples of suitable rhodium compounds include chloro(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.

[0085] When the crystal (Z) contains an organic compound, a transition metal complex, an inorganic substance, or a substance of a simple element, it 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 simple element may be added to the obtained crystal.

[0086] When the crystal (Z) 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)).

[0087] [Step of Preparing Crystal (Z)] The method for producing the compound of this embodiment includes a step of preparing crystal (Z).

[0088] (Octamer and Decamer) Crystal (Z) can be produced, for example, in the case of an octamer and a decamer, by preparing a solution containing the octamer and decamer silanol compound, optionally 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, and recrystallizing the solution by a vapor diffusion method; or optionally 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, and concentrating the solution under reduced pressure to recrystallize; or optionally 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, and cooling the solution. That is, one method for producing crystal (Z) is a method comprising the steps of: preparing a solution containing the silanol compound; and optionally 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, and recrystallizing the solution by a vapor diffusion method. One method for producing crystalline (Z) 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 crystalline (Z) 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 and then allowing it to stand, or cooling the solution to, for example, -80°C to 10°C, preferably -30°C to 10°C. These methods can also be performed in combination.

[0089] (Dedecomer) In addition, in the case of a dodecamer, the crystal (Z) 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 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; optionally 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, and recrystallizing the solution by a poor solvent method; optionally 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, and concentrating the solution under reduced pressure to recrystallize; optionally 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, and cooling the solution to recrystallize; or optionally 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, and recrystallizing the solution by heating the solution. That is, one method for producing crystal (Z) is a method 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. Here, the vapor diffusion method refers, for example, to a method in which a poor solvent is added to the solution by vapor diffusion. Also, one method for producing crystal (Z) is a method 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. Here, the poor solvent method refers, for example, to a method in which a poor solvent is added to the solution all at once.One method for producing the crystal (Z) 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 the crystal (Z) 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 temporarily heating the solution and then allowing it to stand to cool (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 temporarily heated is preferably, for example, 30 to 180°C. One method for producing crystal (Z) 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.

[0090] In the above-described production method, an interaction between silanol compounds through hydrogen bonding can be generated by evaporating the solvent from the solution containing the silanol compounds, by cooling the solution, or by heating the solution. One embodiment is a method for self-organizing the silanol compounds, which includes a step of forming an interaction through hydrogen bonding by applying a vapor diffusion method to the solution containing the silanol compounds, 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.

[0091] When the crystal (Z) contains an organic compound, a transition metal complex, an inorganic substance, or a simple element, the crystal (Z) may be produced by impregnating the crystal obtained by recrystallization as described above with a substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements, or a solution thereof. This method allows various crystals containing organic compounds, transition metal complexes, inorganic substances, and simple elements to be obtained using the crystal obtained by recrystallization as a starting material. The crystal to be impregnated is not particularly limited as long as it is crystal (Z). Specifically, it may be any of the following: a crystal having a one-dimensional structure in which the silanol compound is linearly aligned due to the interaction via the hydrogen bonds; a crystal having a two-dimensional structure in which the silanol compound is planarly aligned due to the interaction via the hydrogen bonds; or a crystal having a three-dimensional structure in which the silanol compound is sterically aligned due to the interaction via the hydrogen bonds.

[0092] 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).

[0093] 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.

[0094] 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 an organic compound, a transition metal complex, an inorganic substance, and a simple element. The method for producing the crystal (P) includes the steps of: preparing a crystal (S) containing a plurality of at least one silanol compound selected from the group consisting of an octamer represented by formula (1), a decamer represented by formula (2), and a dodecamer represented by formula (3), wherein the silanol compounds interact with each other via a hydrogen bond formed by at least one hydroxyl group; and 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; 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 replace at least a portion of the first substance contained in the crystal (S) with the second substance, thereby obtaining a crystal (P).

[0095] Here, it is preferable that at least a part of the substance after substitution is a substance different from the substance before substitution.

[0096] That is, one of the present embodiments is a method for producing a crystal (P) containing a plurality of at least one kind of silanol compound selected from the group consisting of an octamer represented by formula (1), a decamer represented by formula (2), and a dodecamer represented by formula (3), the silanol compounds interacting with each other via a hydrogen bond through 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 the steps of: preparing a crystal (S) containing a plurality of at least one kind of silanol compound selected from the group consisting of an octamer represented by formula (1), a decamer represented by formula (2), and a dodecamer represented by formula (3), the silanol compounds interacting with each other via a hydrogen bond through at least one hydroxy group, the silanol compounds having a linearly aligned one-dimensional structure, and 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; the production method comprising the step of 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).

[0097] Also, one of the present embodiments is a method for producing a crystal (P) comprising a plurality of at least one silanol compound selected from the group consisting of an octamer represented by formula (1), a decamer represented by formula (2), and a dodecamer represented by formula (3), the silanol compounds interacting with each other via a hydrogen bond through 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 the steps of: preparing a crystal (S) comprising a plurality of at least one silanol compound selected from the group consisting of an octamer represented by formula (1), a decamer represented by formula (2), and a dodecamer represented by formula (3), the silanol compounds interacting with each other via a hydrogen bond through 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 first substance selected from the group consisting of an organic compound, a transition metal complex, an inorganic substance, and a simple element; the production method comprising the step of 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).

[0098] 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.

[0099] 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 an organic compound, a transition metal complex, an inorganic substance, and a simple element. The method for producing the crystal (P) includes the steps of: preparing a crystal (S) containing a plurality of at least one silanol compound selected from the group consisting of an octamer represented by formula (1), a decamer represented by formula (2), and a dodecamer represented by formula (3), wherein the silanol compounds interact with each other via a hydrogen bond between at least one hydroxy group, and the silanol compounds have a three-dimensional structure in which they are sterically aligned due to the interaction via the hydrogen bond; and 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 to obtain a crystal (P).

[0100] 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.

[0101] The crystal (S) may be prepared, for example, by the above-described method for producing a crystal, specifically, by a production method including the steps of: preparing a solution containing at least one compound selected from the group consisting of an octamer represented by formula (1), a decamer represented by formula (2), and a dodecamer represented by formula (3); and adding, if necessary, 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, 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 at least one compound selected from the group consisting of the octamer represented by formula (1), the decamer represented by formula (2), and the dodecamer represented by formula (3); 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.

[0102] 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 unaligned silanol compounds in the recrystallization step and / or reagents used in the production of the octamer, decamer, and dodecamer silanol compounds 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.

[0103] 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.

[0104] [Method for Producing Octameric and Decamer Silanol Compounds] Octameric and decamer silanol compounds can be produced by organic synthesis techniques. Specifically, they can be produced as follows.

[0105] The octamer and decamer silanol compounds are respectively formed by dissolving silicates (hereinafter sometimes abbreviated as "silicates") having structures represented by the following formulas (1') and (2') with an acid dissociation constant pK ａ (hereinafter referred to as “pK ａ The silicate having the structure represented by the following formula (1') or (2') may be produced by an organic synthesis method or may be commercially available.

[0106]

[0107]

[0108] pK ａ (DMSO) means a known value calculated from the concentration of each component in the acid dissociation equilibrium of an acidic compound in DMSO at 25°C. Specifically, the value K calculated by the following formula ａ is the common logarithm of

[0109]

[0110] Q in silicates ＋ Examples of the lithium ion (Li ＋ ), sodium ions (Na ＋ ), potassium ions (K ＋ ), alkali metal ions such as magnesium ions (Mg ２＋ ), calcium ions (Ca ２＋ ), alkaline earth metal ions such as iron (III) ions (Fe ３＋), copper (II) ions (Cu ２＋ ), 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 (NEt ３ Me ＋ ), tetraethylammonium ion (NEt ４ ＋ ), tetrapropylammonium ion (NPr ４ ＋ ), tetrabutylammonium ion (NBu ４ ＋ Among these, sodium ions (Na ＋ ), potassium ions (K ＋ ), tetramethylammonium ion (NMe ４ ＋ ), tetraethylammonium ion (NEt ４ ＋ ), ethyltrimethylammonium ion (NEtMe ３ ＋ ) is preferred.

[0111] Acidic compounds have a pK ａ (DMSO) is a compound having a pK ａ (DMSO) is preferably 0 or more, more preferably 1 or more, even more preferably 3 or more, and preferably 16 or less, more preferably 14 or less, even more preferably 8 or less. When it is within the above range, the silanol compound can be produced efficiently. ａ As long as (DMSO) is −1 to 20, the specific structure etc. is not particularly limited.

[0112] Acidic compounds include nitric acid (pK ａ(DMSO) is 1.4), sulfuric acid (pK ａ 1 (DMSO) is 1.4, pK ａ 2 (DMSO) is 14.7), hydrochloric acid (pK ａ (DMSO) 2.1), phosphate (pK ａ 1 (DMSO) is 1.83, pK ａ 2 (DMSO) is 6.43, pK ａ 3 (DMSO) is 11.46), or an organic acid which is at least one selected from the group consisting of acetic acid or compounds having a structure represented by the following formulas (b-1) to (b-5).

[0113]

[0114] (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.

[0115] The wavy lines in 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 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 in the following formula. Furthermore, for example, the acidic compound having the structure represented by 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 in the following formula:

[0116]

[0117] When a proton exchange reaction using an organic acid is carried out in a reaction medium such as N,N-dimethylacetamide (DMAc) and / or methanol (MeOH), the ammonium salt produced dissolves in the reaction medium. Therefore, it is necessary to separate the ammonium salt, which is a by-product, 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 (THF), the ammonium salt produced does not dissolve in the reaction medium. Therefore, the ammonium salt can be separated by a simple separation method such as filter filtration, and a silanol compound solution is obtained as a filtrate. Therefore, the acidic compound is preferably an inorganic acid.

[0118] Among inorganic acids, nitric acid, sulfuric acid, hydrochloric acid, and phosphoric acid are preferred, with nitric acid or sulfuric acid being particularly preferred. Nitrate ions, hydrogen sulfate ions, and sulfate ions have weak interactions (e.g., hydrogen bonds) with silanol compounds, making it difficult for the silanol compound and the by-produced ammonium salt to form an insoluble complex in the reaction medium. On the other hand, chloride ions, dihydrogen phosphate ions, hydrogen phosphate ions, and phosphate ions have strong interactions (e.g., hydrogen bonds) with silanol compounds. For this reason, in proton exchange using hydrochloric acid or phosphoric acid, the silanol compound and the ammonium salt may form an insoluble complex in the reaction medium, resulting in a slight decrease in the yield of the target silanol compound.

[0119] 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 Examples of the alkyl group include a hydrogen atom, a methyl group (-Me), an ethyl group (-Et), an n-propyl group (- ｎ Pr), i-propyl group (- ｉ Pr), n-butyl group (- ｎ Examples of the alkyl group include a phenyl group (-Bu), a phenyl group (-Ph), etc., but a hydrogen atom is preferred.

[0120] R ２When 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 (- ｎ Pr), i-propyl group (- ｉ Pr), n-butyl group (- ｎ Bu), etc., but a hydrogen atom is preferred.

[0121] Examples of the acidic compound represented by formula (b-4) include the acidic compound represented by formula (b-4-1) below. Examples of the acidic compound represented by formula (b-5) include the acidic compound represented by formula (b-5-1) below.

[0122] (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.

[0123] R ４ As 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 -), i-propylene group (-CH(CH ３ ) CH ２ -) etc.

[0124] Acidic compounds include acetic acid (pK ａ (DMSO) is 12.6), benzoic acid (pK ａ (DMSO) is 11.1), Meldrum's acid (pK ａ (DMSO) is 7.3), Meldrum's acid derivatives, dimedone (pK ａ (DMSO) is 11.2), dimedone derivatives, acetylacetone (pK ａ (DMSO) is 13.3), acetylacetone derivatives, etc. (see the formula below).

[0125]

[0126] The acidic compound may be a low molecular weight compound such as Meldrum's acid, or a compound represented by any of formulas (b-2) to (b-5) incorporated into an organic solid material such as a resin, or an inorganic solid material such as silica or carbon. When the acidic compound is in such a solid form, it can be packed into a column and used like an ion exchange resin. This allows for extremely efficient production of silanol compounds.

[0127] In particular, the acidic compound is preferably a resin having at least one structure selected from the group consisting of formulae (b-2) to (b-5), and is preferably one that can be regenerated as the acidic compound by exposing the resin to an acidic aqueous solution such as hydrochloric acid after the proton exchange step.

[0128] 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 1.05 times, more preferably at least 1.1 times, and usually at most 50 times, preferably at most 20 times, more preferably at most 5 times. Within the above range, the silanol compound can be produced efficiently.

[0129] The reaction in the proton exchange step is preferably carried out in a liquid. Examples of such a liquid include tetrahydrofuran (THF), tetrahydropyran, dioxane, and 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; acetone, methyl ethyl ketone, phenyl methyl ketone, DMSO, and water. The liquid is not limited to one type, and two or more types may be combined.

[0130] The amount of liquid 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, and more preferably 20°C or higher, and usually 200°C or lower, preferably 70°C or lower, and 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.

[0131] The method for producing an octamer or decamer silanol compound may include a step other than the proton exchange step. Specific steps other than the proton exchange step include an ammonium salt addition step (hereinafter sometimes abbreviated as "ammonium salt addition step") in which an ammonium salt is added to the product obtained in the proton exchange step, and a freeze-drying step (hereinafter sometimes abbreviated as "freeze-drying step") in which the product obtained in the proton exchange step or the product obtained in the ammonium salt addition step is frozen and exposed to reduced pressure.

[0132] (Ammonium Salt Addition Step) The type and amount of the ammonium salt used are not particularly limited and can be appropriately selected depending on the purpose. The term "ammonium salt" refers to a compound consisting of an ammonium ion and a counter anion, and the structures of the ammonium ion and the counter anion are not particularly limited. It is believed that the addition of an ammonium salt suppresses the condensation of the silanol compound. The ammonium ion may be a tetrahydroammonium ion (NH ４ ＋ ), tetramethylammonium ion (NMe ４ ＋ ), tetrapropylammonium ion (NPr ４ ＋ ), tetrabutylammonium ion (NBu ４ ＋ ), benzyltributylammonium ion (NBnBu ３ ＋ ), tributyl(methyl)ammonium (NBu ３ Me ＋ ) ion, tetrapentylammonium ion (NPen ４ ＋ ), tetrahexylammonium ion (NHex ４ ＋ ), tetraheptylammonium ion (NHep ４ ＋ ), 1-butyl-1-methylpyrrolidium ion (BuMePyr ＋ ), methyltrioctylammonium ion (NMeOct ３ ＋ ), dimethyldioctadecylammonium ion, Meldrum's acid-tetramethylammonium salt, and the like.

[0133] The counter anion is fluoride ion (F － ), chloride ions (Cl － ), bromide ion (Br － ), iodide ion (I － ), acetoxy ion (AcO － ), nitrate ions (NO ３ － ), azide ion (N ３ －), tetrafluoroborate ion (BF ４ － ), perchlorate ion (ClO ４ － ), sulfate ions (SO ４ － ) etc.

[0134] The ammonium salt is tetrabutylammonium chloride (NBu ４ Cl), tetrabutylammonium bromide (NBu ４ Br), tetrapentylammonium chloride (NPen ４ Cl), Meldrum's acid-tetramethylammonium salt, and dimethyldioctadecylammonium chloride are particularly preferred. The ammonium salt contained in the composition is not limited to one type, and may contain two or more types. The amount of the ammonium salt used is preferably 1 to 4 times the amount of the silanol compound in terms of the amount of substance.

[0135] (Freeze-drying step) The freezing temperature, drying temperature, drying pressure, drying time, etc. in the freeze-drying step are not particularly limited and can be appropriately selected depending on the purpose. The freezing temperature is not particularly limited as long as it is a temperature at which the product obtained in the proton exchange step or the product obtained in the ammonium salt addition step freezes, but is usually 10°C or lower, preferably 0°C or lower, more preferably -20°C or lower, and is usually -196°C or higher, preferably -150°C or higher, more preferably -100°C or higher.

[0136] The drying temperature is usually 10° C. or lower, preferably 0° C. or lower, more preferably −20° C. or lower, and usually −196° C. or higher, preferably −150° C. or higher, more preferably −100° C. or higher. The drying pressure is usually 100 Pa or lower, preferably 20 Pa or lower, more preferably 3 Pa or lower, and usually 10 －５ The pressure is at least 1 Pa, preferably at least 0.01 Pa, and more preferably at least 1 Pa. The drying time is usually 200 hours or less, preferably 100 hours or less, and more preferably 50 hours or less, and usually 1 hour or more, preferably 5 hours or more, and more preferably 10 hours or more.

[0137] [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.

[0138] 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 (3') (hereinafter sometimes abbreviated as "silicate") is reacted with an acidic compound to obtain a solution containing a silanol compound represented by the following formula (3): The silicate having the structure represented by the following formula (3') may be produced by an organic synthesis method or may be commercially available.

[0139] (3') (In formula (3'), Q ＋ represents a cation.) (3)

[0140] 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 (3), and isolating the silanol compound represented by formula (3) as a powder (hereinafter, this step may be abbreviated as an “isolation step”).

[0141] The silicate, acidic compound, and other reaction conditions in the proton exchange step will be described in detail below.

[0142] (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.

[0143] 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.

[0144] 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.

[0145] 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:

[0146]

[0147] In the proton exchange step, a silicate having a structure represented by the following formula (3') is reacted with an acidic compound. (3') (In formula (3'), Q ＋ represents a cation.) In formula (3'), 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.

[0148] 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 "Q１２ K １２ ・2αCD・nH ２ 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.

[0149] 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.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] 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:

[0154]

[0155] 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.

[0156]

[0157] 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.

[0158] 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.

[0159] 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):

[0160] (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.

[0161] 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.

[0162] 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).

[0163]

[0164] 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.

[0165] 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.

[0166] 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.

[0167] 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.

[0168] 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.

[0169] (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 (3) obtained in the proton exchange step, precipitating the silanol compound represented by formula (3), and isolating the silanol compound represented by formula (3) 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 (3) can be extremely simply isolated as a single powder.

[0170] The poor solvent for precipitating the silanol compound represented by the above formula (3) is not particularly limited, and examples thereof include hexane, benzene, toluene, dibutyl ether, diisopropyl ether, diethyl ether, dichloromethane, chloroform, methyl acetate, ethyl acetate, ethyl methyl ketone, isopropyl methyl ketone, and isobutyl methyl ketone. Among these, hexane, benzene, diisopropyl ether, ethyl acetate, and ethyl methyl ketone are preferred, and diisopropyl ether and ethyl acetate are particularly preferred. In addition, in the isolation step, a precursor (e.g., Q) having a ligand (e.g., αCD) coordinated thereto may be used as the silicate to be reacted with the acidic compound. １２ K １２ ・2αCD・nH ２ When using a silanol compound represented by formula (3), 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 (3). The boiling point of the poor solvent for precipitating the silanol compound represented by formula (3) 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.

[0171] 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 (3) can be precipitated more efficiently.

[0172] In the isolation step, the time for precipitating the silanol compound represented by formula (3) 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.

[0173] The method for isolating the silanol compound represented by formula (3) 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 (3) 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.

[0174] When producing the crystal (Z), the desired one-dimensional, two-dimensional, or three-dimensional structure can be obtained by controlling the formation of hydrogen bonds in the recrystallization step. Examples of methods for controlling the formation of hydrogen bonds include 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, preferably an organic compound, selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements, in addition to the solvent. Among these control methods, 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, ethyl methyl ketone, isopropyl methyl ketone, isobutyl methyl ketone, methyl acetate, ethyl acetate, 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 the desired one-dimensional structure, two-dimensional structure, or three-dimensional structure can be produced.

[0175] [Step of Obtaining Intermediate] The method for producing the compound of this embodiment includes a step of using the crystal (Z) to obtain an intermediate in which some of the silanol compounds are bonded to each other by dehydration condensation.

[0176] In addition, in the method for producing a compound of the present embodiment, the step of obtaining the intermediate is preferably a step of heating the crystal (Z) at 80 to 250°C in the presence of an additive and a solvent to obtain an intermediate in which some of the silanol compounds are bonded to each other by dehydration condensation.

[0177] The additive used in the step of obtaining an intermediate by heating the crystal (Z) in the presence of an additive and a solvent is an alkylammonium salt NR ４ ＋ X － (Wherein R is CH ３ , C ２ H ５ , C ３ H ７ , or C ４ H ９ and X=Cl, Br, or CH ３ COO), tertiary amines, and amidines, more preferably alkylammonium salts, triethylamine, diisopropylmethylamine, and diazabicycloundecene, and even more preferably tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium acetate, or triethylamine.

[0178] The solvent used in the step of obtaining an intermediate by heating the crystal (Z) in the presence of an additive and a solvent is an alcohol R'OH (wherein R' is CH ３ , C ２ H ５ , C ３ H ７ , C ４ H ９ , C ５ H １１ , (CH ３ ) ２ CH, or (CH ３ ) ３C.), organic acid R″COOH (wherein R″ is H, CH ３ , C ２ H ５ , C ３ H ７ , or C ４ H ９ ), and ester R １ COOR ２ (In the formula, R １ and R ２ are each independently CH ３ , C ２ H ５ , C ３ H ７ , C ４ H ９、 or C ６ H ５ Preferably, the alcohol is at least one selected from the group consisting of butanol, pentanol, acetic acid, propionic acid, and ester R １ COOR ２ (In the formula, R １ and R ２ are the same as above.) is more preferably at least one selected from the group consisting of acetic acid, propionic acid, n-butanol, ethyl acetate, and methyl benzoate, and further preferably acetic acid, propionic acid, n-butanol, ethyl acetate, and methyl benzoate. The mechanism by which a compound having a desired pore structure (e.g., a compound having a regularly arranged pore structure while maintaining the structure of the above-mentioned crystal (Z)) is finally obtained in the heating step described below by carrying out a step of obtaining an intermediate by heating the crystal (Z) in the presence of these additives and solvents is not clear, but the present inventors have speculated as follows. The solvent used (e.g., alcohol, carboxylic acid) generates the corresponding deprotonated anion through dissociation equilibrium in the presence of a base or an ammonium salt. This anion is used as a catalyst to produce, for example, a dodecamer (Q) represented by the above formula (3). １２ H １２ The silanol groups react with the silanol groups of the hydroxybenzoate to produce an intermediate in which dehydration condensation has partially progressed. After the intermediate is obtained by gradually progressing the dehydration condensation in the presence of the additives and solvents described above, the intermediate is further heated to undergo further dehydration condensation in a stepwise manner, which is believed to suppress the effects of volume shrinkage and produce a compound with the desired pore structure.

[0179] In addition, in the step of obtaining an intermediate by heating Crystal (Z) in the presence of an additive and a solvent, the heating temperature is 80 to 250°C, preferably 100 to 200°C, and more preferably 100 to 180°C.

[0180] In the step of obtaining an intermediate by heating the crystal (Z) in the presence of an additive and a solvent, the heating atmosphere is preferably an air atmosphere or an inert gas atmosphere.

[0181] In the step of obtaining an intermediate by heating Crystal (Z) in the presence of an additive and a solvent, the heating time is preferably 6 to 120 hours, more preferably 12 to 48 hours. The preparation of the intermediate can be confirmed by, for example, powder X-ray diffraction (XRD), ２９ Si-magic angle spinning-nuclear magnetic resonance ( ２９ Si-MAS-NMR).

[0182] Furthermore, in the method for producing a compound of this embodiment, the step of obtaining the intermediate may be a step of freeze-drying the crystals (Z) to obtain an intermediate in which some of the silanol compounds are bonded to each other by dehydration condensation.

[0183] In the step of obtaining an intermediate by freeze-drying the crystal (Z), the freezing temperature, drying temperature, drying pressure, drying time, etc. are not particularly limited and can be appropriately selected depending on the purpose. In the step of obtaining an intermediate by freeze-drying the crystal (Z), the freezing temperature is not particularly limited as long as it is a temperature at which the crystal (Z) freezes, but is preferably −196° C. or higher and 50° C. or lower, more preferably −100° C. or higher and 40° C. or lower, and even more preferably −70° C. or higher and 25° C. or lower.

[0184] In the step of obtaining an intermediate by freeze-drying crystalline (Z), the drying temperature is preferably −100° C. or higher and 50° C. or lower, more preferably −70° C. or higher and 40° C. or lower, and even more preferably −40° C. or higher and 25° C. or lower. In the step of obtaining an intermediate by freeze-drying crystalline (Z), the drying pressure is preferably 0.00001 Pa or higher and 100 Pa or lower, more preferably 0.0001 Pa or higher and 10 Pa or lower, and even more preferably 0.001 Pa or higher and 1 Pa or lower. In the step of obtaining an intermediate by freeze-drying crystalline (Z), the drying time is preferably 6 hours or higher and 336 hours or lower, more preferably 12 hours or higher and 240 hours or lower, and even more preferably 24 hours or higher and 168 hours or lower. [Step of Obtaining Compound (Heating Step)] The method for producing a compound of this embodiment includes a step of heating the intermediate at 200 to 900°C, whereby the silanol compounds are bonded to each other by dehydration condensation to obtain a compound having a regularly arranged pore structure (hereinafter also referred to as the "heating step").

[0185] In the heating step, the heating temperature is 200 to 900°C, preferably 600 to 800°C, and more preferably 650 to 750°C.

[0186] In the heating step, the heating pressure is preferably 0 to 1 atmosphere, and more preferably 1 atmosphere.

[0187] In the heating step, the heating atmosphere is preferably atmospheric gas or nitrogen gas, and more preferably atmospheric gas.

[0188] In the heating step, the heating time is preferably 168 hours or less, more preferably 96 hours or less, and even more preferably 48 hours or less. The lower limit of the heating time is not particularly limited as long as the desired compound is obtained, but is, for example, 1 hour or more. The structure of the obtained compound can be determined, for example, by powder X-ray diffraction (XRD), ２９ Si-magic angle spinning-nuclear magnetic resonance ( ２９ The measurement can be carried out using a scanning electron microscope (STEM), Si-MAS-NMR, or a scanning transmission electron microscope (STEM), and specifically, the measurement can be carried out by the method described in the examples below.

[0189] The method for producing a compound of the present embodiment includes the step of obtaining an intermediate and the heating step as described above, and thereby makes it possible to control the crystal structure at the molecular level, and to produce, for example, a compound having a regularly arranged pore structure while maintaining the structure of the above-described crystal (Z).

[0190] The method for producing a compound of this embodiment may include a drying step between the step of obtaining the intermediate and the heating step. In the drying step, the drying temperature is preferably 50°C or higher and 200°C or lower, more preferably 70°C or higher and 150°C or lower, and even more preferably 80°C or higher and 120°C or lower. In the drying step, the drying pressure is preferably 50.7 kPa or higher and 152.0 kPa or lower, more preferably 76.0 kPa or higher and 126.7 kPa or lower, and even more preferably 91.2 kPa or higher and 111.5 kPa or lower. In the drying step, the drying time is preferably 0.5 hours or higher and 12 hours or lower, more preferably 1 hour or higher and 8 hours or lower, and even more preferably 2 hours or higher and 5 hours or lower.

[0191] [Recrystallization Step] In the method for producing a compound of this embodiment, the step of preparing the crystal (Z) preferably includes: a step of preparing a solution containing the silanol compound; and a step of 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 needed, and recrystallizing the solution by a vapor diffusion method, by concentrating the solution under reduced pressure, by cooling the solution, or by heating the solution. Note that each step here is the same as the steps described in the above [Step of Preparing Crystal (Z)].

[0192] [Compound] The compound of the present embodiment is a compound having a pore structure in which at least one silanol compound selected from the group consisting of an octamer represented by the following formula (1), a decamer represented by the following formula (2), and a dodecamer represented by the following formula (3) is bonded to itself by dehydration condensation and arranged in a regular pattern (however, excluding LTA zeolite derived from the octamer represented by the following formula (1), and FAU zeolite and CHA zeolite derived from the dodecamer represented by the following formula (3)).

[0193] The compound of this embodiment is not particularly limited as long as it has a pore structure in which the above-mentioned specific silanol compounds are bonded to each other by dehydration condensation and arranged in an orderly manner, but examples thereof include zeolite, silica nanosheets, silica nanorods, silica nanoparticles, and silica nanowires. Among these, zeolite is preferred. Note that the compound of this embodiment can be produced, for example, by dehydration condensation of crystal (Z) as in the above-mentioned compound production method, but may contain trace amounts of unreacted raw materials used in the production or intermediates generated during the reaction, on the order of impurities.

[0194] In the compound of this embodiment, the pore structure may be a linearly aligned one-dimensional structure, a planarly aligned two-dimensional structure, or a three-dimensionally aligned three-dimensional structure. Examples of the pore structure include a two-dimensional structure in which a plurality of one-dimensional structures are bonded to each other via covalent bonds and aligned to each other via covalent bonds, and a three-dimensional structure in which a plurality of two-dimensional structures are bonded to each other via covalent bonds and aligned to each other via covalent bonds.

[0195] In addition, the compound of this embodiment preferably has a pore structure in which the hydrogen-bonded moieties in the hydrogen-bonded inorganic structure are converted to covalent bonds by dehydration condensation. The hydrogen-bonded inorganic structure is preferably, for example, the above-described crystal (Z), i.e., a crystal containing a plurality of at least one silanol compound selected from the group consisting of the octamer represented by the above formula (1), the decamer represented by the above formula (2), and the dodecamer represented by the above formula (3), and having an interaction between the silanol compounds via a hydrogen bond through at least one hydroxy group. That is, the compound of this embodiment preferably has a structure in which the hydrogen-bonded moieties in the above-described crystal (Z) are converted to covalent bonds. The structure of the compound of this embodiment will be specifically described below, but the structure other than the hydrogen-bonded moieties in the above-described crystal (Z) can be the same as the above-described crystal (Z).

[0196] [One-Dimensional Structure] In the compound of this embodiment, the pore structure is a one-dimensional structure in which two hydroxy groups contained in one silanol compound are bonded to hydroxy groups of another silanol compound by dehydration condensation and linearly aligned, and it is preferred that the two hydroxy groups bonded by dehydration condensation are two hydroxy groups on adjacent silicon atoms in one silanol compound, or two hydroxy groups on silicon atoms separated by one siloxane bond (—O—Si—O— bond) or more.

[0197] Furthermore, in the compound of this embodiment, the pore structure preferably has a linearly aligned one-dimensional structure in which, of the four hydroxy groups contained in one silanol compound, two hydroxy groups bonded to adjacent silicon atoms are bonded by dehydration condensation to two hydroxy groups bonded to adjacent silicon atoms in another silanol compound, and the remaining two hydroxy groups bonded to adjacent silicon atoms in the one silanol compound are further bonded by dehydration condensation to two hydroxy groups bonded to adjacent silicon atoms in another silanol compound.

[0198] In the compound of this embodiment, the pore structure is preferably a one-dimensional structure (rod-like structure) in which a surface of a cyclic silanol contained in one silanol compound in the silanol compound is linearly aligned by being bonded via a covalent bond to a surface of a cyclic silanol contained in another silanol compound.More preferably, the surface of the cyclic silanol is a surface of an 8-membered ring when the silanol compound is an octamer represented by the above formula (1), a surface of an 8- or 10-membered ring when the silanol compound is a decamer represented by the above formula (2), or a surface of an 8- or 12-membered ring when the silanol compound is a dodecamer represented by the above formula (3).

[0199] The one-dimensional structure is preferably at least one structure selected from the group consisting of the following formulas (1-1) to (1-3): (In structural formulas (1-1) to (1-3), one Si—O—Si bond is omitted and represented by one side.)

[0200] [Two-dimensional Structure] In the compound of this embodiment, the pore structure is preferably a two-dimensional structure in which a plurality of the above-described one-dimensional structures are bonded to each other via covalent bonds and aligned in a plane.

[0201] In addition, in the compound of this embodiment, the pore structure is preferably a two-dimensional structure in which the ends of the one-dimensional structure described above are bonded to each other via covalent bonds and aligned in a ring shape.

[0202] In the compound of this embodiment, the pore structure is preferably a two-dimensional structure in which the longitudinal sides of the plurality of rod-shaped structures described above are bonded to each other via covalent bonds and aligned in a plane.

[0203] The two-dimensional structure is preferably at least one structure selected from the group consisting of the following formulas (2-1) and (2-2): (In structural formulas (2-1) to (2-2), one Si—O—Si bond is omitted and represented by one side.)

[0204] [Three-dimensional Structure] In the compound of this embodiment, the pore structure is preferably a three-dimensional structure in which a plurality of the above-described two-dimensional structures are bonded to each other via covalent bonds and sterically aligned.

[0205] The three-dimensional structure is preferably at least one structure selected from the group consisting of the following formulas (3-1) to (3-3): (In structural formulas (3-1) to (3-3), one Si—O—Si bond is omitted and represented by one side.)

[0206] The compound of this embodiment may contain 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 organic compound, the transition metal complex, the inorganic substance, and the simple element may be contained in a pore structure in which silanol compounds are bonded to each other by dehydration condensation and arranged in a regular pattern, or, if the compound has a three-dimensional structure, may be contained within the three-dimensional structure.

[0207] The organic compound, transition metal complex, inorganic substance, and elemental substance that may be contained in the compound of this embodiment are not particularly limited, but preferably have a molecular weight of 2 to 1000 g / mol. Specific examples of the substance that may be contained in the compound of this embodiment are not particularly limited, but are, for example, the same as the substances that may be contained in the above-mentioned crystal (Z).

[0208] When the compound of this embodiment contains an organic compound, a transition metal complex, an inorganic substance, or a simple element, as described above, it may be added to a solution containing a silanol compound used for recrystallization in the step of preparing crystal (Z), or the organic compound, transition metal complex, inorganic substance, or simple element may be added to crystal (Z). Furthermore, the organic compound, transition metal complex, inorganic substance, or simple element may be added to the compound obtained after the heating step described above. The addition method conforms to the addition method described in the above-mentioned [Step of Preparing Crystal (Z)].

[0209] When the crystal (Z) 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)).

[0210] The compound of this embodiment may be, for example, at least partially substituted with at least one second substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements, and may form a complex in which interactions such as van der Waals forces, ionic bonds, covalent bonds, π-π interactions, CH-π interactions, etc. are present between the pore structure and the second substance. Note that the compound of this embodiment also encompasses cases in which it contains other substances such as organic compounds, transition metal complexes, inorganic substances, and simple elements.

[0211] In the compound of this embodiment, the contents of the organic compound, transition metal complex, inorganic substance, and simple element are not particularly limited, but are preferably 20% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less. In the compound of this embodiment, the lower limits of the contents of the organic compound, transition metal complex, inorganic substance, and simple element are not particularly limited, but are, for example, 0% by mass.

[0212] Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples.

[0213] [Synthesis example 1] Q ８ H ８ (Three-dimensional (nano-honeycomb) structure) Octakis(tetramethylammonium)pentacyclo[9.5.1.1 ３，９ .1 ５，１５ .1 ７，１３ . ] Octasiloxane-1,3,5,7,9,11,13,15-octakis(yloxide) hydrate (CAS No. 69667-29-4 (hereinafter referred to as "Q ８ (TMA) ８ ・nH ２ It may be abbreviated as "O".)) Q ８ (TMA) ８ ・48.7H ２8.062 g (4.00 mmol) of nitric acid was suspended in 150 mL of tetrahydrofuran (hereinafter also referred to as "THF") to give a dispersion, to which 3.04 mL (48.04 mmol) of nitric acid was added and stirred for 30 minutes to obtain a suspension. This suspension was filtered (washed with 50 mL of THF). The filtrate was concentrated under conditions of 5°C and a reduced pressure of 6666 Pa (50 torr) to obtain a compound of the composition formula Si ８ O ２０ H ８ (A compound represented by the following formula (1), hereinafter referred to as "Q ８ H ８ A colorless solid (plate-like crystal) containing 79.3% by mass of methyl 2,4-dichloro-3 ... １ H-NMR (DMF-d ７ ): 7.73ppm, ２９ Si-NMR (DMF-d ７ ): -100.1 ppm). Furthermore, single crystal X-ray crystal structure analysis revealed that the obtained crystals consisted of one molecule of Q ８ H ８ and the crystal structure is formed by assembling two molecules of THF, Q ８ H ８ It was revealed that the molecules have a three-dimensional (nano-honeycomb) structure stabilized by hydrogen bonds. The crystal structure determined by single-crystal X-ray crystal structure analysis is shown in Figure 2. Note that hydrogen atoms are omitted in the crystal structure shown in Figure 2.

[0214] Synthesis Example 2 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[13.9.1.13,13.15,11.17,21.19,19.117,23]triacontane-1,3,5,7,9,11,13,15,17,19,21,23-dodecakis(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 (3), 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[13.9.1.13,13.15,11.17,21.19,19.117,23]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 H １２ )) was isolated as a colorless solid (powder) in a yield of 66% (6.116 g).

[0215] [Synthesis Example 3] Q １２ H １２ Three-dimensional (nano-honeycomb) crystals (dioxane-containing composition) of Q prepared by a method in accordance with Synthesis Example 2 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 0.173 g of a colorless solid (columnar crystal) containing 81.4% by mass of １ H-NMR (DMSO-d6): 7.07 ppm, ２９ Si-NMR (DMSO-d6): -101.2 ppm). Furthermore, single crystal X-ray crystal structure analysis showed that the obtained crystals consisted of one molecule of Q １２ H１２ 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 3.

[0216] [Example 1] Q using tetraethylammonium chloride ８ H ８ Dehydration condensation of three-dimensional crystals of Q ８ H ８ 0.108 g of the three-dimensional crystal was precipitated in 4.0 mL of acetic acid, and 0.101 g of tetraethylammonium chloride was dissolved in the solution to obtain a mixed solution. The resulting mixed solution was then stirred at room temperature for 2 hours and then stirred in an oil bath at 100°C for 1 day to obtain a reaction solution. The solvent was removed from the reaction solution by suction filtration and dried at 100°C for 1 hour to obtain 0.063 g of a white powder (crystal). Powder X-ray crystal structure analysis showed that the obtained crystal had peaks at 9.59°, 11.09°, 19.15°, 21.48°, 23.99°, and 24.44°. ２９ From Si-MAS-NMR, it was found that one silicon atom has four "-OSi" bonds (Si-(SiO) ４ ) (hereinafter referred to as “Q ４ A peak (110 ppm) related to the Q ８ H ８ It was revealed that dehydration condensation had progressed in some of the three-dimensional crystals, and the hydrogen bonds had been converted to covalent bonds. ２９ The results of Si-MAS-NMR measurements are shown in FIGS. 4 and 5, respectively.

[0217] [Example 2] Q using tetraethylammonium chloride １２ H １２ Dehydration condensation of three-dimensional crystals of Q １２ H １２0.112 g of the three-dimensional crystal was precipitated in 4.0 mL of acetic acid, and 0.102 g of tetraethylammonium chloride was dissolved in the solution to obtain a mixture. The resulting mixture was then stirred at room temperature for 2 hours and then stirred in an oil bath at 140 ° C for 1 day to obtain a reaction solution. The solvent was removed from the reaction solution by suction filtration, and the mixture was dried at 100 ° C for 1 hour to obtain 0.068 g of a white powder (crystal) as an intermediate. Powder X-ray crystal structure analysis showed that the obtained crystal had peaks at 7.66 °, 11.76 °, 13.98 °, 15.22 °, 19.21 °, 22.44 °, 22.83 °, 24.75 °, and 25.77 °. ２９ Q from Si-MAS-NMR ４ Species were observed, Q １２ H １２ It was revealed that dehydration condensation had progressed in some of the three-dimensional crystals, and the hydrogen bonds had been converted to covalent bonds. ２９ The results of Si-MAS-NMR are shown in Figures 6 and 7, respectively. Furthermore, 0.050 g of the obtained intermediate was dried in an electric furnace at 100°C for 4 hours, and then heated to 750°C at a rate of 1°C / min and maintained at that temperature for 5 hours to obtain a white powder (crystal) (hereinafter sometimes abbreviated as "UPZ-1"). Powder X-ray crystal structure analysis showed that the obtained crystal had peaks at 9.59°, 11.93°, 15.25°, 19.10°, 21.34°, 23.81°, 25.70°, 28.76°, and 31.18°. ２９ Q from Si-MAS-NMR ４ Only species were observed, and Q １２ H １２ In the three-dimensional crystal of Q, it was revealed that dehydration condensation had completely progressed and the hydrogen bond moiety had been converted into a covalent bond. Single-crystal X-ray crystal structure analysis showed that the obtained crystal was Q １２ H １２ It was found that the condensation proceeded while maintaining the hydrogen-bonded three-dimensional crystal structure of the compound. In other words, it was found that the obtained crystal was a compound having a regularly arranged pore structure in which the 12-mer silanol compound represented by the above formula (3) was bonded to each other by dehydration condensation. Powder X-ray crystal structure analysis, ２９ The measurement results of Si-MAS-NMR and single crystal X-ray crystal structure analysis are shown in FIGS. 8, 9, and 10, respectively.

[0218] [Example 3] Q using tetraethylammonium bromide １２ H １２ Dehydration condensation of three-dimensional crystals of Q １２ H １２ 0.110 g of the three-dimensional crystal was precipitated in 4.0 mL of acetic acid, and 0.137 g of tetraethylammonium bromide was dissolved in the solution to obtain a mixture. The resulting mixture was then stirred at room temperature for 2 hours and then stirred in an oil bath at 140 ° C for 1 day to obtain a reaction solution. The solvent was removed from the reaction solution by suction filtration, and the mixture was dried at 100 ° C for 1 hour to obtain 0.055 g of a white powder (crystal) as an intermediate. Powder X-ray crystal structure analysis showed that the obtained crystal had peaks at 7.66 °, 11.76 °, 13.98 °, 15.22 °, 19.21 °, 22.44 °, 22.83 °, 24.75 °, and 25.77 °. ２９ Q from Si-MAS-NMR ４ Species were observed, Q １２ H １２ In a part of the three-dimensional crystal, dehydration condensation proceeded, and the hydrogen bond moiety was converted to a covalent bond. In addition, 0.050 g of the obtained intermediate was dried in an electric furnace at 100 ° C. for 4 hours, and then heated to 750 ° C. at a rate of 1 ° C. / min and held for 5 hours to obtain a white powder (crystal) (UPZ-1). Powder X-ray crystal structure analysis showed that the obtained crystal had peaks at 9.59 °, 11.93 °, 15.25 °, 19.10 °, 21.34 °, 23.81 °, 25.70 °, 28.76 °, and 31.18 °. ２９ Q from Si-MAS-NMR ４ Only species were observed, and Q １２ H １２ In the three-dimensional crystal of (1), dehydration condensation had progressed completely, and the hydrogen bonds had been converted to covalent bonds. In other words, it was found that the obtained crystal was a compound having a pore structure in which the dodecamer silanol compound represented by formula (3) was bonded to each other by dehydration condensation and arranged in a regular pattern.

[0219] [Example 4] Q using triethylamine １２ H １２Dehydration condensation of three-dimensional crystals of Q １２ H １２ 0.100 g of the three-dimensional crystal was precipitated in 4.0 mL of acetic acid, and 3.6 μL of 2.0 mol% triethylamine was added to the solution to obtain a mixture. The resulting mixture was then stirred at room temperature for 2 hours and then stirred in an oil bath at 140 ° C for 12 hours to obtain a reaction solution. The solvent was removed from the reaction solution by suction filtration, and the mixture was dried at 100 ° C for 1 hour to obtain 0.059 g of a white powder (crystal) as an intermediate. Powder X-ray crystal structure analysis showed that the obtained crystal had peaks at 7.66 °, 11.76 °, 13.98 °, 15.22 °, 19.21 °, 22.44 °, 22.83 °, 24.75 °, and 25.77 °. ２９ Q from Si-MAS-NMR ４ Species are observed, Q １２ H １２ In a part of the three-dimensional crystal, dehydration condensation proceeded, and the hydrogen bond moiety was converted to a covalent bond. In addition, 0.050 g of the obtained intermediate was dried in an electric furnace at 100 ° C. for 4 hours, and then heated to 750 ° C. at a rate of 1 ° C. / min and held for 5 hours to obtain a white powder (crystal) (UPZ-1). Powder X-ray crystal structure analysis showed that the obtained crystal had peaks at 9.59 °, 11.93 °, 15.25 °, 19.10 °, 21.34 °, 23.81 °, 25.70 °, 28.76 °, and 31.18 °. ２９ Q from Si-MAS-NMR ４ Only species were observed, and Q １２ H １２ In the three-dimensional crystal of (1), dehydration condensation had progressed completely, and the hydrogen bonds had been converted to covalent bonds. In other words, it was found that the obtained crystal was a compound having a pore structure in which the dodecamer silanol compound represented by formula (3) was bonded to each other by dehydration condensation and arranged in a regular pattern.

[0220] [Example 5] Q using n-butanol as solvent １２ H １２ Dehydration condensation of three-dimensional crystals of Q １２ H １２0.100 g of the three-dimensional crystal was precipitated in 4.0 mL of n-butanol, and 3.6 μL of triethylamine was added to the solution to obtain a mixed solution. The resulting mixed solution was then stirred at room temperature for 2 hours, and then stirred in an oil bath at 140 ° C for 1 day to obtain a reaction solution. The solvent was removed from the reaction solution by suction filtration, and the mixture was dried at 100 ° C for 1 hour to obtain 0.070 g of a white powder (crystal) as an intermediate. Powder X-ray crystal structure analysis showed that the obtained crystal had peaks at 7.66 °, 11.76 °, 13.98 °, 15.22 °, 19.21 °, 22.44 °, 22.83 °, 24.75 °, and 25.77 °. ２９ Q from Si-MAS-NMR ４ Species are observed, Q １２ H １２ In a part of the three-dimensional crystal, dehydration condensation proceeded, and the hydrogen bond moiety was converted to a covalent bond. In addition, 0.050 g of the obtained intermediate was dried in an electric furnace at 100 ° C. for 4 hours, and then heated to 750 ° C. at a rate of 1 ° C. / min and held for 5 hours to obtain a white powder (crystal) (UPZ-1). Powder X-ray crystal structure analysis showed that the obtained crystal had peaks at 9.59 °, 11.93 °, 15.25 °, 19.10 °, 21.34 °, 23.81 °, 25.70 °, 28.76 °, and 31.18 °. ２９ Q from Si-MAS-NMR ４ Only species were observed, and Q １２ H １２ In the three-dimensional crystal of (1), dehydration condensation had progressed completely, and the hydrogen bonds had been converted to covalent bonds. In other words, it was found that the obtained crystal was a compound having a pore structure in which the dodecamer silanol compound represented by formula (3) was bonded to each other by dehydration condensation and arranged in a regular pattern.

[0221] [Example 6] Q １２ H １２ Dehydration condensation of three-dimensional crystals (nanosponge-like structure) of Q １２ H １２ 0.301 g of Q was dissolved in 3.0 mL of 1,4-dioxane and 0.30 mL of water to obtain a solution. 18.0 mL of tetrahydrofuran was added to this solution, mixed, and the mixture was kept at 15°C for 24 hours to recrystallize, thereby obtaining Q １２ H１２ 0.228 g of a colorless solid (columnar crystal) containing 70.9% by mass of １ H-NMR (DMSO-d6): 7.07 ppm, ２９ Si-NMR (DMSO-d6): -101.2 ppm). Furthermore, single crystal X-ray crystal structure analysis showed that the obtained crystals consisted of one molecule of Q １２ H １２ It is a crystal structure consisting of one molecule of 1,4-dioxane, two molecules of tetrahydrofuran, and six molecules of water. １２ H １２ The molecules were stabilized by hydrogen bonds, creating a three-dimensional (nano-sponge-like) structure. １２ H １２ 0.100 g of the three-dimensional crystal was dried for 168 hours under reduced pressure of 0.5 Pa while gradually increasing the temperature from -20°C to 0°C, to obtain 0.081 g of an intermediate white powder (crystal). Powder X-ray crystal structure analysis showed that the obtained crystal had peaks at 9.16°, 9.87°, 15.38°, 18.30°, 21.11°, 23.44°, and 30.87°. ２９ Q from Si-MAS-NMR ４ Species were observed, Q １２ H １２ In a part of the three-dimensional crystal, dehydration condensation proceeded, and hydrogen bonds were converted to covalent bonds. In addition, the obtained intermediate was dried in an electric furnace at 100 ° C for 4 hours, and then heated to 750 ° C at a rate of 1 ° C / min and maintained for 5 hours, and it was confirmed that the existing CHA-type zeolite was produced.

[0222] The method for producing a compound of the present invention makes it possible to obtain a compound having a regularly arranged pore structure while controlling, at the molecular level, the crystal structure in which silanol compounds interact with each other via hydrogen bonding through at least one hydroxy group. In particular, by combining the compound with other organic compounds, transition metal complexes, inorganic substances, elemental substances, and the like, it is possible to create a compound with a finely controlled structure having unprecedented physical properties. Furthermore, due to the characteristics of the pore structure, the compound of the present invention has industrial applicability in the fields of, for example, catalysis (petrochemistry, environmental purification) and separation membranes.

Claims

1. A compound having a regularly arranged pore structure in which at least one silanol compound selected from the group consisting of an octamer represented by the following formula (1), a decamer represented by the following formula (2), and a dodecamer represented by the following formula (3) is bonded to itself by dehydration condensation (however, excluding LTA type zeolite derived from the octamer represented by the following formula (1), and FAU type zeolite and CHA type zeolite derived from the dodecamer represented by the following formula (3)).

2. The compound according to claim 1, wherein the pore structure is a linearly ordered one-dimensional structure.

3. The compound according to claim 1, wherein the pore structure is a two-dimensional structure ordered in a plane.

4. The compound according to claim 1, wherein the pore structure is a two-dimensional structure in which a plurality of linearly aligned one-dimensional structures are bonded to each other via covalent bonds and aligned in a plane.

5. The compound according to claim 1, wherein the pore structure is a spatially ordered three-dimensional structure.

6. The compound according to claim 1, wherein the pore structure is a three-dimensional structure in which a plurality of planarly aligned two-dimensional structures are bonded together via covalent bonds to form a three-dimensionally aligned structure.

7. The compound according to claim 1, wherein the pore structure is a structure in which hydrogen-bonded moieties in a hydrogen-bonded inorganic structure are converted into covalent bonds by dehydration condensation, and the hydrogen-bonded inorganic structure is a crystal containing a plurality of the silanol compounds, and the silanol compounds interact with each other via hydrogen bonds between at least one hydroxy group.

8. The compound according to claim 1, wherein the pore structure is a one-dimensional structure in which two hydroxy groups contained in one silanol compound are linearly aligned by bonding with hydroxy groups of another silanol compound through dehydration condensation, and the two hydroxy groups bonded by dehydration condensation are two hydroxy groups on adjacent silicon atoms in one silanol compound, or two hydroxy groups on silicon atoms separated by one siloxane bond (-O-Si-O- bond) or more.

9. The compound according to claim 1, wherein the pore structure is a linearly aligned one-dimensional structure in which, of four hydroxy groups contained in one silanol compound, two hydroxy groups bonded to adjacent silicon atoms are bonded by dehydration condensation 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 further bonded by dehydration condensation to two hydroxy groups bonded to adjacent silicon atoms of another silanol compound.

10. The compound according to claim 1, wherein the pore structure is a one-dimensional structure in which a cyclic silanol surface contained in one silanol compound and a cyclic silanol surface contained in another silanol compound are bonded via a covalent bond and linearly aligned.

11. The compound according to claim 10, wherein the face of the cyclic silanol is the face of an 8-membered ring when the silanol compound is an octamer represented by formula (1), the face of an 8- or 10-membered ring when the silanol compound is a decamer represented by formula (2), or the face of an 8- or 12-membered ring when the silanol compound is a dodecamer represented by formula (3).

12. The pore structure is a two-dimensional structure in which a plurality of one-dimensional structures are bonded to each other via covalent bonds and aligned in a plane, and the one-dimensional structure is a linearly aligned one-dimensional structure in which two hydroxy groups contained in one silanol compound are bonded to hydroxy groups of another silanol compound by dehydration condensation, and the two hydroxy groups bonded by dehydration condensation are two hydroxy groups on adjacent silicon atoms in one silanol compound, or two hydroxy groups on silicon atoms separated by one siloxane bond (—O—Si—O— bond) or more, or 2. The compound according to claim 1, wherein two of the four hydroxy groups contained in one silanol compound that are bonded to adjacent silicon atoms are bonded to two hydroxy groups that are bonded to adjacent silicon atoms of another silanol compound by dehydration condensation, and the remaining two hydroxy groups that are bonded to adjacent silicon atoms of the one silanol compound are further bonded to two hydroxy groups that are bonded to adjacent silicon atoms of another silanol compound by dehydration condensation, thereby forming a linearly aligned one-dimensional structure.

13. The pore structure is a two-dimensional structure in which the ends of one-dimensional structures are bonded to each other via a covalent bond and aligned in a ring, and the one-dimensional structure is a linearly aligned one-dimensional structure in which two hydroxy groups contained in one silanol compound are bonded to hydroxy groups of another silanol compound by dehydration condensation, and the two hydroxy groups bonded by dehydration condensation are two hydroxy groups on adjacent silicon atoms in one silanol compound, or two hydroxy groups on silicon atoms separated by one siloxane bond (—O—Si—O— bond) or more, or 2. The compound according to claim 1, wherein two of the four hydroxy groups contained in one silanol compound that are bonded to adjacent silicon atoms are bonded to two hydroxy groups that are bonded to adjacent silicon atoms of another silanol compound by dehydration condensation, and the remaining two hydroxy groups that are bonded to adjacent silicon atoms of the one silanol compound are further bonded to two hydroxy groups that are bonded to adjacent silicon atoms of another silanol compound by dehydration condensation, thereby forming a linearly aligned one-dimensional structure.

14. The compound according to claim 1, wherein the pore structure is a two-dimensional structure in which one longitudinal side of a plurality of one-dimensional structures is bonded to each other via a covalent bond and aligned in a plane, and the one-dimensional structure is a one-dimensional structure in which a face of a cyclic silanol contained in one silanol compound in the silanol compound is bonded to a face of a cyclic silanol contained in another silanol compound via a covalent bond and aligned in a linear manner.

15. The pore structure is a three-dimensional structure in which a plurality of two-dimensional structures are bonded together via covalent bonds and arranged three-dimensionally, the two-dimensional structure is a two-dimensional structure in which a plurality of one-dimensional structures are bonded together via covalent bonds and arranged in a plane, the one-dimensional structure is a one-dimensional structure in which two hydroxy groups contained in one silanol compound are bonded to hydroxy groups of another silanol compound by dehydration condensation and arranged linearly, and the two hydroxy groups bonded by dehydration condensation are two hydroxy groups on adjacent silicon atoms in one silanol compound, or two hydroxy groups on silicon atoms separated by one siloxane bond (-O-Si-O- bond) or more, or 2. The compound according to claim 1, wherein two of the four hydroxy groups contained in one silanol compound that are bonded to adjacent silicon atoms are bonded to two hydroxy groups that are bonded to adjacent silicon atoms of another silanol compound by dehydration condensation, and the remaining two hydroxy groups that are bonded to adjacent silicon atoms of the one silanol compound are further bonded to two hydroxy groups that are bonded to adjacent silicon atoms of another silanol compound by dehydration condensation, thereby forming a linearly aligned one-dimensional structure.

16. The pore structure is a three-dimensional structure in which a plurality of two-dimensional structures are bonded together via covalent bonds and arranged three-dimensionally, the two-dimensional structure being a two-dimensional structure in which the ends of one-dimensional structures are bonded together via covalent bonds and arranged in a ring, the one-dimensional structure being a one-dimensional structure in which two hydroxy groups contained in one silanol compound are bonded to hydroxy groups of another silanol compound by dehydration condensation and arranged linearly, and the two hydroxy groups bonded by dehydration condensation are two hydroxy groups on adjacent silicon atoms in one silanol compound, or two hydroxy groups on silicon atoms separated by one siloxane bond (-O-Si-O- bond) or more, or 2. The compound according to claim 1, wherein two of the four hydroxy groups contained in one silanol compound that are bonded to adjacent silicon atoms are bonded to two hydroxy groups that are bonded to adjacent silicon atoms of another silanol compound by dehydration condensation, and the remaining two hydroxy groups that are bonded to adjacent silicon atoms of the one silanol compound are further bonded to two hydroxy groups that are bonded to adjacent silicon atoms of another silanol compound by dehydration condensation, thereby forming a linearly aligned one-dimensional structure.

17. The compound according to claim 1, wherein the pore structure is a three-dimensional structure in which a plurality of two-dimensional structures are bonded together via covalent bonds and arranged in a three-dimensional manner, the two-dimensional structure is a two-dimensional structure in which one longitudinal side of a plurality of one-dimensional structures is bonded together via covalent bonds and arranged in a plane, and the one-dimensional structure is a one-dimensional structure in which a face of a cyclic silanol contained in one silanol compound in the silanol compound is bonded to a face of a cyclic silanol contained in another silanol compound via covalent bonds and arranged linearly.

18. The compound according to claim 2, wherein the one-dimensional structure is at least one structure selected from the group consisting of the following formulas (1-1) to (1-3): (In structural formulas (1-1) to (1-3), one Si—O—Si bond is omitted and represented by one side.) 19. The compound according to claim 3, wherein the two-dimensional structure is at least one structure selected from the group consisting of the following formulas (2-1) and (2-2): (In structural formulas (2-1) to (2-2), one Si—O—Si bond is omitted and represented by one side.) 20. The compound according to claim 5, wherein the three-dimensional structure is at least one structure selected from the group consisting of the following formulas (3-1) to (3-3): (In structural formulas (3-1) to (3-3), one Si—O—Si bond is omitted and represented by one side.) 21. The compound 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.

22. A method for producing a compound, comprising the steps of: preparing a crystal (Z) containing a plurality of at least one silanol compound selected from the group consisting of an octamer represented by formula (1) below, a decamer represented by formula (2) below, and a dodecamer represented by formula (3) below, wherein the silanol compounds interact with each other via a hydrogen bond formed by at least one hydroxy group; using the crystal (Z) to obtain an intermediate in which some of the silanol compounds are bonded together by dehydration condensation; and heating the intermediate at 200 to 900°C to obtain a compound having a regularly arranged pore structure in which the silanol compounds are bonded together by dehydration condensation.

23. The step of obtaining the intermediate is a step of heating the crystal (Z) at 80 to 250°C in the presence of an additive and a solvent to obtain an intermediate in which some of the silanol compounds are bonded to each other by dehydration condensation, and in the step of obtaining the intermediate, the additive is an alkylammonium salt NR ４ ＋ X － (Wherein R is CH ３ , C ２ H ５ , C ３ H ７ , or C ４ H ９ and X=Cl, Br, or CH ３ COO), tertiary amines and amidines, and the solvent is an alcohol R'OH (wherein R' is CH ３ , C ２ H ５ , C ３ H ７ , C ４ H ９ , C ５ H １１ , (CH ３ ) ２ CH, or (CH ３ ) ３ C.), organic acid R″COOH (wherein R″ is H, CH ３ , C ２ H ５ , C ３ H ７ , or C ４ H ９ ), and ester R １ COOR ２ (In the formula, R １ and R ２ are each independently CH ３ , C ２ H ５ , C ３ H ７ , C ４ H ９ , or C ６ H ５ The method for producing the compound according to claim 22, wherein the compound is at least one selected from the group consisting of 24. The method for producing the compound according to claim 22, wherein the step of obtaining the intermediate is a step of freeze-drying the crystals (Z) to obtain an intermediate in which some of the silanol compounds are bonded to each other by dehydration condensation.

25. A method for producing the compound according to any one of claims 22 to 24, wherein the step of preparing the crystal (Z) comprises: a step of preparing a solution containing the silanol compound; and a step of adding to the solution, as necessary, a substance selected from the group consisting of organic compounds, transition metal complexes, inorganic substances, and simple elements, and recrystallizing the solution by a vapor diffusion method, by concentrating the solution under reduced pressure, by cooling the solution, or by heating the solution.

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