Method for producing two-dimensional coordination polymer, two-dimensional coordination polymer, and solution for forming two-dimensional coordination polymer

Abstract

The present invention provides a method for producing a two-dimensional coordination polymer, the method including: a preparation step for preparing a Ni compound, a Pd compound or a Pt compound, or a solution thereof, and benzenehexathiol, a derivative of benzenehexathiol, or a solution of at least one of benzenehexathiol and a derivative of benzenehexathiol; and a polymer formation step for preparing a single-phase solution that contains the Ni compound, the Pd compound, or the Pt compound and the benzenehexathiol so as to produce a two-dimensional coordination polymer in the single-phase solution. The present invention also provides: a two-dimensional coordination polymer which has a constituent unit represented by formula (2) and a constituent unit represented by formula (3), wherein M1 represents Ni or Pt, and M2 represents Mn, Fe, Co, Ni, Cu, Zn, Pd, or Ag; and a solution for forming a two-dimensional coordination polymer.

Description

Method for producing two-dimensional coordination polymer, two-dimensional coordination polymer, and solution for forming two-dimensional coordination polymer

[0001] The present disclosure relates to a method for producing a two-dimensional coordination polymer, a two-dimensional coordination polymer, and a solution for forming a two-dimensional coordination polymer.

[0002] Materials with nanometer-order thicknesses and two-dimensional structures are called nanosheets, and are expected to be applied to electronic device materials. For example, nanosheets (two-dimensional coordination polymers) formed by coordination polymers have been actively studied. Coordination polymers are known as materials with a structure in which structural units formed by the coordination of multidentate ligands to a central metal are continuously linked.

[0003] As a conventional method for producing a two-dimensional coordination polymer, for example, a method using a two-phase interfacial synthesis method as shown in Japanese Patent Application Laid-Open Nos. 2023-74937 and 2023-84127 is known.

[0004] The problem to be solved by the present disclosure is to provide a method for producing a two-dimensional coordination polymer that can be synthesized in large quantities. Another problem to be solved by the present disclosure is to provide a novel two-dimensional coordination polymer.

[0005] Means for solving the above problems include the following aspects. <1> A method for producing a two-dimensional coordination polymer, comprising: a preparation step of preparing a Ni compound, a Pd compound, or a Pt compound, or a solution A thereof, and a solution B of benzenehexathiol, a derivative of benzenehexathiol, or at least one of them; and a polymer formation step of preparing a single-phase solution containing the Ni compound, the Pd compound, or the Pt compound, and the benzenehexathiol, and producing a two-dimensional coordination polymer in the single-phase solution. <2> The method for producing a two-dimensional coordination polymer according to <1>, wherein the obtained two-dimensional coordination polymer has a constitutional unit represented by the following formula (1): In formula (1), M １ represents Ni, Pd or Pt. １is Ni or Pt. <4> The method for producing a two-dimensional coordination polymer according to <1> or <2>, wherein the preparing step is a step of preparing a solution A of the Ni compound, Pd compound, or Pt compound, and a solution B containing at least one of benzenehexathiol and a derivative of benzenehexathiol, and the polymer forming step is a step of mixing the solution A and the solution B to prepare the single-phase solution. <5> The method for producing a two-dimensional coordination polymer according to <4>, wherein the solvent of the solution A is an alcohol compound, and the solvent of the solution B is an aprotic polar solvent. <6> The method for producing a two-dimensional coordination polymer according to <4>, wherein the solvent of the solution A is a mixed solvent of water and an aprotic polar solvent, and the solvent of the solution B is a polar solvent. <7> The method for producing a two-dimensional coordination polymer according to any one of <2> to <6>, further comprising a structural change step of adding the Ni compound, Pd compound, or Pt compound, or a solution A thereof, to the single-phase solution after the polymer formation step to produce a two-dimensional coordination polymer having a constitutional unit represented by the following formula (2): In formula (2), M １represents Ni, Pd, or Pt. <8> The method for producing a two-dimensional coordination polymer according to any one of <1> to <7>, further comprising a heterometallic polymer-forming step of adding a Mn compound, an Fe compound, a Co compound, a Ni compound, a Cu compound, a Zn compound, a Pd compound, or an Ag compound, or a solution C thereof, to the single-phase solution after the polymer-forming step. <9> The method for producing a two-dimensional coordination polymer according to any one of <4> to <8>, wherein the amount of the Ni compound, Pd compound, or Pt compound in the preparing step is 1.4 molar equivalents or more and 1.6 molar equivalents or less relative to 1 molar equivalent of the benzenehexathiol or a derivative thereof. <10> The method for producing a two-dimensional coordination polymer according to any one of <4> to <9>, wherein the amount of the Ni compound, Pd compound, or Pt compound in the preparing step is 2.9 molar equivalents or more and 3.1 molar equivalents or less relative to 1 molar equivalent of the benzenehexathiol or a derivative thereof. <11> A structural unit represented by the following formula (2) and a structural unit represented by the following formula (3), １ is Ni or Pt, and the following M ２ is Mn, Fe, Co, Ni, Cu, Zn, Pd or Ag, １ When is Ni, M ２ does not represent Ni.) Two-dimensional coordination polymer. <12> Said M １ and the aforementioned M ２ The molar ratio (M １ : M ２ <13> A two-dimensional coordination polymer obtained by the method for producing a two-dimensional coordination polymer according to any one of <1> to <10>. <14> A two-dimensional coordination polymer-forming solution, which is a single-phase solution containing a Ni compound, a Pd compound, or a Pt compound, and at least one of benzenehexathiol and a derivative of benzenehexathiol.

[0006] According to the present disclosure, a method for producing a two-dimensional coordination polymer that allows for mass synthesis is provided, and a novel two-dimensional coordination polymer is also provided.

[0007] Figure 1 shows Raman spectra of the two-dimensional coordination polymers of Examples 1, 5, 6, and 7. Figure 2 shows EDS spectra of the two-dimensional coordination polymers of Examples 1, 5, 6, and 7. Figure 3 shows EDS spectra of each Pt １ M ２ 4 shows the Raman spectrum of BHT. Fig. 4 shows the volume average particle diameters of the two-dimensional coordination polymers of Examples 1 and 3 obtained by dynamic light scattering (DLS) analysis.

[0008] Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments. The following embodiments may be modified as appropriate within the scope of the present disclosure.

[0009] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0010] In the numerical ranges described in stages in the present disclosure, the upper limit value described in one numerical range may be replaced with the upper limit value of another numerical range described in stages, and the lower limit value described in one numerical range may be replaced with the lower limit value of another numerical range described in stages. In the numerical ranges described in stages in the present disclosure, the upper or lower limit value described in one numerical range may be replaced with a value shown in the examples.

[0011] In the present disclosure, the term "step" encompasses not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the intended purpose is achieved.

[0012] In the present disclosure, when a composition contains multiple substances corresponding to each component, the amount of each component in the composition means the total amount of the multiple substances present in the composition, unless otherwise specified.

[0013] In the present disclosure, a combination of preferred embodiments is a more preferred embodiment. In the present disclosure, room temperature means an uncontrolled ambient temperature, and includes a temperature range of 15°C to 30°C. Note that room temperature in the measurement conditions means 25°C ± 2°C unless otherwise specified.

[0014] <Method for Producing Two-Dimensional Coordination Polymer> The method for producing a two-dimensional coordination polymer according to the present disclosure includes a preparation step of preparing a Ni compound, a Pd compound, or a Pt compound or a solution thereof A, and a solution B of benzenehexathiol, a derivative of benzenehexathiol, or at least one of them, and a polymer formation step of preparing a single-phase solution containing the Ni compound, the Pd compound, or the Pt compound and the benzenehexathiol, and producing a two-dimensional coordination polymer in the single-phase solution.

[0015] As described above, as a conventional method for producing two-dimensional coordination polymers, methods using two-phase interfacial synthesis, as shown in Japanese Patent Application Laid-Open Nos. 2023-74937 and 2023-84127, are known. However, in the two-phase interfacial synthesis method, since synthesis takes place at an interface, it is difficult to produce large quantities of two-dimensional coordination polymers. In addition, since the interfacial reaction involves complex factors such as transport and diffusion of substances, there is also the problem that reaction control is difficult. The method for producing two-dimensional coordination polymers according to the present disclosure can provide a method for producing two-dimensional coordination polymers that can be easily mass-synthesized by performing synthesis in a single-phase solution. Furthermore, the method for producing two-dimensional coordination polymers according to the present disclosure allows easy reaction control, and the M described below can be easily produced. １．５ BHT type or M ３ It is easy to prepare two-dimensional coordination polymers such as BHT type, and it is also easy to prepare two-dimensional coordination polymers containing different metals.

[0016] In this specification, the term "single phase" refers to a solution phase in which no solid precipitate or layer separation is observed, and is a concept that also includes colloidal solutions.

[0017] The structure of the two-dimensional coordination polymer obtained by the method for producing a two-dimensional coordination polymer according to the present disclosure is not particularly limited as long as it contains a Ni compound, a Pd compound, or a Pt compound and benzenehexathiol and is a two-dimensional coordination polymer that can form a single phase in solution. The two-dimensional coordination polymer obtained by the method for producing a two-dimensional coordination polymer according to the present disclosure preferably has a constitutional unit represented by the following formula (1), for example:

[0018] In formula (1), M１ represents Ni, Pd or Pt, and preferably represents Ni or Pt.

[0019] [Preparation Step] The method for producing a two-dimensional coordination polymer according to the present disclosure includes a preparation step of preparing a Ni compound, a Pd compound, or a Pt compound or a solution thereof (A), and a solution B of benzenehexathiol, a derivative of benzenehexathiol, or at least one of these. From the viewpoint of two-dimensional coordination polymer formation, the Ni compound, Pd compound, or Pt compound is preferably a divalent Ni compound, Pd compound, or Pt compound. Furthermore, from the viewpoint of two-dimensional coordination polymer formation, the Ni compound is preferred. The Ni compound, Pd compound, or Pt compound may be synthesized or commercially available.

[0020] The Ni compound is not particularly limited, and examples thereof include nickel formate, nickel acetate, nickel lactate, nickel chloride, nickel bromide, nickel carbonate, nickel nitrate, nickel sulfate, nickel oxide, nickel acetylacetonate complex, nickel ethylenediamine complex, nickel ethylenediaminetetraacetic acid complex, hydrates thereof, etc. Among these, from the viewpoints of stability and two-dimensional coordination polymer formability, nickel acetate, nickel chloride, nickel bromide, nickel acetylacetonate complex, or hydrates thereof are preferred, and nickel acetate or a hydrate thereof is more preferred.

[0021] The Pd compound is not particularly limited, but for example, potassium hexachloropalladate (IV) (i.e., K ２ [PdCl ６ ]), potassium tetrachloropalladate (II) (i.e., K ２ [PdCl ４ ]), sodium tetrachloropalladate (II) (i.e., Na ２ [PdCl ４ ]), palladium(II) acetate, palladium(II) chloride, palladium(II) bromide, dichlorobis(acetonitrile)palladium(II) (i.e., Pd(CH ３ CN) ２ Cl２ ), dichlorobis(ethylenediamine)palladium(II), palladium(II) acetylacetonate complex, and hydrates thereof.

[0022] The Pt compound is not particularly limited, but for example, potassium hexachloroplatinate (IV) (i.e., K ２ [PtCl ６ ]), potassium tetrachloroplatinate (II) (i.e., K ２ [PtCl ４ ]), sodium tetrachloroplatinate (II) (i.e., Na ２ [PtCl ４ ]), platinum(II) chloride, platinum(II) bromide, dichlorobis(acetonitrile)platinum(II) (i.e., Pt(CH ３ CN) ２ Cl ２ ), dichlorobis(ethylenediamine)platinum(II), platinum(II) acetylacetonate complex, and hydrates thereof.

[0023] In the preparation step, from the viewpoints of reaction rate and two-dimensional coordination polymer formability, it is preferable to prepare a solution A of a Ni compound, a Pd compound, or a Pt compound. The solvent used for the solution A of the Ni compound, the Pd compound, or the Pt compound is not particularly limited as long as it can dissolve the compound. However, from the viewpoints of solubility and two-dimensional coordination polymer formability, a polar solvent is preferable, a protic polar solvent is more preferable, and an alcohol compound is even more preferable. In the present disclosure, a polar solvent refers to a solvent having a relative dielectric constant of 5 or more at 25°C. Specific examples of polar solvents include water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, benzyl alcohol, diethylene glycol, triethylene glycol, glycerin, tetrahydrofuran, dimethoxyethane, acetone, ethyl methyl ketone, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, formaldehyde, N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoric acid amide, acetonitrile, propylonitrile, nitromethane, nitrobenzene, and dimethyl sulfoxide (DMSO). Among these, from the viewpoints of solubility, ease of removal, and two-dimensional coordination polymer formability, polar solvents other than water are preferred, alcohol compounds are more preferred, and at least one solvent selected from the group consisting of methanol, ethanol, and 2-propanol is particularly preferred.

[0024] The solvent used in the solution A of the Ni compound, Pd compound, or Pt compound may be one type alone or two or more types. The content of the solvent is not particularly limited and can be appropriately selected depending on the solubility of each of the Ni compound, Pd compound, and Pt compound, the desired two-dimensional coordination polymer, the solubility of the resulting two-dimensional coordination polymer, etc.

[0025] Benzenehexathiol (BHT) may be a commercially available product or may be produced based on a method described in a known literature, such as Jennifer A. Harnisch, Robert J. Angelici, Inorganica Chimica Acta, Volumes 300-302, 20 April 2000, Pages 273-279.

[0026] In addition, a derivative of benzenehexathiol can also be used. The derivative of benzenehexathiol is not particularly limited as long as it is a compound that can replace benzenehexathiol, and examples thereof include tin-protected benzenehexathiol. Examples of literature include Tigmansu Pal, Shotaro Doi, Hiroaki Maeda, Keisuke Wada, Choon Meng Tan, Naoya Fukui, Ryota Sakamoto, Shinji Tsuneyuki, Sono Sasaki and Hiroshi Nishihara, Chem. Sci., Volume 10, 17 April 2019, Pages 5218-5225. An example of a tin-protected benzenehexathiol is the following compound.

[0027]

[0028] In the preparation step, it is preferable to prepare a solution B of benzenehexathiol or a derivative thereof from the viewpoint of reaction rate and two-dimensional coordination polymer formation ability.

[0029] The solvent used for Solution B of benzenehexathiol or a derivative thereof is not particularly limited as long as it can dissolve benzenehexathiol or a derivative thereof. However, from the viewpoints of solubility and two-dimensional coordination polymer formation, aprotic polar solvents, halogenated solvents, polar solvents, and mixed solvents thereof are preferred. Examples of aprotic polar solvents from the viewpoints of solubility, ease of removal, and two-dimensional coordination polymer formation include tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, acetonitrile, nitromethane, and dimethyl sulfoxide (DMSO). Examples of halogenated solvents include dichloromethane, chloroform, 1,2-dichloroethane, carbon tetrachloride, chlorobenzene, and dichlorobenzene. Examples of polar solvents include those described above. Among the above, it is more preferred that the solvent used for Solution B of benzenehexathiol or a derivative thereof is at least one solvent selected from the group consisting of acetone, dichloromethane, tetrahydrofuran, and dimethyl sulfoxide.

[0030] The solvent used in the solution B of benzenehexathiol or a derivative thereof may be used alone or in combination of two or more. The content of the solvent is not particularly limited and can be appropriately selected depending on the solubility of benzenehexathiol or a derivative thereof, the desired two-dimensional coordination polymer, the solubility of the resulting two-dimensional coordination polymer, etc., but the concentration of benzenehexathiol or a derivative thereof is preferably 0.001 mM (= 0.001 mmol / L) or less, i.e., the saturated concentration of benzenehexathiol or a derivative thereof, more preferably 0.01 mM or more, and particularly preferably 0.05 mM or more.

[0031] In the preparation step, the concentration of solution A is preferably 0.10 mmol / L to 1.00 mmol / L, more preferably 0.17 mmol / L to 0.50 mmol / L, when producing a two-dimensional coordination polymer containing Pt and having a constitutional unit represented by formula (1). When the concentration of solution A is within the above range, the two-dimensional coordination polymer having a constitutional unit represented by formula (1) can be more efficiently synthesized in large quantities.

[0032] In the preparation step, the concentration of solution A is preferably 0.30 mmol / L to 2.00 mmol / L, more preferably 0.50 mmol / L to 1.50 mmol / L, when producing a two-dimensional coordination polymer containing Pt and having a constitutional unit represented by formula (2). When the concentration of solution A is within the above range, the two-dimensional coordination polymer having a constitutional unit represented by formula (2) can be more efficiently synthesized in large quantities.

[0033] In the preparation step, the concentration of solution A is preferably 0.03 mmol / L or more and 0.20 mmol / L or less, and more preferably 0.05 mmol / L or more and 0.15 mmol / L or less, when producing a two-dimensional coordination polymer containing Ni and having a constitutional unit represented by formula (1). When the concentration of solution A is within the above range, the two-dimensional coordination polymer having the constitutional unit represented by formula (1) can be more efficiently mass-synthesized.

[0034] In the preparation step, the concentration of solution A is preferably 0.10 mmol / L to 0.50 mmol / L, more preferably 0.15 mmol / L to 0.45 mmol / L, when producing a two-dimensional coordination polymer containing Ni and having a constitutional unit represented by formula (2). When the concentration of solution A is within the above range, the two-dimensional coordination polymer having the constitutional unit represented by formula (2) can be more efficiently mass-synthesized.

[0035] In the preparation step, the concentration of Solution B is preferably 1.50 mmol / L to 3.50 mmol / L, more preferably 1.00 mmol / L to 3.00 mmol / L, when producing a two-dimensional coordination polymer containing Pt, for example. When the concentration of Solution B is within the above range, the two-dimensional coordination polymer can be more efficiently synthesized in large quantities.

[0036] In the preparation step, the concentration of Solution B is preferably 0.03 mmol / L to 0.20 mmol / L, more preferably 0.10 mmol / L to 0.20 mmol / L, when producing a Ni-containing two-dimensional coordination polymer, for example. When the concentration of Solution B is within the above range, the two-dimensional coordination polymer can be more efficiently synthesized in large quantities.

[0037] In one aspect, in the method for producing a two-dimensional coordination polymer according to the present disclosure, the preparation step is preferably a step of preparing a solution A containing a Ni compound, a Pd compound, or a Pt compound, and a solution B containing at least one of benzenehexathiol and a derivative of benzenehexathiol, and the polymer formation step is preferably a step of mixing the solution A and the solution B to prepare the single-phase solution. In this aspect, the two-dimensional coordination polymer described above can be more efficiently mass-synthesized.

[0038] In one embodiment, in the production of a two-dimensional coordination polymer having constitutional units represented by formulas (1) to (3), M １ is Ni, it is preferable that the solution A is an alcohol compound and the solution B is an aprotic polar solvent. When the combination of solvent A and solvent B in the preparation step is in the above-mentioned embodiment, the two-dimensional coordination polymer is easily synthesized in large quantities more efficiently. Note that the preferred embodiments of the alcohol compound and the aprotic polar solvent are as described above.

[0039] In one embodiment, in the production of a two-dimensional coordination polymer having constitutional units represented by formulas (1) to (3), M １is Pt, the solvent of the solution A is preferably a mixed solvent of water and an aprotic polar solvent, and the solvent of the solution B is preferably a polar solvent. When the combination of solvent A and solvent B in the preparation step is in the above-mentioned embodiment, the two-dimensional coordination polymer is easily synthesized in large quantities more efficiently. Note that the preferred embodiments of the polar solvent and the aprotic polar solvent are as described above.

[0040] [Polymer Formation Step] The method for producing a two-dimensional coordination polymer according to the present disclosure includes a polymer formation step of preparing a single-phase solution containing the Ni compound, the Pd compound, or the Pt compound and the benzenehexathiol, and producing a two-dimensional coordination polymer in the single-phase solution.

[0041] In the polymer formation step, from the viewpoints of reaction rate and two-dimensional coordination polymer formation ability, it is preferable to mix the solution of the Ni compound, Pd compound, or Pt compound with the solution of benzenehexathiol or a derivative thereof to prepare a single-phase solution.

[0042] The mixing ratio of the Ni compound, Pd compound, or Pt compound to the benzenehexathiol or a derivative thereof in the polymer formation step is not particularly limited. However, from the viewpoint of two-dimensional coordination polymer formability, the amount of the Ni compound, Pd compound, or Pt compound relative to 1 molar equivalent of the benzenehexathiol or a derivative thereof is preferably 0.9 molar equivalents to 3.4 molar equivalents, more preferably 1.4 molar equivalents to 3.1 molar equivalents, even more preferably 1.4 molar equivalents to 1.6 molar equivalents or 2.9 molar equivalents to 3.1 molar equivalents, and particularly preferably 1.45 molar equivalents to 1.55 molar equivalents or 2.95 molar equivalents to 3.05 molar equivalents.

[0043] The two-dimensional coordination polymer may be dissolved in a single-phase solution or may be in the form of colloidal particles. When the two-dimensional coordination polymer is a colloidal particle, the volume-average particle diameter of the two-dimensional coordination polymer is preferably 10 nm to 100 nm, more preferably 20 nm to 80 nm, and even more preferably 20 nm to 70 nm. The volume-average particle diameter of the two-dimensional coordination polymer is a value measured by dynamic light scattering using a particle size distribution analyzer (Horiba, Ltd., SZ-100V2).

[0044] When the solution of the Ni compound, Pd compound, or Pt compound is mixed with the solution of benzenehexathiol to prepare a single-phase solution, the solvent for the solution of the Ni compound, Pd compound, or Pt compound and the solvent for the solution of the benzenehexathiol or a derivative thereof are not particularly limited as long as they form a single-phase solution, and the solvent for the solution of the Ni compound, Pd compound, or Pt compound and the solvent for the solution of the benzenehexathiol or a derivative thereof may be different solvents or the same solvent.

[0045] In one embodiment, from the viewpoint of two-dimensional coordination polymer formability, the preparation step may be a step of preparing a solution A of a Ni compound and a solution B of benzenehexathiol, and the polymer formation step may be a step of mixing the solution A and the solution B to prepare the single-phase solution. In this case, it is more preferable that the solvent of the solution A is an alcohol compound and the solvent of the solution B is an aprotic polar solvent, and it is particularly preferable that the solvent of the solution A is methanol and the solvent B of the solution is at least one of tetrahydrofuran and acetone.

[0046] In one embodiment, from the viewpoint of two-dimensional coordination polymer formability, the preparation step may be a step of preparing a solution A of a Pt compound and a solution B of a benzenehexathiol derivative, and the polymer formation step may be a step of mixing the solution A and the solution B to prepare the single-phase solution. In this case, it is more preferable that the solvent of the solution A is a mixed solvent of water and an aprotic polar solvent, and the solvent of the solution B is a polar solvent, and it is particularly preferable that the solvent of the solution A is a mixed solvent of water and DMSO, and the solvent B of the solution is dichloromethane.

[0047] The reaction temperature in the polymer formation step may be determined in consideration of the reaction rate. The reaction temperature may be determined in the range of not less than the freezing point of the solvent used but not more than the boiling point of the solvent. The reaction temperature may be 10°C to 90°C, 10°C to 70°C, or 20°C to 50°C. The reaction time in the polymer formation step may be determined in consideration of the reactivity, the degree of growth of the two-dimensional coordination polymer, and the like. The reaction time may be 1 second to 1 month, 1 hour to 1 week, or 5 hours to 1 day.

[0048] The polymer formation step is preferably carried out in an atmosphere of an inert gas, such as nitrogen or argon.

[0049] The two-dimensional coordination polymer obtained in the polymer formation step preferably has at least one of the constitutional units represented by the following formula (1) and the following formula (2), and from the viewpoint of synthesis difficulty, it is more preferable that it has the constitutional unit represented by the following formula (1). A two-dimensional coordination polymer having a constitutional unit represented by formula (1) may have the constitutional unit represented by formula (1) in a partial region of its molecular structure. A two-dimensional coordination polymer having a constitutional unit represented by formula (2) may have the constitutional unit represented by formula (2) in a partial region of its molecular structure. A two-dimensional coordination polymer may have the constitutional units of each of formulas (1) to (2) in the same molecular skeleton. In this case, for convenience, the two-dimensional coordination polymer is identified as having the constitutional unit of each of formulas (1) to (2) that can be contained in the largest amount based on theoretical values.

[0050]

[0051] In formula (1), M １ represents Ni, Pd or Pt, and preferably represents Ni or Pt.

[0052]

[0053] In formula (2), M １ represents Ni, Pd or Pt, and preferably represents Ni or Pt.

[0054] In the present disclosure, the two-dimensional coordination polymer having the constitutional unit represented by the formula (1) is a two-dimensional coordination polymer in which 1.5 molar equivalents of a metal atom are present per 1 molar equivalent of benzenehexathiol or a derivative thereof, and M １．５ BHT type two-dimensional coordination polymer or M １．５ An example of a two-dimensional coordination polymer having a constitutional unit represented by the formula (1) is a two-dimensional coordination polymer having a structure represented by the following formula (1A):

[0055]

[0056] In the present disclosure, the two-dimensional coordination polymer having the constitutional unit represented by the formula (2) is a two-dimensional coordination polymer in which 3 molar equivalents of metal atoms are present per 1 molar equivalent of benzenehexathiol or a derivative thereof, and M ３ BHT type two-dimensional coordination polymer or M ３ An example of a two-dimensional coordination polymer having a constitutional unit represented by the formula (2) is a two-dimensional coordination polymer having a structure represented by the following formula (2A).

[0057]

[0058] The particle size of the two-dimensional coordination polymer is not particularly limited, but is preferably in the range of 3 nm to 1 μm, more preferably in the range of 10 nm to 300 nm, and even more preferably in the range of 30 nm to 100 nm. The particle size of the two-dimensional coordination polymer is measured by dynamic light scattering (DLS). Furthermore, the two-dimensional coordination polymer obtained by the method for producing a two-dimensional coordination polymer according to the present disclosure may be a monolayer film or a multilayer film, or may be an aggregate of two-dimensional coordination polymers containing at least one type selected from the group consisting of monolayer films and multilayer films.

[0059] [Structural Change Step] The method for producing a two-dimensional coordination polymer according to the present disclosure may further include a structural change step of adding a Ni compound, a Pd compound, or a Pt compound, or a solution A thereof, to the single-phase solution after the polymer formation step to prepare a two-dimensional coordination polymer having a constitutional unit represented by formula (2).

[0060] In the structural change step, the two-dimensional coordination polymer having the constitutional unit represented by formula (1) obtained in the polymer formation step can be changed into a two-dimensional coordination polymer having the constitutional unit represented by formula (2), and the method for producing a two-dimensional coordination polymer according to the present disclosure can selectively synthesize each of the two-dimensional coordination polymers described above. Furthermore, by including the structural change step, the method for producing a two-dimensional coordination polymer according to the present disclosure can easily produce a two-dimensional coordination polymer having the constitutional unit represented by formula (1) and a two-dimensional coordination polymer having the constitutional unit represented by formula (2).

[0061] The type of the Ni compound, Pd compound, or Pt compound in the structural change step is M in the two-dimensional coordination polymer having the constitutional unit represented by formula (1). １ M in a two-dimensional coordination polymer having a constitutional unit represented by formula (2) １ As long as these compounds are the same metal, they may be the same as or different from the Ni compound, Pd compound or Pt compound contained in solution A.

[0062] When the structural modification step is included, the amount of the Ni compound, Pd compound, or Pt compound in the polymer formation step is preferably 0.5 to 1.9 molar equivalents relative to 1 molar equivalent of the benzenehexathiol or its derivative, more preferably 1.0 to 1.5 molar equivalents, from the viewpoint of forming a two-dimensional coordination polymer having a structural unit represented by formula (1). Furthermore, the amount of the Ni compound, Pd compound, or Pt compound added in the structural modification step is preferably 1.1 to 2.5 molar equivalents relative to 1 molar equivalent of the benzenehexathiol or its derivative used in the polymer formation step, more preferably 1.5 to 2.0 molar equivalents, from the viewpoint of forming a two-dimensional coordination polymer having a structural unit represented by formula (2). Furthermore, in the structural modification step, it is preferable to use a Ni compound from the viewpoint of two-dimensional coordination polymer formation.

[0063] In the structural modification step, from the viewpoints of reaction rate and two-dimensional coordination polymer formation, it is preferable to use a solution of the Ni compound, Pd compound, or Pt compound. The solvent used for the solution of the Ni compound, Pd compound, or Pt compound is the same as the solvent used for the solution of the Ni compound, Pd compound, or Pt compound in the preparation step, and preferred embodiments are also the same.

[0064] The reaction temperature in the structural modification step may be determined in consideration of the reaction rate. The reaction temperature may be determined in the range of from the freezing point of the solvent used to the boiling point of the solvent. The reaction temperature may be 10°C to 90°C, 10°C to 70°C, or 20°C to 50°C. The reaction time in the structural modification step may be determined in consideration of the reactivity, the progress of the structural modification of the two-dimensional coordination polymer, and the like. The reaction time may be 1 second to 1 month, 1 minute to 1 week, or 2.5 hours to 15 hours.

[0065] The structural modification step is preferably carried out in an atmosphere of an inert gas, such as nitrogen or argon.

[0066] [Heterometallic Polymer Formation Step] The method for producing a two-dimensional coordination polymer according to the present disclosure preferably further includes, after the polymer formation step, a heterometallic polymer formation step of adding a Mn compound, an Fe compound, a Co compound, a Ni compound, a Cu compound, a Zn compound, a Pd compound, or an Ag compound, or a solution C thereof, to the single-phase solution.

[0067] In the heterometallic polymer formation step, a metal compound different from the metal species of the compound contained in solution A prepared in the preparation step is selected from Mn compounds, Fe compounds, Co compounds, Ni compounds, Cu compounds, Zn compounds, Pd compounds, or Ag compounds, and the metal compound or its solution C is added. For example, in the production of a two-dimensional coordination polymer having a constitutional unit represented by formula (1), if solution A containing a Ni compound is prepared in the preparation step, then in the heterometallic polymer formation step, a compound other than the Ni compound, i.e., "solution C of a Mn compound, Fe compound, Co compound, Cu compound, Zn compound, Pd compound, or Ag compound," is added to the single-phase solution.

[0068] In one embodiment, in the production of a two-dimensional coordination polymer having constitutional units represented by formulas (1) to (3), M １ is Ni, it is preferable to add a Mn compound, a Co compound, a Cu compound, or a Zn compound, or a solution thereof, C, in the heterometallic polymer formation step. In the above embodiment, a two-dimensional coordination polymer containing heterometals can be synthesized in large quantities more efficiently in a single-phase liquid.

[0069] In one embodiment, in the production of a two-dimensional coordination polymer having constitutional units represented by formulas (1) to (3), M １ is Pt, it is preferable to add an Fe compound, a Ni compound, a Cu compound, a Pd compound, or an Ag compound, or a solution thereof, C, in the heterometallic polymer formation step. In the above embodiment, a two-dimensional coordination polymer containing heterometals can be synthesized in large quantities more efficiently in a single-phase liquid.

[0070] The Ni compound is as described above.

[0071] The Mn compound is not particularly limited, and examples thereof include manganese chloride, manganese bromide, manganese sulfate, manganese nitrate, manganese tetrafluoroborate complex, manganese acetylacetonate complex, manganese ethylenediamine complex, manganese ethylenediaminetetraacetic acid complex, and hydrates thereof.

[0072] The Fe compound is not particularly limited, and examples thereof include ferrous chloride, ferrous bromide, ferrous iodide, ferrous nitrate, ferrous sulfate, ferrous acetate, ferrous benzoate, iron tetrafluoroborate complex, iron acetylacetonate complex, iron ethylenediamine complex, iron ethylenediaminetetraacetic acid complex, and hydrates thereof.

[0073] The Co compound is not particularly limited, and examples thereof include cobalt chloride, cobalt bromide, cobalt iodide, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt benzoate, cobalt tetrafluoroborate complex, cobalt acetylacetonate complex, cobalt ethylenediamine complex, cobalt ethylenediaminetetraacetic acid complex, and hydrates thereof.

[0074] The Cu compound is not particularly limited, and examples thereof include cupric chloride, cupric bromide, cupric iodide, cupric nitrate, cupric sulfate, cupric acetate, cupric benzoate, copper tetrafluoroborate complex, copper acetylacetonate complex, copper ethylenediamine complex, copper ethylenediaminetetraacetic acid complex, and hydrates thereof.

[0075] The Ag compound is not particularly limited, but examples thereof include silver tetrafluoroborate complex, silver nitrate, silver perchlorate, silver acetate, and hydrates thereof.

[0076] The Zn compound is not particularly limited, and examples thereof include zinc formate, zinc acetate, zinc lactate, zinc chloride, zinc bromide, zinc carbonate, zinc nitrate, zinc sulfate, zinc oxide, zinc tetrafluoroborate complex, zinc acetylacetonate complex, zinc ethylenediamine complex, zinc ethylenediaminetetraacetic acid complex, and hydrates thereof. Among these, from the viewpoints of reactivity, stability, and two-dimensional coordination polymer formability, zinc acetate, zinc tetrafluoroborate complex, or hydrates thereof are preferred as the Zn compound.

[0077] In the heterometallic polymer formation step, from the viewpoints of reaction rate and two-dimensional coordination polymer formation ability, it is preferable to prepare a solution C of a Mn compound, an Fe compound, a Co compound, a Ni compound, a Cu compound, a Zn compound, a Pd compound, or an Ag compound. The solvent used for solution C is not particularly limited as long as it can dissolve the compound, but from the viewpoints of solubility and two-dimensional coordination polymer formation ability, a polar solvent is preferable, a protic polar solvent is more preferable, and an alcohol compound is even more preferable. Specific solvents are the same as those used for the Ni compound, Pd compound, or Pt compound solution in the preparation step, and preferred embodiments are also the same.

[0078] From the viewpoint of forming a two-dimensional coordination polymer having a constitutional unit represented by formula (2), the amount of the Mn compound, Fe compound, Co compound, Ni compound, Cu compound, Zn compound, Pd compound, or Ag compound added in the heterometallic polymer formation step is preferably 0.1 to 10.0 molar equivalents, more preferably 1.1 to 2.5 molar equivalents, and even more preferably 1.5 to 2.0 molar equivalents, relative to 1 molar equivalent of the Ni compound, Pd compound, or Pt compound.

[0079] The two-dimensional coordination polymer obtained in the heterometallic polymer formation step has a constitutional unit represented by the formula (2) and a constitutional unit represented by the following formula (3), and M １ is Ni or Pt, and M ２may be a two-dimensional coordination polymer in which M is Mn, Fe, Co, Ni, Cu, Zn, Pd, or Ag. １ When is Ni, M ２ does not represent Ni.

[0080]

[0081]

[0082] A two-dimensional coordination polymer having constitutional units represented by formulas (2) to (3) may have constitutional units represented by formulas (2) to (3) in at least a partial region of its molecular structure. A two-dimensional coordination polymer having constitutional units represented by formulas (2) to (3) may further have a constitutional unit represented by formula (1) in the same molecular skeleton. In this case, for convenience of identification, the two-dimensional coordination polymer is referred to as a two-dimensional coordination polymer having constitutional units represented by formulas (2) and (3).

[0083] An example of the two-dimensional coordination polymer obtained in the heterometallic polymer formation step is a two-dimensional coordination polymer having a structure represented by the following formula (3A).

[0084] The two-dimensional coordination polymer having the structure represented by the following formula (3A) is prepared by mixing 1 molar equivalent of benzenehexathiol or a derivative thereof with a metal atom (M １ and M ２ The sum of M １ １ M ２ ２ The number of moles is a theoretical value, and may vary depending on factors such as the reactivity of the metal species. １ and M ２ The ratio may vary.

[0085]

[0086] The two-dimensional coordination polymer obtained in the heterometallic polymer formation step is １ and M in the formula (3) ２ The molar ratio (M １ : M ２) is preferably 1.0:0.1 or more and 1.0:3.0 or less, more preferably 1.0:0.1 or more and 1.0:2.5 or less, and even more preferably 1.0:0.1 or more and 1.0:2.3 or less. １ : M ２ When the value of (R) is within the above range, a two-dimensional coordination polymer having the constitutional unit represented by the following formula (2) and the constitutional unit represented by the following formula (3) can be more efficiently mass-synthesized.

[0087] The concentration of solution C is, for example, preferably 10.00 mmol / L or more and 40.00 mmol / L or less, and more preferably 20.00 mmol / L or more and 30.00 mmol / L or less. When the concentration of solution C is within the above range, two-dimensional coordination polymers having constitutional units represented by formulas (2) and (3) can be more efficiently and easily synthesized in large quantities.

[0088] The method for producing a two-dimensional coordination polymer according to the present disclosure may include other steps in addition to those described above. The other steps are not particularly limited, and examples thereof include an isolation step of isolating the obtained two-dimensional coordination polymer, a washing step of washing the isolated two-dimensional coordination polymer, and a drying step of drying the isolated or washed two-dimensional coordination polymer.

[0089] [Uses] The uses of the two-dimensional coordination polymer produced by the method for producing a two-dimensional coordination polymer according to the present disclosure are not particularly limited, and preferred examples include conductive materials, catalysts, electrochemical catalysts, photocatalysts, energy storage materials, optical sensors (e.g., ultraviolet to near-infrared), chemiresistive sensors, electrochemical sensors, solution-gate FET (field-effect transistor) sensors, hole transport materials, magnetic materials, electrode materials, etc. Furthermore, depending on the use, the two-dimensional coordination polymer produced by the method for producing a two-dimensional coordination polymer according to the present disclosure may be isolated and used as is or in combination with other components, a single-phase solution containing the obtained two-dimensional coordination polymer may be used as is or in combination with other components, or the single-phase solution containing the obtained two-dimensional coordination polymer may be applied to a substrate as is or in combination with other components and then dried.

[0090] <Two-dimensional Coordination Polymer> The two-dimensional coordination polymer according to the present disclosure has a constitutional unit represented by the following formula (2) and a constitutional unit represented by the following formula (3), and １ is Ni or Pt, and the following M ２ is Mn, Fe, Co, Ni, Cu, Zn, Pd or Ag, provided that M １ When is Ni, M ２ does not represent Ni.

[0091]

[0092]

[0093] The M in the two-dimensional coordination polymer according to the present disclosure １ and the aforementioned M ２ The molar ratio (M １ : M ２ The molar ratio (M) is preferably 1.0:0.1 or more and 1.0:3.0 or less, more preferably 1.0:0.1 or more and 1.0:2.5 or less, and even more preferably 1.0:0.1 or more and 1.0:2.3 or less. １ : M ２ When the molar ratio (M) is within the above range, a two-dimensional coordination polymer having the constitutional unit represented by the following formula (2) and the constitutional unit represented by the following formula (3) can be more efficiently mass-synthesized. １ : M ２ ) is determined by scanning electron microscope energy dispersive X-ray spectroscopy (SEM-EDX) using a JEOL JCM-7000.

[0094] The two-dimensional coordination polymer according to the present disclosure is preferably produced by the method for producing a two-dimensional coordination polymer according to the present disclosure. The use of the two-dimensional coordination polymer according to the present disclosure is not particularly limited, but preferred uses include the use of the two-dimensional coordination polymer produced by the method for producing a two-dimensional coordination polymer according to the present disclosure.

[0095] The two-dimensional coordination polymer according to the present disclosure can be obtained by the method for producing the two-dimensional coordination polymer according to the present disclosure. １．５ BHT type or M ３Two-dimensional coordination polymers such as BHT type (M=Ni, etc.) can be efficiently obtained by mass synthesis.

[0096] The preferred structure and aspects of the two-dimensional coordination polymer according to the present disclosure are the same as the preferred structure and aspects of the method for producing a two-dimensional coordination polymer according to the present disclosure.

[0097] The solution for forming a two-dimensional coordination polymer according to the present disclosure is a single-phase solution containing a Ni compound, a Pd compound, or a Pt compound, and at least one of benzenehexathiol and a benzenehexathiol derivative. According to the present disclosure, the two-dimensional coordination polymer can be mass-synthesized.

[0098] Preferred aspects of the Ni, Pd, and Pt compounds are the same as the preferred aspects of the "Ni compound, Pd compound, or Pt compound" in the method for producing a two-dimensional coordination polymer according to the present disclosure described above.

[0099] The solvent contained in the two-dimensional coordination polymer forming solution according to the present disclosure is not particularly limited, and may be any solvent that can dissolve the raw materials for forming the two-dimensional coordination polymer, i.e., a Ni compound, a Pd compound, or a Pt compound, and at least one of benzenehexathiol and a benzenehexathiol derivative, to form a single phase. Examples of the solvent include the solvents exemplified in the method for producing a two-dimensional coordination polymer according to the present disclosure.

[0100] The present disclosure will be described in detail below using examples. However, the present disclosure is not limited to the following examples. The matters shown in the following examples may be appropriately changed without departing from the spirit of the present disclosure.

[0101] <Reagents> Details of the reagents used in the examples and comparative examples are shown below: Ni(OAc) ２ : Nickel acetate tetrahydrate, manufactured by Kanto Chemical Co., Ltd. BHT: Benzenehexathiol, synthesized by the following method Methanol: manufactured by Kanto Chemical Co., Ltd. Tetrahydrofuran: manufactured by Kanto Chemical Co., Ltd. Mn(OAc) ２ Manganese (II) acetate tetrahydrate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Zn(OAc) ２Zinc acetate dihydrate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Cu(OAc) ２ Copper (II) acetate monohydrate, manufactured by Kanto Chemical Co., Ltd., FeSO ４ Iron (II) sulfate heptahydrate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Co(OAc) ２ Cobalt (II) acetate tetrahydrate, manufactured by Kanto Chemical Co., Ltd.

[0102] <Synthesis of BHT> Benzenehexathiol (BHT) was synthesized according to the literature description (Jennifer A. Harnisch, Robert J. Angelici, Inorganica Chimica Acta, Volumes 300-302, 20 April 2000, Pages 273-279).

[0103] <Synthesis of SnBHT> Tin-protected benzenehexathiol (SnBHT) was synthesized according to the description in the literature (Tigmansu Pal, Shotaro Doi, Hiroaki Maeda, Keisuke Wada, Choon Meng Tan, Naoya Fukui, Ryota Sakamoto, Shinji Tsuneyuki, Sono Sasaki and Hiroshi Nishihara, Chem. Sci., Volume 10, 17 April 2019, Pages 5218-5225).

[0104] <Pretreatment> Unless otherwise specified, all solvents were degassed with nitrogen gas before use.

[0105] <Analysis Methods> Ultraviolet-Visible-Near-Infrared (UV-Vis-NIR) Spectroscopy Analysis by ultraviolet-visible-near-infrared spectroscopy was carried out using a "V-770" (manufactured by JASCO Corporation).

[0106] Raman Spectroscopy Analysis by Raman spectroscopy was carried out using an "NRS-5500" (manufactured by JASCO Corporation).

[0107] Energy Dispersive X-ray Spectroscopy (EDS) Analysis by energy dispersive X-ray spectroscopy was carried out using a "JCM-7000" (manufactured by JEOL Ltd.).

[0108] Dynamic Light Scattering (DLS) Analysis by dynamic light scattering was carried out using "SZ-100V2" (manufactured by Horiba Ltd.).

[0109] Table 1 shows the Ni content measured by UV-Vis-NIR spectroscopy and Raman spectroscopy. １．５ The characteristic peak tops in BHT and the two-dimensional coordination polymers prepared as described below are shown. Table 2 also shows the Kα ray energy of each element in EDS analysis. In the examples described below, the obtained two-dimensional coordination polymers were identified by comparing them with the characteristic peak tops and energy values ​​shown in Tables 1 and 2 below.

[0110]

[0111]

[0112] (Example 1: Ni １．５ Synthesis of BHT: The following operations were carried out in an argon atmosphere in a glove box. Nickel acetate (Ni(OAc) ２ ) was dissolved in methanol to prepare a 0.225 mM (=0.225 mmol / L) nickel acetate methanol solution. Benzenehexathiol (BHT) was also dissolved in tetrahydrofuran to prepare a 0.15 mM (=0.15 mmol / L) BHT tetrahydrofuran solution. 10 mL of the prepared nickel acetate methanol solution was quickly added to 10 mL of the prepared BHT tetrahydrofuran solution at 25°C, and the mixture was allowed to stand for 6 hours to obtain a brownish-red Ni １．５ A BHT solution was obtained. １．５BHT was identified by ultraviolet-visible-near-infrared (UV-Vis-NIR) spectroscopy, Raman spectroscopy, and energy dispersive X-ray spectroscopy (EDS), and the obtained data was compared with the characteristic peak tops and energy values ​​shown in Tables 1 and 2. The elements were also identified by comparing the EDS spectrum with the Kα ray energy values ​​of each element in the EDS analysis shown in Table 2. Figure 4 shows the volume-average particle size results of the two-dimensional coordination polymers of Examples 1 and 3, obtained by dynamic light scattering (DLS) analysis. As shown in Figure 4, the two-dimensional coordination polymer of Example 1 had a volume-average particle size of 25 nm with a standard error of 5 nm.

[0113] (Example 2: Ni １．５ Synthesis of BHT: The following operations were carried out in an argon atmosphere in a glove box. Nickel acetate (Ni(OAc) ２ ) was dissolved in methanol to prepare a 0.15 mM (=0.15 mmol / L) nickel acetate methanol solution. Benzenehexathiol (BHT) was also dissolved in tetrahydrofuran to prepare a 0.15 mM (=0.15 mmol / L) BHT tetrahydrofuran solution. 10 mL of the prepared nickel acetate methanol solution was quickly added to 10 mL of the prepared BHT tetrahydrofuran solution at 25°C, and the mixture was allowed to stand for 6 hours to obtain a brownish-red Ni １．５ A BHT solution was obtained. １．５ BHT was identified by analyzing ultraviolet-visible-near-infrared (UV-Vis-NIR) spectroscopy, energy dispersive X-ray spectroscopy (EDS), and Raman spectroscopy, and comparing the obtained data with the characteristic peak tops and energy values ​​shown in Tables 1 and 2. Dynamic light scattering (DLS) analysis also identified the brown Ni １．５ The BHT solution was found to be a single-phase colloidal solution. The elements were identified by comparing the EDS spectrum with the Kα ray energy values ​​of each element in the EDS analysis shown in Table 2.

[0114] (Example 3: Ni ３Synthesis of BHT: The following operations were carried out in an argon atmosphere in a glove box. Nickel acetate (Ni(OAc) ２ ) was dissolved in methanol to prepare a 0.45 mM (=0.45 mmol / L) nickel acetate methanol solution. Benzenehexathiol (BHT) was also dissolved in tetrahydrofuran to prepare a 0.15 mM (=0.15 mmol / L) BHT tetrahydrofuran solution. 10 mL of the prepared nickel acetate methanol solution was quickly added to 10 mL of the prepared BHT tetrahydrofuran solution at 25°C, and the mixture was allowed to stand for 6 hours to obtain a black-brown Ni ３ A BHT solution was obtained. ３ BHT was identified using ultraviolet-visible-near-infrared (UV-Vis-NIR) spectroscopy, energy dispersive X-ray spectroscopy (EDS), and Raman spectroscopy. Figure 4 shows the volume-average particle size of the two-dimensional coordination polymers of Examples 1 and 3 obtained by dynamic light scattering (DLS) analysis. As shown in Figure 4, the two-dimensional coordination polymer of Example 3 had a volume-average particle size of 43 nm with a standard error of 12 nm. Furthermore, the dynamic light scattering (DLS) analysis of the obtained brownish-red Ni １．５ The BHT solution was found to be a single-phase colloidal solution. The elements were identified by comparing the EDS spectrum with the Kα ray energy values ​​of each element in the EDS analysis shown in Table 2.

[0115] (Example 4: Ni １．５ Ni from BHT ３ Synthesis of BHT: The following operations were carried out in an argon atmosphere in a glove box. Nickel acetate (Ni(OAc) ２ ) was dissolved in methanol to prepare a 30 mM (=30 mmol / L) nickel acetate methanol solution. １．５ 0.1 mL of the prepared nickel acetate methanol solution was quickly added to the entire BHT solution, and then the solution was left to stand for 2.5 hours. ３ A BHT solution was obtained. ３BHT was identified using ultraviolet-visible-near-infrared (UV-Vis-NIR) spectroscopy, energy dispersive X-ray spectroscopy (EDS), and Raman spectroscopy. Dynamic light scattering (DLS) analysis also confirmed the brownish-red Ni １．５ The BHT solution was found to be a single-phase colloidal solution. The elements were identified by comparing the EDS spectrum with the Kα ray energy values ​​of each element in the EDS analysis shown in Table 2.

[0116] Example 5: Ni １ Mn ２ Synthesis of BHT: The following operations were carried out in a glove box under an argon atmosphere. ２ ) was dissolved in methanol to prepare a 30 mM (=30 mmol / L) manganese acetate methanol solution. １．５ 10 mL of the prepared manganese acetate methanol solution was quickly added to the entire BHT solution, and then the mixture was left to stand for 2.5 hours. １ Mn ２ A BHT solution was obtained. １ Mn ２ BHT was identified using ultraviolet-visible-near-infrared (UV-Vis-NIR) spectroscopy, energy dispersive X-ray spectroscopy (EDS), and Raman spectroscopy. Table 1 shows the characteristic peak tops observed in the UV-Vis-NIR spectrum and Raman spectrum. The elements were also identified by comparing the EDS spectrum with the Kα ray energy values ​​of each element in the EDS analysis shown in Table 2.

[0117] Example 6: Ni １ Zn ２ Synthesis of BHT) The following operations were carried out in a glove box under an argon atmosphere. Zinc acetate (Zn(OAc) ２ ) was dissolved in methanol to prepare a 30 mM (=30 mmol / L) zinc acetate methanol solution. １．５ 10 mL of the zinc acetate methanol solution was quickly added to the entire BHT solution, and then the solution was left to stand for 2.5 hours. １ Zn ２A BHT solution was obtained. １ Zn ２ BHT was identified using ultraviolet-visible-near-infrared (UV-Vis-NIR) spectroscopy, energy dispersive X-ray spectroscopy (EDS), and Raman spectroscopy. Table 1 shows the characteristic peak tops observed in the UV-Vis-NIR spectrum and Raman spectrum. The elements were also identified by comparing the EDS spectrum with the Kα ray energy values ​​of each element in the EDS analysis shown in Table 2.

[0118] Example 7: Ni １ Cu ２ Synthesis of BHT: The following operations were carried out in an argon atmosphere in a glove box. ２ ) was dissolved in methanol to prepare a 30 mM (=30 mmol / L) copper acetate methanol solution. １．５ 10 mL of the prepared copper acetate methanol solution was quickly added to the entire BHT solution, and then the solution was left to stand for 2.5 hours. １ Cu ２ A BHT solution was obtained. １ Cu ２ BHT was identified using ultraviolet-visible-near-infrared (UV-Vis-NIR) spectroscopy, energy dispersive X-ray spectroscopy (EDS), and Raman spectroscopy. Table 1 shows the characteristic peak tops observed in the UV-Vis-NIR spectrum and Raman spectrum. The elements were also identified by comparing the EDS spectrum with the Kα ray energy values ​​of each element in the EDS analysis shown in Table 2.

[0119] Example 8: Ni １ Co ２ Synthesis of BHT: The following operations were carried out in a glove box under an argon atmosphere. Cobalt acetate (Co(OAc) ２ ) was dissolved in methanol to prepare a 30 mM (=30 mmol / L) copper acetate methanol solution. １．５ 10 mL of the prepared cobalt acetate methanol solution was quickly added to the entire BHT solution, and then the mixture was left to stand for 2.5 hours.１ Co ２ A BHT solution was obtained. １ Co ２ BHT was identified using ultraviolet-visible-near-infrared (UV-Vis-NIR) spectroscopy, energy dispersive X-ray spectroscopy (EDS), and Raman spectroscopy. Table 1 shows the characteristic peak tops observed in the UV-Vis-NIR spectrum and Raman spectrum. The elements were also identified by comparing the EDS spectrum with the Kα ray energy values ​​of each element in the EDS analysis shown in Table 2.

[0120] Example 9: Ni １ Fe ２ Synthesis of BHT) The following operations were carried out in an argon atmosphere in a glove box. Iron (II) sulfate (FeSO ４ ) was dissolved in methanol to prepare a 30 mM (=30 mmol / L) methanol solution of iron (II) sulfate. １．５ 10 mL of the prepared cobalt acetate methanol solution was quickly added to the entire BHT solution, and then the mixture was left to stand for 2.5 hours. １ Fe ２ A BHT precipitate was obtained. １ Fe ２ BHT was identified using energy dispersive X-ray spectroscopy (EDS). Table 1 shows the characteristic peak tops observed in the UV-Vis-NIR and Raman spectra.

[0121] Example 10: Pt １．５ Synthesis of BHT) All steps were carried out under air. Potassium tetrachloroplatinate (II) (K ２ [PtCl ４]) was dissolved in pure water to prepare a 0.5 mM (=0.5 mmol / L) aqueous solution of potassium tetrachloroplatinate(II). Also, tin-protected benzenehexathiol (SnBHT) was dissolved in dichloromethane to prepare a 1 mM (=1 mmol / L) SnBHT dichloromethane solution. At 25°C, 2.5 mL of the prepared aqueous solution of potassium tetrachloroplatinate(II) was mixed with 5 mL of dimethyl sulfoxide (DMSO), and then this was quickly mixed with 1.25 mL of the SnBHT dichloromethane solution. The mixture was then left to stand for 22.5 hours, resulting in the formation of a brownish-red Pt １．５ A BHT solution was obtained. １．５ BHT was identified by ultraviolet-visible-near-infrared (UV-Vis-NIR) spectroscopy, energy dispersive X-ray spectroscopy (EDS), and Raman spectroscopy. Table 1 shows the characteristic peak tops observed in the UV-Vis-NIR and Raman spectra.

[0122] FIG. 1 shows Raman spectra of the two-dimensional coordination polymers of Examples 1, 5, 6, and 7. As shown in FIG. 1, peaks characteristic of Ni and BHT were observed in the two-dimensional coordination polymers of each example. FIG. 2 shows EDS spectra of the two-dimensional coordination polymers of Examples 1, 5, 6, and 7. As shown in FIG. 2, energy values ​​characteristic of Ni and BHT were observed in the two-dimensional coordination polymers of each example.

[0123] Example 11: Ni １．５ Synthesis of BHT: The following operations were carried out in an argon atmosphere in a glove box. Nickel acetate (Ni(OAc) ２ ) was dissolved in methanol to prepare a 0.15 mmol / L nickel acetate methanol solution. Benzenehexathiol (BHT) was also dissolved in acetone to prepare a 0.15 mM (=0.15 mmol / L) BHT acetone solution. 10 mL of the prepared nickel acetate methanol solution was quickly added to 10 mL of the prepared BHT acetone solution at 25°C, and then the mixture was left to stand at room temperature (25±1°C) for 6 hours to obtain a brownish-red Ni １．５ A BHT solution was obtained.

[0124] Example 12: Ni３ Synthesis of BHT: The following operations were carried out in an argon atmosphere in a glove box. Nickel acetate (Ni(OAc) ２ ) was dissolved in methanol to prepare a 0.45 mmol / L nickel acetate methanol solution. Benzenehexathiol (BHT) was also dissolved in acetone to prepare a 0.15 mmol / L BHT acetone solution. At 25°C, 10 mL of the prepared nickel acetate methanol solution was quickly added to 10 mL of the prepared BHT acetone solution, and the mixture was left to stand at room temperature (25±1°C) for 6 hours to obtain a brownish-red Ni ３ A BHT solution was obtained.

[0125] The two-dimensional coordination polymers in Examples 11 and 12 were identified using ultraviolet-visible-near infrared (UV-Vis-NIR) spectroscopy.

[0126] Example 13: Pt １ M ２ Synthesis of BHT (M = Ag, Cu, Fe, Ni, or Pd) Iron (II) tetrafluoroborate was dissolved in pure water to prepare a 20 mM (= 20 mmol / L) aqueous solution of iron (II) tetrafluoroborate. １．５ 1.285 mL of the prepared aqueous solution of iron (II) tetrafluoroborate was quickly added to 5 mL of the BHT solution, and then the mixture was left to stand for 2.5 hours. １ Fe ２ A single-phase solution containing BHT was obtained. Iron(II) tetrafluoroborate (Fe(BF) ４ ) ２ ) instead of AgBF ４ , Cu(BF ４ ) ２ , Ni(BF ４ ) ２ , and K ２ [PdCl ４ ], but with the same specifications as Pt １ Ag ２ BHT, Pt １ Cu ２ BHT, Pt １ Ni ２ BHT and Pt １ Pd ２ BHT was obtained respectively.

[0127] In addition, each Pt １ M ２ The BHT was identified by energy dispersive X-ray spectroscopy (EDS) and Raman spectroscopy. １ M ２ As shown in FIG. １ M ２ In the Raman spectrum of BHT, both peaks characteristic of Pt and peaks characteristic of BHT were observed.

[0128] As shown in the above examples, the method for producing a two-dimensional coordination polymer according to the present disclosure enables the mass synthesis of two-dimensional coordination polymers. It has also been found that a novel two-dimensional coordination polymer can be produced.

[0129] The disclosure of Japanese Patent Application No. 2023-149526, filed on September 14, 2023, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A method for producing a two-dimensional coordination polymer, comprising: a preparation step of preparing a Ni compound, a Pd compound, a Pt compound, or a solution thereof A, and a solution B of benzenehexathiol, a derivative of benzenehexathiol, or at least one of them; and a polymer formation step of preparing a single-phase solution containing the Ni compound, the Pd compound, or the Pt compound, and the benzenehexathiol, and producing a two-dimensional coordination polymer in the single-phase solution.

2. The method for producing a two-dimensional coordination polymer according to claim 1, wherein the obtained two-dimensional coordination polymer has a constitutional unit represented by the following formula (1): In formula (1), M １ represents Ni, Pd or Pt.

3. Said M １ The method for producing a two-dimensional coordination polymer according to claim 2, wherein is Ni or Pt.

4. The method for producing a two-dimensional coordination polymer according to claim 1, wherein the preparation step is a step of preparing a solution A of the Ni compound, Pd compound or Pt compound, and a solution B containing at least one of the benzenehexathiol and a derivative of benzenehexathiol, and the polymer formation step is a step of mixing the solution A and the solution B to prepare the single-phase solution.

5. The method for producing a two-dimensional coordination polymer according to claim 4, wherein the solvent of the solution A is an alcohol compound, and the solvent of the solution B is an aprotic polar solvent.

6. The method for producing a two-dimensional coordination polymer according to claim 4, wherein the solvent of the solution A is a mixed solvent of water and an aprotic polar solvent, and the solvent of the solution B is a polar solvent.

7. The method for producing a two-dimensional coordination polymer according to claim 2, further comprising a structural change step of adding the Ni compound, Pd compound or Pt compound or solution A thereof to the single-phase solution after the polymer formation step, to produce a two-dimensional coordination polymer having a constitutional unit represented by the following formula (2): In formula (2), M １ represents Ni, Pd or Pt.

8. The method for producing a two-dimensional coordination polymer according to claim 1 or 2, further comprising a heterometallic polymer formation step of adding a Mn compound, an Fe compound, a Co compound, a Ni compound, a Cu compound, a Zn compound, a Pd compound or an Ag compound, or a solution C thereof, to the single-phase solution after the polymer formation step.

9. A method for producing a two-dimensional coordination polymer described in claim 4 or claim 5, wherein the amount of the Ni compound, Pd compound or Pt compound in the preparation step is 1.4 molar equivalents or more and 1.6 molar equivalents or less per 1 molar equivalent of the benzenehexathiol or its derivative.

10. A method for producing a two-dimensional coordination polymer described in claim 4 or claim 5, wherein the amount of the Ni compound, Pd compound or Pt compound in the preparation step is 2.9 molar equivalents or more and 3.1 molar equivalents or less per 1 molar equivalent of the benzenehexathiol or its derivative.

11. A structural unit represented by the following formula (2) and a structural unit represented by the following formula (3), １ is Ni or Pt, ２ is Mn, Fe, Co, Ni, Cu, Zn, Pd or Ag, １ When is Ni, M ２ does not represent Ni.) Two-dimensional coordination polymer.

12. Said M １ and the above M ２ Molar ratio (M １ : M ２ 12. The two-dimensional coordination polymer according to claim 11, wherein the ratio of the t-type molecular weight to the t-type molecular weight is 1.0:0.1 or more and 1.0:3.0 or less.

13. A two-dimensional coordination polymer obtained by the method for producing a two-dimensional coordination polymer according to claim 1 or 2.

14. A solution for forming a two-dimensional coordination polymer, which is a single-phase solution containing a Ni compound, a Pd compound or a Pt compound, and at least one of benzenehexathiol and a derivative of benzenehexathiol.

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