Inorganic-organic hybrid compound crystal and preparation method thereof

Abstract

The invention discloses an inorganic-organic hybrid compound crystal and a preparation method thereof, and belongs to the technical field of organic-inorganic hybrid materials. The preparation method comprises the following steps: mixing raw materials containing hydroiodic acid, organic cage molecules RCC3 and a lead source with a solvent, and carrying out solvothermal reaction to obtain the inorganic-organic hybrid compound crystal. The chemical formula of the prepared inorganic-organic hybrid compound crystal is ({H18 [C72H108N12] 2 [(Pb10I36)]}. 2I), wherein [C72H108N12] is RCC3 acidified by hydroiodic acid, the crystal has a supramolecular three-dimensional structure assembled by a [Pb5I8] 3-anion cluster unit and a protonated RCC3 molecular cage through electrostatic and hydrogen-bond interaction, and belongs to a monoclinic system, and the space group is P21. The crystal structure is a metal halide-based organic-inorganic hybrid crystal constructed by taking an organic molecular cage as nitrogen-containing cations and lead iodide for the first time.

Description

Technical Field

[0001] The present application relates to an inorganic-organic hybrid compound crystal and a preparation method thereof, belonging to the technical field of organic-inorganic hybrid materials. Background Art

[0002] Perovskites, represented by lead halides, have become a research hotspot in materials science due to their diverse structures and widespread applications in optics, electronics, catalysis, and other fields. Many properties of these materials exhibit a dependence on structure. For example, as the structural dimension decreases from two-dimensional, one-dimensional, to zero-dimensional structures, their carrier transport decreases, the band gap increases, and the light absorption efficiency decreases (Chem. Rev. 2023, 123, 15, 9565). It can be seen that material structure determines performance, and a clear structure also helps to deepen the understanding of the structure-activity relationship of materials and is the basis for material design. Organic-inorganic hybrid metal halides exhibit a richer variety of structural types and properties than pure inorganic systems, becoming an important research direction in this field. Organic components, acting as coordinating agents or charge counteracting agents, have become important components in modifying and tailoring the inorganic modular structure. By forming molecular-level encapsulation layers and confined spaces, the structure and properties of the inorganic components can be adjusted. Summary of the Invention

[0003] In order to solve the problem that the types of traditional organic ammonium ions in the existing technology of organic-inorganic hybrid metal halide crystal materials are limited, resulting in the lack of novelty in the structure of the resulting crystal materials, this application first proposes to introduce an organic cage molecule RCC3 as an organic ammonium to prepare a new type of inorganic-organic hybrid lead iodine crystal. The compound structure is based on lead iodide [Pb5I8] 3- The anionic clusters and protonated RCC3 are assembled through electrostatic and hydrogen bonding. Compared with existing hybrid crystalline materials, the introduction of organic cage molecules as organoammonium is expected to develop a new class of organic-inorganic hybrid crystalline materials.

[0004] This application adopts the following technical solutions:

[0005] According to the first aspect of the present application, an inorganic-organic hybrid compound crystal is provided, wherein the chemical formula of the inorganic-organic hybrid compound crystal is {H 18 [C 72 H 108 N 12 ]2·(Pb5I 18 )2}·2I;

[0006] Among them, [C 72 H 108 N 12 ] is RCC3 protonated with hydroiodic acid.

[0007] Optionally, the RCC3 has the structure shown in Formula I;

[0008]

[0009] In Formula I, Slashes are used to simplify the representation that all the rings are six-membered rings, which is a commonly used expression in this field.

[0010] Organic molecular cages have become a research hotspot in organic porous materials in recent years (CCS Chem. 2024, 6, 149-156; Chem. Rev. 2023, 123, 4602). From the perspective of constituent components, organic cages can be seen as a class of organic amine molecules with a cage-like structure, which can be further reduced and protonated, and can be regarded as a completely new class of ammonium molecules. Compared with the existing organic ammoniums used to synthesize hybrid perovskites, organic cage ammonium molecules are more variable in structure and have richer spatial dimensions. They will form a variety of confined spaces, structurally tailor the lead halide bulk material, and obtain organic-inorganic hybrid crystalline materials containing novel inorganic lead halide units. Assembling organic cages and inorganic lead halide components into a new class of organic-inorganic hybrid crystalline materials will give new vitality to the research fields of organic cages and inorganic perovskites. At present, there have been no reports on the design and synthesis of lead halide-organic cage hybrid materials using this method.

[0011] Optionally, the inorganic-organic hybrid compound crystal has a supramolecular three-dimensional structure;

[0012] In the supramolecular three-dimensional structure, [Pb5I8] 3- The anionic cluster units are assembled into the supramolecular three-dimensional structure through electrostatic and hydrogen bonding interactions with the protonated RCC3 molecular cage.

[0013] Optionally, the inorganic-organic hybrid compound crystal belongs to the monoclinic system and has a space group of P21.

[0014] Optionally, the unit cell parameters of the inorganic-organic hybrid compound crystal are β=94.20~94.60°, Z=2.

[0015] Optionally, the unit cell parameters of the inorganic-organic hybrid compound crystal are β=94.4170(10)°, Z=2.

[0016] According to another aspect of the present application, a method for preparing the above-mentioned inorganic-organic hybrid compound crystal is provided, comprising the following steps:

[0017] The raw materials containing hydroiodic acid, RCC3 and a lead source are mixed with a solvent to undergo a solvothermal reaction to obtain the inorganic-organic hybrid compound crystal.

[0018] Optionally, the lead source is selected from at least one of lead acetate and lead iodide.

[0019] Optionally, the solvent is selected from at least one of water, methanol and ethanol.

[0020] Optionally, the RCC3 is obtained by reducing the organic molecular cage CC3 with NaBH4 and protonating it with hydroiodic acid.

[0021] Optionally, the organic molecular cage CC3 is obtained by condensing 1,3,5-trimethylbenzaldehyde with R,R-cyclohexanediamine or S,S-cyclohexanediamine.

[0022] Optionally, the solid-liquid ratio of the RCC3 to hydroiodic acid is 1 mg: 0.01-0.05 mL;

[0023] The mass ratio of the RCC3 to the lead source is 1:1-5;

[0024] The solid-liquid ratio of the RCC3 to the solvent is 1 mg: 0.01-0.05 mL;

[0025] The mass of the hydroiodic acid is calculated based on a 47% HI aqueous solution.

[0026] Optionally, the lead source and RCC3 are solid, and HI is liquid.

[0027] Optionally, the lead source and RCC3 are powders.

[0028] Optionally, it is characterized in that the conditions of the solvent thermal reaction include: the reaction temperature is 40 to 100° C., and the reaction time is 2 to 6 days.

[0029] Optionally, the conditions of the solvent thermal reaction include: a reaction temperature of 80 to 100° C. and a reaction time of 3 to 5 days.

[0030] Optionally, the temperature of the solvent thermal reaction is 100° C., and the reaction time is 4 days.

[0031] Optionally, the inorganic-organic hybrid compound is washed with anhydrous ethanol 2 to 3 times.

[0032] The beneficial effects of this application include:

[0033] Compared with the original traditional organic ammonium as the counter ion, the inorganic-organic hybrid compound crystals prepared in this application use molecular cages as organic ammonium cations for the first time, which is expected to develop a new type of hybrid metal halide crystalline material. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 Schematic diagram of the crystal structure of sample 1# in this application. DETAILED DESCRIPTION

[0035] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0036] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0037] Unless otherwise specified, conventional methods were used for testing, and instrument settings were those recommended by the manufacturer.

[0038] X-ray single crystal diffraction was performed on a Bruker D8 single crystal diffractometer from Rigaku Oxford Diffraction Co., Ltd. For sample 1, a Mo target and a K α Radiation source (λ = 0.71073 nm), test temperature 296 (2) K. The structure was elucidated by Shelx 2018.

[0039] The source of the RCC3 powder acidified with HI (47%) used in the examples of this application is:

[0040]

[0041] Preparation of CC3: Dissolve 500 mg of 1,3,5-benzenetricarboxaldehyde in 10 mL of dichloromethane, add 10 μL of trifluoroacetic acid as a catalyst, and add 10 mL of a dichloromethane solution containing 500 mg of (R,R)-1,2-diaminocyclohexane. After magnetic stirring for one week, collect the white sample, wash it with dichloromethane and methanol several times, and dry it at 60°C to obtain CC3.

[0042] Preparation of R-CC3: 463 mg of CC3 powder was dissolved in 25 mL of a mixture of dichloromethane and methanol (volume ratio of 1:1). 500 mg of sodium borohydride was added and stirred magnetically for 19 hours. 1 mL of water was then added and stirring continued for 1 hour. Solid powder was obtained by vacuum distillation, which was washed with water several times and dried to obtain R-CC3.

[0043] Preparation of acidified sample C-CC3: 100 mg of R-CC3 was suspended in 5 mL of water, and 300 μL of HI was added to dissolve it into a clear solution. The solution was stirred for 1 hour and then dried in an oven to obtain a brown sample C-CC3.

[0044] Example 1 Preparation of Sample 1#

[0045] Mix 10 mg of PbI powder, 10 mg of RCC3 powder acidified with HI (47%), 3 ml of water, 2 ml of methanol, and 10 μL of HI (47%), add the mixture to a glass bottle, and heat it in an oven to 100°C. After 4 days, remove the mixture, cool it, and wash it three times with anhydrous ethanol at room temperature. Dry it to obtain the corresponding crystal sample 1#.

[0046] Sample 1# was characterized by X-ray single crystal diffraction, and its structure was analyzed by Shelx 2016. The results showed that the chemical formula of sample 1# was ({H 18 [C 72 H 108 N 12 ]2[(Pb 10 I 36 )]}·2I), where [C 72 H 108 N 12 ] is RCC3 protonated by hydroiodic acid, which is described in detail below: The crystal structure of sample 1# was obtained by X-ray single crystal diffraction, as shown in Figure 1 As shown, sample 1# crystal belongs to the P21 space group, and its unit cell parameters are: β=94.4170(10)°, Z=2, Figure 1 The large black balls in the white net represent I atoms, the black balls connected to them represent Pb atoms, the gray balls represent C atoms, and the gray balls in the white net represent N atoms. Sample 1# has a supramolecular three-dimensional structure; X-ray single crystal diffraction data analysis revealed that in the supramolecular three-dimensional structure, [Pb5I8] 3- The anionic cluster units are assembled into the supramolecular three-dimensional structure through electrostatic and hydrogen bonding interactions with the protonated RCC3 molecular cage.

[0047] Sample 1# contains two structures: lead iodine clusters and organic cages. The two can be used for photothermal catalytic conversion of phenylethanol to phenylacetaldehyde through charge transfer, which has potential application value.

[0048] The above descriptions are merely a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application discloses the preferred embodiments as above, they are not intended to limit the present application. Any technical personnel familiar with the present profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. An inorganic-organic hybrid compound crystal, characterized in that: The chemical formula of the inorganic-organic hybrid compound crystal is ({H 18 [C 72 H 108 N 12 ]2[(Pb 10 I 36 )]}·2I); Among them, [C 72 H 108 N 12 ] is RCC3 protonated with hydroiodic acid.

2. The inorganic-organic hybrid compound crystal according to claim 1, characterized in that The RCC3 has the structure shown in Formula 1; 3. The inorganic-organic hybrid compound crystal according to claim 1, characterized in that The inorganic-organic hybrid compound crystal has a supramolecular three-dimensional structure; In the supramolecular three-dimensional structure, [Pb5I8] 3- The anionic cluster units are assembled into the supramolecular three-dimensional structure through electrostatic and hydrogen bonding interactions with the protonated RCC3 molecular cage.

4. The inorganic-organic hybrid compound crystal according to claim 1, characterized in that The inorganic-organic hybrid compound crystal belongs to the monoclinic system and has a space group of P21; Preferably, the unit cell parameters of the inorganic-organic hybrid compound crystal are β=94.20~94.60°, Z = 2; Preferably, the unit cell parameters of the inorganic-organic hybrid compound crystal are β=94.4170(10)°, Z=2.

5. The method for preparing the inorganic-organic hybrid compound crystal according to any one of claims 1 to 4, characterized in that: The steps include: The raw materials containing hydroiodic acid, RCC3 and a lead source are mixed with a solvent to undergo a solvothermal reaction to obtain the inorganic-organic hybrid compound crystal.

6. The preparation method according to claim 5, characterized in that The lead source is selected from at least one of lead acetate and lead iodide; Preferably, the solvent is selected from at least one of water and methanol.

7. The preparation method according to claim 5, characterized in that The RCC3 is obtained by reducing the organic molecular cage CC3 with NaBH4 and protonating it with hydroiodic acid.

8. The preparation method according to claim 7, characterized in that The organic molecular cage CC3 is obtained by condensing 1,3,5-trimethylbenzaldehyde and R,R-cyclohexanediamine or S,S-cyclohexanediamine.

9. The preparation method according to claim 5, characterized in that The solid-liquid ratio of RCC3 to hydroiodic acid is 1 mg: 0.01-0.05 mL; The mass ratio of the RCC3 to the lead source is 1:1-5; The solid-liquid ratio of the RCC3 to the solvent is 1 mg: 0.01-0.05 mL; Wherein, the mass of the hydroiodic acid is calculated based on 47% HI aqueous solution.

10. The preparation method according to claim 5, characterized in that: The conditions of the solvent thermal reaction include: a reaction temperature of 40 to 100° C. and a reaction time of 2 to 6 days.

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