A hydrogen-bonded organic framework material, and a preparation method and application thereof

Abstract

The application discloses a hydrogen-bonded organic framework material and a preparation method and application thereof; the hydrogen-bonded organic framework material comprises an organic ligand and an organic solvent molecule, and a chemical formula of the hydrogen-bonded organic framework material is [(L) x (G) y ], wherein L is 1,3,6,8-tetra (4-methoxyphenyl) pyrene, G represents a good solvent; x=1-2, and y=1-4. In the HOFs construction, different solvent molecules are introduced, a hydrogen-bonded organic framework material with adjustable multi-color light emitting characteristics of fluorescence and phosphorescence is constructed, the material is controlled from blue light to blue-green light to yellow-orange light, and the fluorescence and the phosphorescence are controlled in the hydrogen-bonded organic material containing different solvents. The application provides a new way for constructing multi-emitting materials by using a single molecule platform.

Description

Technical Field

[0001] This invention relates to the field of organic optoelectronic functional materials technology, and in particular to a hydrogen-bonded organic framework material, its preparation method, and its application. Background Technology

[0002] Multicolor luminescent materials have long been a research hotspot due to their wide application potential in fields such as lighting displays, sensing, bioimaging, information encryption, and high-density optical storage.

[0003] Hydrogen-bonded organic frameworks (HOFs), as a new type of crystalline porous material, possess advantages such as high specific surface area, porosity, low density, easy recombination, tunable structure, and good biocompatibility due to their unique self-assembly mechanism and structural tunability. They combine the advantages of MOFs and COFs and have been widely used in gas adsorption and separation, heterogeneous catalysis, fluorescence and sensing, and biological applications.

[0004] Compared to metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), the hydrogen bonding in HOFs is dynamic and flexible, enabling reversible changes in structure and properties in response to external stimuli. This provides a unique research platform for achieving tunable and controllable luminescence behavior. However, how to independently program the timing and color of photon emission within the same material system remains a crucial challenge.

[0005] Therefore, it is necessary to develop a hydrogen-bonded organic framework material that emits multiple colors and can achieve fluorescence and phosphorescence modulation. Summary of the Invention

[0006] The present invention aims to at least solve one of the technical problems existing in the prior art. To this end, the first aspect of the present invention proposes a hydrogen-bonded organic framework material that can achieve multicolor emission and can achieve modulation of fluorescence and phosphorescence.

[0007] A second aspect of the present invention also provides a method for preparing a hydrogen-bonded organic framework material.

[0008] A third aspect of the present invention also provides an application of hydrogen-bonded organic framework materials.

[0009] The hydrogen-bonded organic framework material provided according to a first aspect of the present invention comprises an organic ligand and an organic solvent molecule, wherein the chemical formula of the hydrogen-bonded organic framework material is [(L...]. x (G) y ], where L is 1,3,6,8-tetra(4-methoxyphenyl)pyrene, G represents a good solvent; x = 1~2, y = 1~4.

[0010] According to a preferred embodiment of the present invention, the good solvent is at least one of dichloromethane, trichloromethane, tetrahydrofuran, or N,N-dimethylformamide.

[0011] According to a preferred embodiment of the present invention, x = 1 to 2, y = 1 to 2.

[0012] According to a preferred embodiment of the present invention, G is dichloromethane, x = 1, y = 2; the crystal structure of the hydrogen-bonded organic framework material belongs to the monoclinic crystal system, space group C2 / c; the cell parameters are: a = 24.8053(5) Å, b = 16.7255(3) Å, c = 8.4154(2) Å, α = 90°, β = 94.638(2)°, γ = 90°, V = 3479.96(13) Å 3 Z=4.

[0013] According to a preferred embodiment of the present invention, G is chloroform, x = 2, y = 1. The crystal structure belongs to the monoclinic crystal system, space group P21 / c, and the cell parameters of the hydrogen-bonded organic framework material are: a = 14.05350(10) Å, b = 9.79120(10) Å, c = 26.4624(3) Å, α = 90°, β = 95.2230(10)°, γ = 90°V = 3626.12(6) Å. 3 Z=4.

[0014] According to a preferred embodiment of the present invention, G is chloroform, x = 1, y = 1. The crystal structure belongs to the monoclinic crystal system, and the space group is P21 / n; the cell parameters of the hydrogen-bonded organic framework material are: a = 15.3922(2) Å, b = 6.95040(10) Å, c = 19.4051(3) Å, α = 90°, β = 107.005(2)°, γ = 90°, V = 1985.23(5) Å. 3 Z=2.

[0015] According to a preferred embodiment of the present invention, G is tetrahydrofuran, x=2, y=1. The crystal structure belongs to the monoclinic crystal system, space group P21 / c; the cell parameters of the hydrogen-bonded organic framework material are: a=13.95030(10)Å, b=9.89320(10)Å, c=26.1703(2)Å, α=90°, β=96.3390(10)°, γ=90°, V=3589.76(5)Å. 3 Z=4.

[0016] According to a preferred embodiment of the present invention, G is tetrahydrofuran, x = 1, y = 1. The crystal structure belongs to the monoclinic crystal system, and the space group is P21 / n; the cell parameters of the hydrogen-bonded organic framework material are: a = 11.4956(2) Å, b = 7.06140(10) Å, c = 25.2700(4) Å, α = 90°, β = 92.5970(10)°, γ = 90°V = 2049.19(6) Å. 3 Z=2.

[0017] According to a preferred embodiment of the present invention, G is N,N-dimethylformamide, x=1, y=1. The crystal structure belongs to the monoclinic crystal system, and the space group is C2 / c; the cell parameters of the hydrogen-bonded organic framework material are: a=15.7632(3)Å, b=9.36020(10)Å, c=25.0823(4)Å, α=90°, β=96.588(2)°, γ=90°V=3676.37(10)Å. 3 Z=4.

[0018] The hydrogen-bonded organic framework material according to embodiments of the present invention has at least the following beneficial effects: This invention introduces different solvent molecules into the construction of HOFs (Hydrogen-Bonded Organic Frameworks) to construct hydrogen-bonded organic framework materials with tunable multicolor emission properties, exhibiting both fluorescence and phosphorescence. This allows for the modulation of the material's emission from blue light to blue-green light to yellow-orange light, and simultaneously achieves the modulation of fluorescence and phosphorescence in hydrogen-bonded organic materials containing different solvents. This invention provides a new approach for constructing multi-emission materials using a single molecular platform.

[0019] According to a second aspect of the present invention, a method for preparing a hydrogen-bonded organic framework material is provided, comprising the following steps: Mix the organic ligand L with the good solvent G, then add the poor solvent R, let stand, and culture the crystals by solvent diffusion or slow solvent evaporation. Alternatively, the organic ligand L can be dissolved in a good solvent G, and the crystals can be cultured by slow solvent evaporation.

[0020] According to a preferred embodiment of the present invention, the undesirable solvent R is selected from at least one of methanol, ethanol, alkanes, water, acetonitrile, and dimethyl sulfoxide.

[0021] According to a preferred embodiment of the present invention, the volume ratio of the good solvent G to the poor solvent R is (0.2 to 5):1. For example, the volume ratio includes 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, or any sub-range of any two of the above volume ratios.

[0022] According to a preferred embodiment of the present invention, the concentration of the organic ligand L in the good solvent G is 0.5 mmol / L to 5 mmol / L. For example, the concentration includes 0.5 mmol / L, 0.6 mmol / L, 0.7 mmol / L, 0.8 mmol / L, 0.9 mmol / L, 1.0 mmol / L, 1.2 mmol / L, 1.4 mmol / L, 1.6 mmol / L, 1.8 mmol / L, 2 mmol / L, 2.5 mmol / L, 3 mmol / L, 3.5 mmol / L, 4.0 mmol / L, 4.5 mmol / L, 5 mmol / L, or any subrange consisting of two of the above values.

[0023] According to a preferred embodiment of the present invention, the resting time is 7 to 30 days. For example, the time is 7 days, 8 days, 10 days, 12 days, 14 days, 16 days, 18 days, 20 days, 22 days, 24 days, 26 days, 28 days, 30 days, or any sub-range composed of two of the above values.

[0024] In this invention, a good solvent is defined as a solvent that has very good or good solubility for the target compound, indicating that the Gibbs free energy change ΔG < 0 during the dissolution process.

[0025] Definition of a poor solvent: The solvent has poor solubility for the target compound or the target compound does not dissolve in the solvent, indicating that the Gibbs free energy change ΔG > 0.

[0026] The third aspect of this invention provides an application of the hydrogen-bonded organic framework material described in the first aspect of this invention in lighting displays, sensing, and bioimaging.

[0027] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. Attached Figure Description

[0028] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which: Figure 1This is a crystal structure diagram of HOF-1, a hydrogen-bonded organic framework material provided in Example 1 of this invention. In the diagram, the atomic colors are: gray: C; white: H; red: oxygen; green: Cl.

[0029] Figure 2 This is a crystal structure diagram of HOF-2, a hydrogen-bonded organic framework material provided in Example 1 of this invention. In the diagram, the atomic colors are: gray: C; white: H; red: oxygen; green: Cl.

[0030] Figure 3 This is a crystal structure diagram of HOF-3, a hydrogen-bonded organic framework material provided in Example 1 of this invention. In the diagram, the atomic colors are: gray: C; white: H; red: oxygen; green: Cl.

[0031] Figure 4 This is a crystal structure diagram of HOF-4, a hydrogen-bonded organic framework material provided in Example 1 of this invention. In the diagram, the atomic colors are: gray: C; white: H; red: oxygen.

[0032] Figure 5 This is a crystal structure diagram of HOF-5, a hydrogen-bonded organic framework material provided in Example 1 of this invention. In the diagram, the atomic colors are: gray: C; white: H; red: oxygen.

[0033] Figure 6 This is a crystal structure diagram of HOF-6, the hydrogen-bonded organic framework material provided in Example 1 of this invention. In the diagram, the atomic colors are: gray: C; white: H; red: oxygen; purple: nitrogen.

[0034] Figure 7 These are the room-temperature steady-state fluorescence spectra of the hydrogen-bonded organic framework materials of Examples 1-6 of this invention.

[0035] Figure 8 This is the CIE chromaticity diagram of the hydrogen-bonded organic framework material of the present invention (the inset from left to right are fluorescence photographs of HOF-1 to HOF-6 under 365nm light source excitation).

[0036] Figure 9 These are (a) time-resolved plots of the room temperature transient fluorescence decay curve and (b) room temperature transient phosphorescence decay curve of the HOF-1 of the present invention.

[0037] Figure 10 These are time-resolved plots of (a) the room temperature transient fluorescence decay curve and (b) the room temperature transient phosphorescence decay curve of the HOF-2 of the present invention.

[0038] Figure 11 This is a time-resolved plot of the transient fluorescence decay curve of HOF-3 at room temperature according to the present invention.

[0039] Figure 12 This is a time-resolved plot of the transient fluorescence decay curve of HOF-4 at room temperature according to the present invention.

[0040] Figure 13 This is a time-resolved plot of the transient fluorescence decay curve of HOF-5 at room temperature according to the present invention.

[0041] Figure 14 This is a time-resolved plot of the transient fluorescence decay curve of HOF-6 at room temperature according to the present invention. Detailed Implementation

[0042] The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described in conjunction with the embodiments, but the present invention is not limited to these embodiments.

[0043] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in this technical field.

[0044] The reaction equation and preparation method of the organic monomer 1,3,6,8-tetrakis(4-methoxyphenyl)pyrene in the embodiments of the present invention are as follows:

[0045] 1,3,6,8-Tetrabromopyrene (0.5 g, 965.55 µmol) was added to a 250 mL three-necked flask, followed by 90 mL of solution A and 10 mL of anhydrous ethanol. The mixture was bubbled under an argon atmosphere to remove oxygen, and then 2 M K₂CO₃ aqueous solution (800.66 mg, 5.79 mmol) was added. After stirring the mixture under an argon atmosphere for 30 min, an appropriate amount of Pd(PPh₃)₄ was added, and the mixture was bubbled under aeration for 15 min. Then, 4-methoxyphenylboronic acid (733.60 mg, 4.83 mmol) was added, and the reaction was carried out at 120 °C for 24 h. After the reaction was complete, the mixture was cooled to room temperature, and the crude product was purified by silica gel column chromatography using DCM / PE (v / v = 1:1.5) as the eluent. The product, Py-OMe, was then purified by recrystallization from DCM / MeOH. The product, Py-OMe, was a light blue solid with a yield of 72%.

[0046] The 1H NMR data are shown below. 1 H NMR (500 MHz, Chloroform- d ) δ 8.18 (s, 4H),7.98 (s, 2H), 7.62 (d, J = 8.0 Hz, 8H), 7.11 (d, J = 8.1 Hz, 8H), 3.94 (s, 12H).

[0047] Example 1 This example provides a hydrogen-bonded organic framework material (HOF-1) with the chemical formula [(L)x(G)y], where L is 1,3,6,8-tetra(4-methoxyphenyl)pyrene, G is dichloromethane, x = 1, and y = 2. The crystal structure belongs to the monoclinic system with space group C2 / c. The cell parameters of the hydrogen-bonded organic framework material are: a = 24.8053(5) Å, b = 16.7255(3) Å, c = 8.4154(2) Å, α = 90°, β = 94.638(2)°, γ = 90°, V = 3479.96(13) Å. 3 Z=4, the preparation method is as follows: 10 mg was added to a sample vial and dissolved by sonication in 20 mL of dichloromethane. Then, 10 mL of methanol, a poor solvent, was added to the vial, which was sealed and allowed to stand for two weeks to slowly evaporate, thus cultivating the target crystal and obtaining the hydrogen-bonded organic framework product. Its crystal structure was analyzed by single-crystal X-ray diffraction.

[0048] Example 2 This example provides a hydrogen-bonded organic framework material (HOF-2) with the chemical formula [(L)x(G)y], where L is 1,3,6,8-tetra(4-methoxyphenyl)pyrene, G is trichloromethane, x = 2, and y = 1. The crystal structure belongs to the monoclinic system with space group P21 / c. The cell parameters of the hydrogen-bonded organic framework material are: a = 14.05350(10) Å, b = 9.79120(10) Å, c = 26.4624(3) Å, α = 90°, β = 95.2230(10)°, γ = 90°V = 3626.12(6) Å. 3 Z=4. The preparation method is as follows: 10 mg was added to a sample vial and dissolved by sonication in 8 mL of chloroform. Then, 4 mL of the unsuitable solvent n-hexane was added to the vial, which was sealed and allowed to stand for three weeks to slowly evaporate, thus cultivating the target crystal and obtaining the hydrogen-bonded organic framework product. Its crystal structure was analyzed by single-crystal X-ray diffraction.

[0049] Example 3 This example provides a hydrogen-bonded organic framework material (HOF-3) with the chemical formula [(L)x(G)y], where L is 1,3,6,8-tetra(4-methoxyphenyl)pyrene, G is trichloromethane, x = 1, y = 1. The crystal structure belongs to the monoclinic system with space group P21 / n. The cell parameters of the hydrogen-bonded organic framework material are: a = 15.3922(2) Å, b = 6.95040(10) Å, c = 19.4051(3) Å, α = 90°, β = 107.005(2)°, γ = 90°, V = 1985.23(5) Å. 3 Z=2. The preparation method is as follows: 10 mg was added to a sample vial and dissolved by sonication in 8 mL of chloroform. Then, 8 mL of methanol, a poor solvent, was added to the vial, which was sealed and left to stand for one week to cultivate the target crystals, yielding a hydrogen-bonded organic framework product. Its crystal structure was analyzed using a single-crystal X-ray diffraction instrument.

[0050] Example 4 This example provides a hydrogen-bonded organic framework material (HOF-4) with the chemical formula [(L)x(G)y], where L is 1,3,6,8-tetra(4-methoxyphenyl)pyrene, G is tetrahydrofuran, x=2, and y=1. The crystal structure belongs to the monoclinic system with space group P21 / c. The cell parameters of the hydrogen-bonded organic framework material are: a=13.95030(10)Å, b=9.89320(10)Å, c=26.1703(2)Å, α=90°, β=96.3390(10)°, γ=90°V=3589.76(5)Å. 3 Z=4. The preparation method is as follows: 10 mg was added to a sample vial and dissolved in 20 mL of tetrahydrofuran by sonication. Then, 10 mL of ethanol, a poor solvent, was added to the vial, which was sealed and allowed to stand for two weeks to slowly evaporate, thus cultivating the target crystal and obtaining the hydrogen-bonded organic framework product. Its crystal structure was analyzed by single-crystal X-ray diffraction.

[0051] Example 5 This example provides a hydrogen-bonded organic framework material (HOF-5) with the chemical formula [(L)x(G)y], where L is 1,3,6,8-tetra(4-methoxyphenyl)pyrene, G is tetrahydrofuran, x = 1, y = 1. The crystal structure belongs to the monoclinic system with space group P21 / n; the cell parameters of the hydrogen-bonded organic framework material are: a = 11.4956(2) Å, b = 7.06140(10) Å, c = 25.2700(4) Å, α = 90°, β = 92.5970(10)°, γ = 90°, V = 2049.19(6) ų, Z = 2. The preparation method is as follows: 10 mg was added to a sample vial and dissolved by sonication in 20 mL of tetrahydrofuran. Then, 20 mL of methanol, a poor solvent, was added to the vial, which was then sealed and allowed to stand for two weeks to cultivate the target crystals, yielding a hydrogen-bonded organic framework product. Its crystal structure was analyzed using single-crystal X-ray diffraction.

[0052] Example 6 This example provides a hydrogen-bonded organic framework material (HOF-6) with the chemical formula [(L)x(G)y], where L is 1,3,6,8-tetra(4-methoxyphenyl)pyrene, G is N,N-dimethylformamide, x = 1, y = 1. The crystal structure belongs to the monoclinic system with space group C2 / c. The cell parameters of the hydrogen-bonded organic framework material are: a = 15.7632(3) Å, b = 9.36020(10) Å, c = 25.0823(4) Å, α = 90°, β = 96.588(2)°, γ = 90°, V = 3676.37(10) Å. 3 Z=4. The preparation method is as follows: 10 mg was added to a sample vial and dissolved by sonication in 15 ml of N,N-dimethylformamide. The vial was sealed and allowed to stand for one week to slowly evaporate, thus cultivating the target crystal and obtaining a hydrogen-bonded organic framework. Its crystal structure was analyzed by single-crystal X-ray diffraction.

[0053] Performance testing The hydrogen-bonded organic framework materials obtained in Examples 1-6 were subjected to single-crystal structure testing, and the results are as follows: Figure 1 , Figure 2 , Figure 3 , Figure 4 , Figure 5 and Figure 6 As shown, the results of single-crystal X-ray diffraction demonstrate that by cultivating crystals through solvent diffusion or slow solvent evaporation, a framework structure formed by a single building molecule, 1,3,6,8-tetra(4-methoxyphenyl)pyrene, and a corresponding good solvent can be obtained.

[0054] Furthermore, the crystals obtained in Examples 1-6 were subjected to steady-state and transient fluorescence spectroscopy tests, and the results are as follows: Figures 7-14 As shown. In Figure 7 and Figure 8 It can be clearly seen that HOF materials grown in different solvent systems can exhibit multicolor luminescence. From Figure 7 and Figure 9 It can be seen that the single crystals (HOF-1) cultured in the DCM / MeOH system in Example 1 have nanosecond-level lifetimes in the 400nm–500nm range and microsecond-level lifetimes in the 550nm–620nm range. This indicates that the peaks at 468nm and 491nm in its steady-state fluorescence spectrum are fluorescence peaks of the pyrene excitonomer, and the peaks at 560nm and 612nm can be attributed to the phosphorescence peaks of pyrene. This suggests that the emission of this compound mainly originates from the combined effect of fluorescence and phosphorescence. Figure 7 and Figure 10It can be seen that the single crystals (HOF-2) cultured in the TCM / nH system in Example 2 have nanosecond-level lifetimes in the 400nm–500nm range and microsecond-level lifetimes in the 550nm–650nm range. This indicates that the peaks at 474nm and 491nm in its steady-state fluorescence spectrum are fluorescence peaks of the pyrene excitonomer, and the peaks at 580nm and 633nm can be attributed to the phosphorescence peaks of pyrene. This suggests that the yellow-orange light emission of this compound mainly originates from the combined effect of fluorescence and phosphorescence. Figure 11 , Figure 12 , Figure 13 , Figure 14 It can be seen that the lifetimes of HOF-3, HOF-4, HOF-5, and HOF-6 at room temperature are all in the nanosecond range, and their luminescence is fluorescence. Combined with the single crystal structure diagrams of different HOFs, it can be seen that the blue to blue-green fluorescence emission of HOF-3, HOF-4, HOF-5, and HOF-6 originates from the synergistic effect of pyrene unit luminescence, crystal stacking, and intermolecular interactions.

[0055] In summary, this invention introduces different solvent molecules into the construction of HOFs, enabling the regulation of material emission from blue to blue-green to yellow-orange. Simultaneously, it achieves the regulation of fluorescence and phosphorescence in hydrogen-bonded organic materials containing different solvents. This invention provides a new approach for constructing multi-emission materials using a single molecular platform.

[0056] The present invention has been described in detail above with reference to the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention.

Claims

1. A hydrogen-bonded organic framework material, characterized in that, Including organic ligands and organic solvent molecules, the chemical formula of the hydrogen-bonded organic framework material is [(L)]. x (G) y ], where L is 1,3,6,8-tetra(4-methoxyphenyl)pyrene, G represents a good solvent; x = 1~2, y = 1~4.

2. The hydrogen-bonded organic framework material according to claim 1, characterized in that, The good solvent is at least one of dichloromethane, trichloromethane, tetrahydrofuran, or N,N-dimethylformamide.

3. The hydrogen-bonded organic framework material according to claim 1, characterized in that, x = 1 to 2, y = 1 to 2.

4. The hydrogen-bonded organic framework material according to claim 1, characterized in that, G is dichloromethane, x = 1, y = 2; the crystal structure of the hydrogen-bonded organic framework material belongs to the monoclinic crystal system, space group C2 / c; the cell parameters are: a = 24.8053(5) Å, b = 16.7255(3) Å, c = 8.4154(2) Å, α = 90°, β = 94.638(2)°, γ = 90°, V = 3479.96(13) Å 3 ; And / or, G is chloroform, x = 2, y = 1, the crystal structure belongs to the monoclinic crystal system, the space group is P21 / c; the unit cell parameters of the hydrogen-bonded organic framework material are: a = 14.05350(10) Å, b = 9.79120(10) Å, c = 26.4624(3) Å, α = 90°, β = 95.2230(10)°, γ = 90°, V = 3626.12(6) Å 3 ; And / or, G is chloroform, x=1, y=1, the crystal structure belongs to the monoclinic crystal system, and the space group is P21 / n; the unit cell parameters of the hydrogen-bonded organic framework material are: a=15.3922(2)Å, b=6.95040(10)Å, c=19.4051(3)Å, α=90°, β=107.005(2)°, γ=90°, V=1985.23(5)Å 3 ; And / or, G is tetrahydrofuran, x=2, y=1, the crystal structure belongs to the monoclinic crystal system, and the space group is P21 / c; the unit cell parameters of the hydrogen-bonded organic framework material are: a=13.95030(10)Å, b=9.89320(10)Å, c=26.1703(2)Å, α=90°, β=96.3390(10)°, γ=90°, V=3589.76(5)Å 3 ; And / or, G is tetrahydrofuran, x=1, y=1, the crystal structure belongs to the monoclinic crystal system, and the space group is P21 / n; the cell parameters of the hydrogen-bonded organic framework material are: a=11.4956(2)Å, b=7.06140(10)Å, c=25.2700(4)Å, α=90°, β=92.5970(10)°, γ=90°, V=2049.19(6)Å 3 ; And / or, G is N,N-dimethylformamide, x=1, y=1, the crystal structure belongs to the monoclinic crystal system, the space group is C2 / c; the cell parameters of the hydrogen-bonded organic framework material are: a=15.7632(3)Å, b=9.36020(10)Å, c=25.0823(4)Å, α=90°, β=96.588(2)°, γ=90°, V=3676.37(10)Å 3 .

5. A method for preparing the hydrogen-bonded organic framework material as described in any one of claims 1 to 4, characterized in that, Includes the following steps: Mix the organic ligand L with the good solvent G, then add the poor solvent R, let stand, and culture the crystals by solvent diffusion or slow solvent evaporation. Alternatively, the organic ligand L can be dissolved in a good solvent G, and the crystals can be cultured by slow solvent evaporation.

6. The method for preparing the hydrogen-bonded organic framework material according to claim 5, characterized in that, The undesirable solvent R is selected from at least one of methanol, ethanol, alkanes, water, acetonitrile, and dimethyl sulfoxide.

7. The method for preparing the hydrogen-bonded organic framework material according to claim 5, characterized in that, The volume ratio of the good solvent G to the bad solvent R is (0.2~5):

1.

8. The method for preparing the hydrogen-bonded organic framework material according to claim 5, characterized in that, The concentration of the organic ligand L in the good solvent G is 0.5 mmol / L to 5 mmol / L.

9. The method for preparing the hydrogen-bonded organic framework material according to claim 5, characterized in that, The settling time is 7 to 30 days.

10. The application of the hydrogen-bonded organic framework material according to any one of claims 1 to 4 in lighting displays, sensing, and bioimaging.

Images