Meltable aluminum-oxygen cluster crystalline material and macro preparation method and application thereof

Abstract

The invention provides a meltable aluminum-oxygen cluster crystalline material as well as a macro preparation method and application thereof. The molecular formula of the molten aluminum oxygen cluster crystalline material is {B [Al8 (C) 8 (mu2-OH) 4 (D) 12]} (A) (En), in which mu2-OH represents a two-connected hydroxyl group; a represents a positive ion selected from nitrogen-containing positive ions; b represents one or more than two free first guest molecules or first guest ions; c represents one or more than two groups selected from residues of C1-C40 organic alcohols; d represents one or more than two groups selected from residues of C1-C40 organic acids; e represents one or more than two free second guest molecules or second guest ions; and n represents the number of E and is selected from 1-30. The aluminum-oxygen cluster crystalline material enriches the structural types of aluminum-oxygen clusters, and widens the application prospect of the aluminum-oxygen cluster material. The macro preparation method is simple in process requirement, short in reaction time and convenient for large-scale production; and the post-treatment is simple and feasible, the preparation process has less pollution, and the green and environment-friendly requirements are met.

Description

Technical Field

[0001] The present invention belongs to the technical field of crystal material preparation, and particularly relates to a fusible aluminum oxide cluster crystalline material, a method for its mass preparation, and uses thereof. Background Art

[0002] Crystals - liquids - glasses combine the processability of glasses and the atomically precise nature of crystalline compounds, allowing the use of coordination and reticular chemistry to fine - tune desired properties for the fabrication of bulk - formable devices for practical applications, which is not achievable in traditional glasses. Although a large number of metal - organic frameworks / coordination polymers have been discovered, since most metal - organic frameworks / coordination polymers undergo irreversible thermal decomposition upon heating, only a small number have been found to exhibit macroscopic melting behavior. Therefore, it is necessary to develop a general method that can convert crystals into crystal - liquid - glass materials on the premise of mass - preparing crystals.

[0003] The coupling of cluster compounds with lattice - doped ionic liquids may provide a feasible solution for developing a rich library of glass families, expanding the functions of glasses, and establishing the connection between the structure, physical properties, and potential chemistry of glasses. The low melting point of ionic liquids and the coordination sites they possess are helpful for the binding of cluster materials. Therefore, it is necessary to develop a general preparation method for fusible cluster materials that combines low - melting - point ionic liquid solvents with molecular clusters to achieve the mass preparation of fusible cluster crystal glasses. Summary of the Invention

[0004] To solve the above - mentioned technical problems, the present invention provides a fusible aluminum oxide cluster crystalline material, a method for its mass preparation, and uses thereof.

[0005] The present invention proposes the following technical solutions:

[0006] An aluminum oxide cluster crystalline material, the molecular formula of the aluminum oxide cluster crystalline material is:

[0007] {B[Al8(C)8(μ2 - OH)4(D) 12}·(A)·(E n )

[0008] wherein, μ2 - OH represents a di - connected hydroxyl group;

[0009] A represents a positive ion selected from nitrogen - containing positive ions, for example, the positive ion of an organic nitride with C1 - C40;

[0010] B represents one or more than two free first guest molecules or first guest ions;

[0011] C represents the residue of one or more groups selected from C1-C40 organic alcohols, and the residue of the organic alcohol refers to the group remaining after removing the hydrogen on all hydroxyl groups of the organic alcohol;

[0012] D represents the residue of one or more groups selected from C1-C40 organic acids, and the residue refers to the group remaining after removing the hydrogen on all carboxyl groups of the organic acid;

[0013] E represents one or more free second guest molecules or second guest ions;

[0014] n represents the number of E, selected from 1-30, for example, an integer or a decimal between 1-30.

[0015] According to an embodiment of the present invention, in the aluminoxane crystalline material, A, B, μ2-OH, C, D, and Al form the aluminoxane cluster structure of the aluminoxane crystalline material, and B exists freely inside the aluminoxane cluster structure.

[0016] According to an embodiment of the present invention, the periphery of the aluminoxane cluster structure is formed by coordination of C and D.

[0017] According to an embodiment of the present invention, in the aluminoxane crystalline material, two Al atoms form a bridging coordination with the bicoordinate O atom in the organic alcohol hydroxyl group to form μ2-OH.

[0018] According to an embodiment of the present invention, in the aluminoxane crystalline material, E is freely adsorbed outside the aluminoxane cluster structure.

[0019] According to an embodiment of the present invention, the aluminoxane cluster structure in the aluminoxane crystalline material includes an aluminoxane cluster core. Preferably, the size of the aluminoxane cluster core is 1 nm to 5 nm, for example, 2.3 ± 0.8 nm, and for another example, 2.29 nm or 2.31 nm.

[0020] According to an embodiment of the present invention, the aluminoxane cluster structure is a symmetric structure.

[0021] According to an embodiment of the present invention, the aluminoxane cluster structure includes at least 8 aluminum metal cores. In the present invention, the aluminum metal core refers to the coordinated aluminum atom in the structure.

[0022] According to an embodiment of the present invention, the nitrogen positive ion is preferably at least one of the positive ion of a substituted ammonium salt and the positive ion of a substituted imidazole salt. Further, the substituent is a substituent known in the art, for example, selected from hydroxyl, C 1-6 alkyl, C 1-6 alkoxy, amino, nitro, carboxyl, phenyl or halogen atom, preferably hydroxyl, methyl, amino or halogen atom, and more preferably C 1-6 alkyl.

[0023] According to an embodiment of the present invention, B is selected from at least one of nitrate, sulfate, phosphate, water molecule, ethanol molecule, n-propanol molecule, ethanolate, n-propanolate, and halide ion, and is preferably a halide ion.

[0024] According to an embodiment of the present invention, C is selected from at least one of the residues of phenol and the residues of substituted phenols. Preferably, C is selected from the residues of phenol.

[0025] Exemplarily, C is selected from at least one of the residues of phenol, 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, and 1,3,5-trihydroxybenzene, and is preferably the residue of phenol.

[0026] According to an embodiment of the present invention, D is selected from at least one of the residues of naphthoic acid and the residues of substituted naphthoic acids, wherein the substituents have the meanings as described above, for example, selected from hydroxyl, C 1-6 alkyl, C 1-6 alkoxy, amino, nitro, carboxyl, phenyl, or halogen atom. Preferably, D is selected from the residues of naphthoic acid.

[0027] Exemplarily, D is selected from at least one of the residues of 1-naphthoic acid, 2-naphthoic acid, 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 1,4-naphthalenedicarboxylic acid, and is preferably the residue of 1-naphthoic acid.

[0028] According to an embodiment of the present invention, n is an integer selected from 1 to 30; more preferably an integer selected from 4 to 10; further preferably an integer selected from 4 to 8; and even more preferably 4 or 6.

[0029] According to an embodiment of the present invention, E is selected from at least one of nitrate, sulfate, phosphate, water molecule, acetonitrile molecule, ethanol molecule, n-propanol molecule, isopropanol molecule, phenol molecule, and N,N-dimethylformamide molecule; and is preferably at least one of phenol molecule and N,N-dimethylformamide molecule.

[0030] According to an embodiment of the present invention, the aluminoxane crystalline material is a pure phase, and preferably a pure phase having a crystal structure.

[0031] According to an embodiment of the present invention, the aluminoxane crystalline material is an organic-inorganic hybrid compound.

[0032] According to a preferred embodiment of the present invention, the molecular formula of the aluminoxane crystalline material is:

[0033] {B[Al8(C)8(μ2-OH)4(D) 12}·(A)·(E n )

[0034] Wherein, A is selected from a substituted ammonium cation or a substituted imidazolium salt cation; B is a chloride anion; C is a residue of phenol; D is a residue of 1-naphthoic acid; E is selected from one or both of a free phenol molecule and an N,N-dimethylformamide molecule;

[0035] n is selected from 2 or 4.

[0036] According to an exemplary embodiment of the present invention, the aluminoxane crystalline material is aluminoxane crystalline material a, and its molecular formula is {Cl[Al8(C 11 H7O2)8(μ2-OH)4(C6H5O) 12}·(C4H 12 N)·(C6H6O)2·(C3H7NO)2 (denoted as C 202 H 166 Al8ClN3O 40 ), its crystal system is triclinic, the space group is P1, and the unit cell parameters a are b is c is α is 64.321°, β is 74.042°, γ is 82.708°.

[0037] Preferably, the relative molecular mass Mr of the aluminoxane crystalline material a is 3526.66.

[0038] Preferably, the aluminoxane crystalline material a has an X-ray powder diffraction pattern substantially as Figure 3 shown.

[0039] Preferably, the crystal parameters of the crystalline substance of the aluminoxane crystalline material a are shown in Table 1.

[0040] Table 1

[0041]

[0042] According to an exemplary embodiment of the present invention, the aluminoxane crystalline material is aluminoxane crystalline material b, and its molecular formula is {Cl[Al8(C 11 H7O2)8(μ2-OH)4(C6H5O) 12}·(C8H 15 N2)·(C6H6O)2·(C3H7NO)2 (denoted as C 206 H 169 Al8ClN4O 40), its crystal system is triclinic, space group is P-1, and the unit cell parameter a is b is c is α is 83.561°, β is 88.099°, and γ is 72.368°.

[0043] Preferably, the relative molecular mass Mr of the aluminoxane crystalline material b is 3591.73.

[0044] Preferably, the aluminoxane crystalline material b has substantially as Figure 3 the X-ray powder diffraction pattern shown.

[0045] Preferably, the crystal parameters of the crystalline substance of the aluminoxane crystalline material b are shown in Table 2.

[0046] Table 2

[0047]

[0048] The present invention also provides a method for the bulk preparation of the above aluminoxane crystalline material. The bulk preparation method includes the following steps: mixing reaction raw materials, heating and reacting to prepare the aluminoxane crystalline material, wherein the reaction raw materials include a raw material containing a nitrogen cation and a first guest, an organic alcohol, an aluminum salt, an organic acid, and a raw material containing a second guest.

[0049] According to an embodiment of the present invention, the preparation method specifically includes the following steps:

[0050] 1) Mix the raw material containing a nitrogen cation and a first guest and the organic alcohol to obtain a preliminary mixture;

[0051] 2) After mixing the aluminum salt, the organic acid, and the raw material containing a second guest with the preliminary mixture in step 1), carry out a heating reaction to obtain a mixture;

[0052] 3) Purify the mixture in step 2) to obtain the aluminoxane crystalline material.

[0053] According to an embodiment of the present invention, the raw material containing a nitrogen cation and a first guest provides A and B in the aluminoxane crystalline material. Preferably, the raw material containing a nitrogen cation and a first guest is, for example, an ammonium chloride salt or an imidazole chloride salt.

[0054] According to an embodiment of the present invention, the aluminum salt is selected from compounds formed by aluminum ions and alcohols after removing the hydrogen on the alcohol hydroxyl group, and provides Al in the aluminoxane crystalline material.

[0055] According to an embodiment of the present invention, the aluminum salt is selected from at least one of aluminum ethoxide, aluminum n-propoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum sec-butoxide, and aluminum tert-butoxide, and preferably is aluminum isopropoxide.

[0056] According to an embodiment of the present invention, the organic alcohol provides C in the aluminoxane crystalline material, and the organic alcohol has the selections as shown above, for example, is selected from phenol.

[0057] According to an embodiment of the present invention, the organic acid provides D in the aluminoxane crystalline material, and the organic acid has the selections as shown above, for example, is selected from organic acids with C1-C40.

[0058] According to an embodiment of the present invention, the raw material containing the second guest provides E in the aluminoxane crystalline material.

[0059] According to an embodiment of the present invention, the molar ratio of the aluminum salt to the organic acid is 1:(0.01-10), for example, 1:(0.1-5), and further, 1:(0.2-3).

[0060] According to an embodiment of the present invention, the molar ratio of the aluminum salt to the raw material containing a nitrogen positive ion and the first guest is 1:(0.01-20), for example, 1:(0.1-20), and further, 1:(0.5-10).

[0061] According to an embodiment of the present invention, the molar ratio of the aluminum salt to the organic alcohol is 1:(0.01-100), for example, 1:(0.1-80), and further, 1:(1-50).

[0062] According to an embodiment of the present invention, the molar ratio of the aluminum salt to the second guest is 1:(0.01-100), for example, 1:(0.1-80), and further, 1:(1-50).

[0063] According to an embodiment of the present invention, the temperature of the heating reaction is 50-150 °C; preferably 70-120 °C, for example, 85-110 °C, such as 100 °C. If the temperature of the heating reaction is too low, it will lead to a longer reaction time and smaller crystal size.

[0064] According to an embodiment of the present invention, the time of the heating reaction is 36-288 hours; preferably 72-240 hours, such as 168 hours, 192 hours.

[0065] Exemplarily, the heating reaction can be carried out at 80 °C for 240 hours or 288 hours, or at 100 °C for 168 hours or 192 hours.

[0066] According to an embodiment of the present invention, step 1) specifically includes: mixing the raw material containing nitrogen cations and the first guest with an organic alcohol in a glass bottle and stirring thoroughly at room temperature.

[0067] According to an embodiment of the present invention, in step 2), the heating reaction refers to standing and reacting at a constant temperature. For example, the reaction raw materials are placed in an oven for heating reaction.

[0068] According to an embodiment of the present invention, in step 3), purification means separating the mixture and / or washing and / or drying the separated solid.

[0069] Preferably, the washing can use a solvent known in the art. For example, the separated solid is washed with N,N-dimethylformamide and air-dried at room temperature.

[0070] The present invention also provides the use of the above aluminoxane cluster crystalline material, specifically for optical glass materials.

[0071] The present invention also provides an optical glass material, and the optical glass material includes the above aluminoxane cluster crystalline material.

[0072] According to an embodiment of the present invention, the optical glass material is prepared from the above aluminoxane cluster crystalline material.

[0073] According to an embodiment of the present invention, the preparation method of the optical glass material specifically includes: heating and melting the aluminoxane cluster crystalline material and then solidifying to obtain the optical glass material.

[0074] According to an embodiment of the present invention, the optical glass material is a cluster glass.

[0075] According to an embodiment of the present invention, the temperature of the heating and melting is 250-400°C; preferably 300-350°C, such as 302°C. If the temperature of the heating and melting is too low, it will cause the aluminoxane cluster crystalline material not to melt completely and unable to form a cluster glass.

[0076] Beneficial effects

[0077] The aluminoxane cluster crystalline material of the present invention enriches the structural types of aluminoxane clusters and broadens the application prospects of aluminoxane cluster materials;

[0078] The preparation method of the aluminoxane cluster crystalline material of the present invention has simple and efficient process requirements, short reaction time, and is convenient for large-scale production; and the post-treatment process of the preparation method of the present invention is simple. Only by washing and separating and natural air-drying can the crystalline product be obtained. The crystalline product only needs to be melted and then solidified to make a glass film. At the same time, the raw materials of the preparation method of the present invention are low-toxic, inexpensive, less polluting, and meet the requirements of green environmental protection.

[0079] Term definitions and explanations

[0080] Unless otherwise specified, the definitions of groups and terms recited in the specification and claims of this application, including their definitions by way of example, exemplary definitions, preferred definitions, definitions recited in tables, definitions of specific compounds in examples, etc., can be combined and combined with each other arbitrarily. The definitions of groups and the compound structures after such combination and combination should be understood to be within the scope recited in the specification and / or claims of this application.

[0081] The "cluster" is a relatively stable microscopic or submicroscopic aggregate composed of several to thousands of atoms, molecules or ions through physical or chemical binding forces, and its physical and chemical properties vary with the number of atoms contained. If the cluster is electrically neutral, it is a cluster molecule. If the cluster is positively or negatively charged, it is a cluster ion.

[0082] It should be understood that when describing "1 or more" herein, "more than one" should mean greater than 1, for example, an integer greater than or equal to 2, such as 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0083] The term "C 1-6 alkyl" means straight-chain and branched-chain alkyls having 1, 2, 3, 4, 5 or 6 carbon atoms. The alkyls are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl, etc. or their isomers.

[0084] The above definition of the term "alkyl", such as "C 1-6 alkyl", also applies to other terms containing "C 1-6 alkyl", such as the term "C 1-6 alkoxy" and other terms.

[0085] The term "organic alcohol with 1 - 40 carbon atoms" or "organic acid with 1 - 40 carbon atoms" means an organic alcohol or organic acid having 1, 2, 3, 4, 5, …, 38, 39 or 40 carbon atoms. Description of the Drawings

[0086] Figure 1 It is a schematic diagram of the crystal structure of the aluminum oxide cluster crystalline material a prepared in Example 1;

[0087] Figure 2Schematic diagram of the crystal structure of the aluminum oxide cluster crystalline material b prepared in Example 2;

[0088] Figure 3 X-ray powder diffraction pattern of the aluminum oxide cluster crystalline material a prepared in Example 1; wherein, the "simulated pattern" is the X-ray powder diffraction pattern simulated according to the crystal structure; the "experimental pattern" is the X-ray powder diffraction pattern obtained by testing on an X-ray powder diffractometer;

[0089] Figure 4 Infrared spectrum of the aluminum oxide cluster crystalline material a prepared in Example 1;

[0090] Figure 5 Ultraviolet spectrum of the aluminum oxide cluster crystalline material a prepared in Example 1;

[0091] Figure 6 X-ray powder diffraction pattern of the aluminum oxide cluster crystalline material b prepared in Example 2; wherein, the "simulated pattern" is the X-ray powder diffraction pattern simulated according to the crystal structure; the "experimental pattern" is the X-ray powder diffraction pattern obtained by testing on an X-ray powder diffractometer;

[0092] Figure 7 Infrared spectrum of the aluminum oxide cluster crystalline material b prepared in Example 2;

[0093] Figure 8 Ultraviolet spectrum of the aluminum oxide cluster crystalline material b prepared in Example 2;

[0094] Figure 9 Schematic diagram of the large-scale preparation of the aluminum oxide cluster crystalline material a prepared in Example 1 and the aluminum oxide cluster crystalline material b prepared in Example 2;

[0095] Figure 10 Glass film diagram prepared by melting and solidifying the aluminum oxide cluster crystalline material a prepared in Example 1 and the aluminum oxide cluster crystalline material b prepared in Example 2. Detailed implementation manners

[0096] The technical solutions of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are only for illustrative and explanatory purposes of the present invention, and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0097] Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products, or can be prepared by known methods.

[0098] The single crystal structure analysis of the present invention uses a Rigaku Metal Jet D2 single crystal diffractometer.

[0099] The X-ray source used for the X-ray powder diffraction pattern is Cu-Kα ray.

[0100] Example 1

[0101] Prepare the fusible aluminum-oxygen cluster crystalline material a(C 202 H 166 Al8ClN3O 40 )

[0102] The specific preparation method is as follows: Mix tetramethylammonium chloride (31.25 mmol) and phenol (500 mmol) in a 100 mL glass bottle, and stir thoroughly at room temperature for 30 minutes to form a colorless solvent DES-1, which requires no further treatment.

[0103] Put aluminum isopropoxide (1.0 mmol), 1-naphthoic acid (1.0 mmol), DES-1 (5 mL), and N,N-dimethylformamide (2 mL) into a 20 mL glass bottle, mix evenly at room temperature, keep it at a constant temperature of 100 °C in an oven for 7 days, take it out, cool it naturally to room temperature, separate the solid phase, rinse it with N,N-dimethylformamide, and dry it naturally in the air to obtain the colorless crystalline target product aluminum-oxygen cluster crystalline material, a(C 202 H 166 Al8ClN3O 40 ). The yield is about 60% (based on the mass of aluminum isopropoxide).

[0104] Figure 1 It is a schematic diagram of the crystal structure of the aluminum-oxygen cluster crystalline material a prepared in Example 1. As can be seen from Figure 1 , the aluminum-oxygen cluster crystalline material a has 8 aluminum atoms, the peripheral ligands are 1-naphthoic acid and phenol, and there are two phenol and two N,N-dimethylformamide molecular guests outside the ring. Therefore, the molecular formula of the aluminum-oxygen cluster crystalline material a in this example can be expressed as {Cl[Al8(C 11 H7O2)8(μ2-OH)4(C6H5O) 12}·(C4H 12 N)·(C6H6O)2·(C3H7NO)2;

[0105] Take the aluminum-oxygen cluster crystalline material a of this example and conduct X-ray powder diffraction, infrared spectroscopy and ultraviolet spectroscopy tests respectively, as follows:

[0106] Figure 3 It is the X-ray powder diffraction pattern of the aluminum-oxygen cluster crystalline material a prepared in Example 1; among them, the "simulated diagram" is the X-ray powder diffraction pattern simulated according to the crystal structure; the "experimental diagram" is the X-ray powder diffraction pattern obtained by testing on an X-ray diffractometer; as can be seen from Figure 3It can be seen that the X-ray powder diffraction pattern of the aluminum oxide cluster crystalline material a is consistent with the theoretical simulation. The aluminum oxide cluster crystalline material a has a high purity (95%) and is stable in air. Its crystal form parameters are as follows: The crystal system of the aluminum oxide cluster crystalline material a is triclinic, the space group is P1, and the unit cell parameter a is b is c is α is 64.321°, β is 74.042°, γ is 82.708°, and V is

[0107] Through single crystal X-ray analysis, the crystal parameters of the aluminum oxide nanotube crystalline material a are shown in Table 1:

[0108] Table 1

[0109]

[0110] Figure 4 is the infrared spectrum of the aluminum oxide cluster crystalline material a prepared in Example 1; from Figure 4 it can be seen that the aluminum oxide nanotube crystalline material a has obvious vibration peaks of organic carboxylic acids;

[0111] Figure 5 is the ultraviolet spectrum of the aluminum oxide cluster crystalline material a prepared in Example 1; from Figure 5 it can be seen that the band gap of the aluminum oxide nanotube crystalline material a is 3.54 eV.

[0112] Example 2

[0113] Prepare aluminum oxide nanotube crystalline material b (C 206 H 169 Al8ClN4O 40 )

[0114] The specific preparation method is as follows: Mix 1-butyl-3-methylimidazolium chloride (31.25 mmol) and phenol (500 mmol) in a 100 mL glass bottle, and stir thoroughly at room temperature for 30 minutes to form a colorless solvent DES-2, which does not require further treatment.

[0115] Place aluminum isopropoxide (1.0 mmol), 1-naphthoic acid (1.0 mmol), DES-2 (5 mL), and N,N-dimethylformamide (2 mL) in a 20 mL glass bottle, mix evenly at room temperature, keep it at a constant temperature of 100 °C in an oven for 7 days, take it out, naturally cool it to room temperature, separate the solid phase, rinse it with N,N-dimethylformamide, and air-dry it naturally to obtain the colorless crystalline target product aluminum oxide cluster crystalline material, b (C 206 H 169 Al8ClN4O 40)。The yield is about 23.5% (based on the mass of aluminum isopropoxide).

[0116] Figure 2 It is a schematic diagram of the crystal structure of the aluminoxane crystalline material b prepared in Example 2. It can be seen from Figure 2 that the aluminoxane crystalline material b has 8 aluminum atoms, with 1-naphthoic acid and phenol as peripheral ligands, and there are two phenol and two N,N-dimethylformamide molecular guests outside the ring. Therefore, it can be expressed as {Cl@[Al8(C 11 H7O2)8(μ2-OH)4(C6H5O) 12}·(C8H 15 N2)·(C6H6O)2·(C3H7NO)2;

[0117] The aluminoxane crystalline material b was taken for X-ray powder diffraction, infrared spectroscopy and ultraviolet spectroscopy tests respectively:

[0118] It can be seen from Figure 6 that the X-ray powder diffraction pattern of the aluminoxane crystalline material b is consistent with the theoretical simulation. The aluminoxane crystalline material b has a high purity (95%) and is stable in air; its crystal form parameters are as follows: the crystal system of the aluminoxane crystalline material b is triclinic, the space group is P-1, and the lattice parameter a is b is c is α is 83.561°, β is 88.099°, γ is 72.368°, and V is

[0119] Through single crystal X-ray analysis, the crystal parameters of the aluminoxane crystalline material b are shown in Table 2:

[0120] Table 2

[0121]

[0122] It can be seen from Figure 7 that the aluminoxane crystalline material b has obvious vibration peaks of organic carboxylic acid;

[0123] It can be seen from Figure 8 that the band gap of the aluminoxane crystalline material b is 3.62 eV.

[0124] Example 3

[0125] Macroscale preparation of aluminoxane crystalline material a

[0126] The specific preparation method is as follows: Mix tetraethylammonium chloride (31.25 mmol) and phenol (500 mmol) in a 100 mL glass bottle, and stir thoroughly at room temperature for 30 minutes to form a colorless solvent DES-1, which requires no further treatment.

[0127] Put aluminum isopropoxide (1.0 mmol), 1-naphthoic acid (1.0 mmol), DES-1 (5 mL), and N,N-dimethylformamide (2 mL) into a 20 mL glass bottle, mix them evenly at room temperature, keep them at a constant temperature of 100 °C in an oven for 7 days, take them out, naturally cool to room temperature, separate the solid phase, rinse it with N,N-dimethylformamide, and dry it naturally in the air to obtain the colorless crystalline target product aluminum oxo cluster crystalline material, a(C 202 H 166 Al8ClN3O 40 ). The yield is about 60% (based on the mass of aluminum isopropoxide).

[0128] From Figure 9 It can be seen that in Example 9, the gram-scale preparation of the aluminum oxo cluster crystalline material a in Example 1 and the aluminum oxo cluster crystalline material b in Example 2 was achieved.

[0129] Example 4

[0130] Preparation of cluster glass film

[0131] The specific preparation method is as follows. Take the aluminum oxo cluster crystalline materials prepared in Examples 1-2 above and place them in the middle layer of two microscope slides. After heating and melting and then solidifying, the colorless crystal powder can be converted into a large transparent and bubble-free glass film, as shown in Figure 10 .

[0132] From Figure 10 It can be seen that both the aluminum oxo cluster crystalline material a prepared in Example 1 and the aluminum oxo cluster crystalline material b prepared in Example 2 can be formed into a glass film by melting and then solidifying, and the glass film is colorless and transparent, having good light transmittance.

[0133] The above describes the exemplary embodiments of the present invention. However, the protection scope of this application is not limited to the above embodiments. Any modifications, equivalent replacements, improvements, etc. made by those skilled in the art within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A crystalline aluminum oxide cluster material, characterized in that, The molecular formula of the aluminoxane crystalline material is: {B[Al8(C)8(μ2-OH)4(D) 12}·(A)·(E n ), Among them, μ2-OH represents a di-connected hydroxyl group; A represents a positive ion selected from nitrogen-containing positive ions; B represents one or more than two free first guest molecules or first guest ions; C represents one or more than two groups selected from the residues of C1-C40 organic alcohols, and the residue of the organic alcohol refers to the group remaining after removing the hydrogen on all hydroxyl groups of the organic alcohol; D represents one or more than two groups selected from the residues of C1-C40 organic acids, and the residue refers to the group remaining after removing the hydrogen on all carboxyl groups of the organic acid; E represents one or more than two free second guest molecules or second guest ions; n represents the number of E, selected from 1-30.

2. The aluminoxane cluster crystalline material according to claim 1, wherein In the aluminoxane crystalline material, the A, B, μ2-OH, C, D, and Al constitute the aluminoxane cluster structure of the aluminoxane crystalline material, and the B exists freely inside the aluminoxane cluster structure. Preferably, the periphery of the aluminoxane cluster structure is formed by coordination of C and D. Preferably, two Al in the aluminoxane crystalline material form bridging coordination with the bidentate O atom in the organic alcohol hydroxyl group to form μ2-OH. Preferably, in the aluminoxane crystalline material, the E is adsorbed freely outside the aluminoxane cluster structure. Preferably, the aluminoxane cluster structure in the aluminoxane crystalline material includes an aluminoxane cluster core. Preferably, the size of the aluminoxane cluster core is 1 nm to 5 nm. Preferably, the aluminoxane cluster structure is a symmetric structure. Preferably, the aluminoxane cluster structure includes at least 8 aluminum metal cores. Preferably, the nitrogen-containing positive ion is selected from the positive ions of C1-C40 organic nitrides.

3. The aluminoxane cluster crystalline material according to claim 1 or 2, characterized in that, The nitrogen positive ion is at least one of a positive ion containing a substituted ammonium salt and a positive ion containing a substituted imidazole salt. Further, the substituent is selected from a hydroxyl group, a C 1-6 alkyl group, a C 1-6 alkoxy group, an amino group, a nitro group, a carboxyl group, a phenyl group or a halogen atom. Preferably, the B is selected from at least one of nitrate, sulfate, phosphate, water molecule, ethanol molecule, n-propanol molecule, ethanolate, n-propanolate, and halogen ion. Preferably, the C is selected from at least one of the residues of phenol and the residues of substituted phenols. Preferably, the D is selected from at least one of the residues of naphthoic acid and the residues of substituted naphthoic acids. Preferably, the n is selected from integers from 1 to 30. Preferably, the E is selected from at least one of nitrate, sulfate, phosphate, water molecule, acetonitrile molecule, ethanol molecule, n-propanol molecule, isopropanol molecule, phenol molecule, and N,N-dimethylformamide molecule.

4. The aluminoxane cluster crystalline material according to any one of claims 1-3, characterized in that The aluminoxane crystalline material is a pure phase. Preferably, the aluminoxane crystalline material is an organic-inorganic hybrid compound. Preferably, the molecular formula of the aluminoxane crystalline material is: {B[Al8(C)8(μ2-OH)4(D) 12}·(A)·(E n ) Among them, A is selected from substituted ammonium positive ions or imidazolium salt positive ions with substituents; B is a chloride ion; C is the residue of phenol; D is the residue of 1-naphthoic acid; E is selected from one or two of free phenol molecules and N,N-dimethylformamide molecules; n is selected from 2 or 4. Exemplarily, the aluminoxane crystalline material is aluminoxane crystalline material a, and its molecular formula is {Cl[Al8(C 11 H7O2)8(μ2-OH)4(C6H5O) 12}·(C4H 12 N)·(C6H6O)2·(C3H7NO)2 (denoted as C 202 H 166 Al8ClN3O 40 ), its crystal system is triclinic, the space group is P1, the lattice parameter a is b is c is α is 64.321°, β is 74.042°, γ is 82.708°. Preferably, the relative molecular mass Mr of the aluminoxane crystalline material a is 3526.

66. Exemplarily, the aluminoxane crystalline material is aluminoxane crystalline material b with the molecular formula {Cl[Al8(C 11 H7O2)8(μ2-OH)4(C6H5O) 12}·(C8H 15 N2)·(C6H6O)2·(C3H7NO)2 (denoted as C 206 H 169 Al8ClN4O 40 ), which belongs to the triclinic crystal system, has the space group P-1, and the unit cell parameters a is b is c is α is 83.561°, β is 88.099°, and γ is 72.368°. Preferably, the relative molecular mass Mr of the aluminoxane crystalline material b is 3591.

73.

5. The method for the large-scale preparation of the aluminum oxide cluster crystalline material according to any one of claims 1 to 4, characterized in that, The macro-preparation method includes the following steps: mixing reaction raw materials, heating and reacting to prepare the aluminoxane crystalline material, wherein the reaction raw materials include a raw material containing a nitrogen positive ion and a first guest, an organic alcohol, an aluminum salt, an organic acid, and a raw material containing a second guest.

6. The bulk preparation method according to claim 5, characterized in that, The preparation method specifically includes the following steps: 1) Mix the raw material containing a nitrogen positive ion and a first guest with the organic alcohol to obtain a preliminary mixture; 2) After mixing the aluminum salt, the organic acid, and the raw material containing a second guest with the preliminary mixture in step 1), carry out a heating reaction to obtain a mixture; 3) Purify the mixture in step 2) to obtain the aluminoxane crystalline material.

7. The bulk preparation method according to claim 5 or 6, characterized in that, The raw material containing a nitrogen positive ion and a first guest provides A and B in the aluminoxane crystalline material. Preferably, the aluminum salt is selected from compounds formed by the aluminum ion and the alcohol after removing the hydrogen on the alcohol hydroxyl group, and provides Al in the aluminoxane crystalline material. Preferably, the aluminum salt is selected from at least one of aluminum ethoxide, aluminum n-propoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum sec-butoxide, and aluminum tert-butoxide. Preferably, the organic alcohol provides C in the aluminoxane crystalline material, and the organic alcohol is selected from phenol. Preferably, the organic acid provides D in the aluminoxane crystalline material, and the organic acid is selected from organic acids with C1-C40. Preferably, the raw material containing a second guest provides E in the aluminoxane crystalline material. Preferably, the molar ratio of the aluminum salt to the organic acid is 1:(0.01-10). Preferably, the molar ratio of the aluminum salt to the raw material containing a nitrogen positive ion and a first guest is 1:(0.01-20). Preferably, the molar ratio of the aluminum salt to the organic alcohol is 1:(0.01-100). Preferably, the molar ratio of the aluminum salt to the second guest is 1:(0.01-100).

8. The large-scale preparation method according to any one of claims 5-7, characterized in that, The temperature of the heating reaction is 50-150 °C. Preferably, the time of the heating reaction is 36-288 hours. Preferably, step 1) specifically includes: mixing the raw material containing a nitrogen positive ion and a first guest with the organic alcohol in a glass bottle and stirring thoroughly at room temperature. According to the embodiment of the present invention, the heating reaction in step 2) refers to a static reaction at a constant temperature. Preferably, in step 3), purification refers to separating the mixture.

9. Use of the aluminoxane crystalline material according to any one of claims 1-4, specifically for an optical glass material.

10. An optical glass material, wherein the optical glass material includes the aluminoxane crystalline material according to any one of claims 1-4.

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