Two isomorphic pentaphene octacarboxylate-based hydrogen-bonded organic framework composites with white light emission, preparation and applications thereof

Abstract

The application discloses two kinds of isomorphic five-porphyrin octacarboxylic acid base hydrogen bond organic framework composite materials with white light emission and preparation and application thereof, and belongs to the field of hydrogen bond organic framework (HOFs) materials. The chemical formulae of the two kinds of hydrogen bond organic framework materials are (H8PEP-OBu)(MB)3 and (H8PEP-OMe)(MB)3 respectively, wherein H8PEP-OBu is 6,13-dibutoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl) pentaphyrin, MB is methyl benzoate, and H8PEP-OMe is 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(3'-carboxyphenyl) pentaphyrin. The two kinds of hydrogen bond organic framework materials are crystallized in an orthorhombic Pnma space group. The unit cell parameters of NKM-HOF-1 are a=18.3338(5), b=25.9671(7), c=37.9645(8), and alpha=beta=gamma=90 degrees. The unit cell parameters of NKM-HOF-2 are a=18.3974(3), b=26.3784(3), c=37.7312(4), and alpha=beta=gamma=90 degrees. The application further provides a preparation method of the white light emission five-porphyrin octacarboxylic acid base hydrogen bond organic framework composite material. The preparation method of the white light emission composite material provided by the application has the advantages of simple route process, mild reaction condition, high yield and good repeatability.

Description

Technical Field

[0001] This invention belongs to the field of hydrogen-bonded organic frameworks (HOFs) materials, specifically involving two novel pentaphenene octacarboxylic acid-based hydrogen-bonded organic framework complexes with white light emission and their preparation and application. Technical Background

[0002] Hydrogen-bonded organic frameworks (HOFs) represent a new class of crystalline porous materials, formed by organic ligands or metal-organic units bonded together by hydrogen bonds, π-π bonds, and CH4 bonds. …The material is self-assembled through non-covalent interactions such as π-covalent bonding and electrostatic interactions. It exhibits high crystallinity, large specific surface area, tunable pore size, functionalized pore environment, mild synthesis conditions, easy regeneration and solution processability, low cytotoxicity, and improved biocompatibility. Therefore, it shows great promise for various applications including gas adsorption and separation, proton conduction, catalysis, fluorescence detection, and biomedicine. See (Y Cai, J Gao, JH Li, P Liu, YZheng, W Zhou, H Wu, L Li, RB Lin, B Chen.[J] Angewandte ChemieInternational Edition, 2023, 62, e202308579. S Chen, Y Ju, H Zhang, Y Zou, SLin, Y Li, S Wang, E Ma, W Deng, S Xiang, B Chen, Z Zhang.[J] AngewandteChemie International Edition, 2023, 62, e202308418. C Huang, C Zhao, Q Deng,H Zhang, D Yu, J Ren, 14399. H Zhang, D Yu, S Liu, C Liu, Z Liu, J Ren, X Qu. [J] Angewandte Chemie International Edition, 2022, 61, e202109068.) However, compared to covalent and coordinate bonds, hydrogen bonds are more reversible, weaker, and less directional. Subtle changes in ligands can have a significant impact on the structure and properties of hydrogen-bonded organic frameworks. See (ZJ Lin, SAR Mahammed, TF Liu, RCao. [J] ACS Central Science, 2022, 8, 1589.) The difficulty in directionally constructing hydrogen-bonded organic frameworks hinders their structural modification and further regulation of properties.

[0003] The enormous potential of white light emitting materials in solid-state light sources has attracted widespread attention. See (Z Wu, H Choi, ZM Hudson. [J] Angewandte Chemie International Edition, 2023, 62, e202301186.) There are two common methods for fabricating white light emitting devices: one is a complex and expensive multi-chip system that integrates chips emitting the three primary colors (red, green, and blue); the other is to coat a yellow phosphor onto a blue light-emitting diode (LED) chip, or to coat a white phosphor onto a UV LED chip. See (YCui, T Song, J Yu, Y Yang, Z Wang, G Qian.[J] Advanced Functional Materials,2015, 459, 4796. Z Hu, G Huang, WP Lustig, F Wang, H Wang, SJ Teat, DBanerjee, D Zhang, J Li.[J] Chem. Commun., 2015, 51, 3045). White phosphors prepared by mechanically mixing three primary color phosphors suffer from low energy transfer efficiency due to mixing inhomogeneities. Furthermore, due to aggregation-induced quenching (ACQ), many organic fluorescent dyes exhibit low luminescence efficiency or even no luminescence in the solid state. Encapsulating organic fluorescent dyes within porous organic framework materials not only increases the uniformity of dye dispersion but also effectively mitigates the aggregation-induced quenching effect, thus facilitating white light emission. Summary of the Invention

[0004] This invention provides two hydrogen-bonded organic framework composite materials with white light emission based on pentaphenene octacarboxylic acid ligands, and also provides their preparation methods and applications. These fluorescent hydrogen-bonded organic framework compounds have high crystallinity and large pore structure, and have good application prospects in white light emitting diodes.

[0005] Firstly, the objective of the first aspect of this invention is to provide two isomorphic pentaphenene octacarboxylic acid-based hydrogen-bonded organic framework composite materials with white light emission:

[0006] The HOFs (NKM-HOF-1 and NKM-HOF-2) materials in this invention have the chemical formulas (H8PEP-OBu)(MB)3 and (H8PEP-OMe)(MB)3, respectively. H8PEP-OBu is 6,13-dibutoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentapterene, MB is methyl benzoate, and H8PEP-OMe is 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentapterene. The HOFs materials in this invention are crystallized in the orthorhombic Pnma space group. The cell parameters of NKM-HOF-1 are a = 18.3338(5), b = 25.9671(7), c = 37.9645(8), α = β = γ = The cell parameters of NKM-HOF-2 are a = 18.3974(3), b = 26.3784(3), c = 37.7312(4), α = β = γ = 90°.

[0007] The crystal structure of NKM-HOF-1 in this invention is described as follows: Each tetragonal prism-shaped H8PEP-OBu molecule is connected by eight pairs of intermolecular -COOH groups. ... The HOOC-hydrogen bond is linked to eight adjacent H8PEP-OBu molecules, O … H distance, O … O distance and OH … The angular ranges of O are 1.737–1.807 Å, 2.573–2.637 Å, and 166.8–173.3°, all within the range of strong hydrogen bonding. This allows for the formation of a three-dimensional hydrogen-bonded framework. Topologically, if the H8PEP-OBu molecule is considered as an eight-connected node, NKM-HOF-1 possesses a double-interpenetrating bcu topology. The activated NKM-HOF-1a exhibits irregular two-dimensional channels (7.8 × 11.6 Å). 2 The porosity is 64.5%.

[0008] The crystal structure of NKM-HOF-2 in this invention is described as follows: Each tetragonal prism-shaped H8PEP-OMe molecule is connected by eight pairs of intermolecular -COOH groups. ... The HOOC-hydrogen bond is linked to eight adjacent H8PEP-OMe molecules, O … H distance, O … O distance and OH …The angular ranges of O are 1.760–1.806 Å, 2.578–2.634 Å, and 158.3–176.7°, all within the range of strong hydrogen bonding. This allows for the formation of a three-dimensional hydrogen-bonded framework. Topologically, if the H8PEP-OMe molecule is considered as an eight-connected node, NKM-HOF-2 possesses a double-interpenetrating bcu topology. The activated NKM-HOF-2a exhibits irregular two-dimensional channels (8.4 × 16.2 Å). 2 The porosity is 68.6%.

[0009] In this invention, NKM-HOF-1 (7.8 × 11.6 Å) 2 ) and NKM-HOF-2 (8.4 × 16.2 Å 2 The large pore size of these materials endows them with excellent guest molecule encapsulation capabilities, successfully introducing yellowish 3,6-bis(2-thienyl)dione pyrrolopyrrole (DPP) and yellowish-green 9-anthracitel (AnC) as guest molecules into HOFs to achieve white light emission. By fine-tuning the content of the two dyes, two white-emitting composite materials, NKM-HOF-1, were obtained. DPP-0.13 / AnC-3.5 and NKM-HOF-2 The CIE coordinates of the two optimized white light emitting composite materials, DPP-0.12 and AnC-3, are (0.29, 0.33) and (0.32, 0.34), respectively, with corresponding color temperatures of 7815 K and 6073 K.

[0010] The structural formulas of H8PEP-OBu and H8PEP-OMe in this invention are respectively

[0011] .

[0012] The second objective of this invention is to provide a method for preparing the above-mentioned two isomorphic pentaphenene octacarboxylic acid hydrogen-bonded organic framework composite materials with white light emission.

[0013] The preparation methods of the two novel pentaphyllum octacarboxylic acid hydrogen-bonded organic framework composite materials with white light emission in this invention mainly include the following steps:

[0014] (1) Preparation of pentaphenylene dione:

[0015] Anthracene, 1,4-benzoquinone and p-tetrachlorobenzoquinone were dissolved in anhydrous acetic acid, and the mixture was stirred at 125°C for 16 hours. After the reaction was completed, the mixture was cooled to room temperature, poured into water, filtered to collect the precipitate, washed several times with hot water, and dried under vacuum to obtain pentaphenylene dione.

[0016] (2) Preparation of 6,13-dihydroxypentaphenene:

[0017] Pentylenedione was dissolved in anhydrous tetrahydrofuran, and then an aqueous solution of sodium dithionite was added. The reaction mixture was stirred at 40°C for 15 hours under a nitrogen atmosphere, then cooled to room temperature. The tetrahydrofuran was removed by rotary evaporation, and the resulting precipitate was filtered and washed successively with hot water and acetone. After vacuum drying, 6,13-dihydroxypentylene was obtained.

[0018] (3) Preparation of 6,13-dibutoxypentadiene:

[0019] 6,13-Dihydroxypentaphenene, potassium carbonate, a catalytic amount of 18-crown-6, and bromobutane were dissolved in acetone. The reaction mixture was refluxed at 65°C for 15 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled to room temperature, and acetone was removed by rotary evaporation. The solid was collected by filtration, washed with hot water, and dried to obtain 6,13-dibutoxypentaphenene.

[0020] (4) Preparation of 6,13-dibutoxy-2,3,9,10,18,19,24,25-octabromopentadiene:

[0021] 6,13-Dibutoxypentaphenene and a catalytic amount of iron powder were dissolved in anhydrous dichloromethane, and then liquid bromine was added. The reaction mixture was refluxed at 45°C for 1.5 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled to room temperature, washed with an aqueous sodium thiosulfate solution, and then extracted with dichloromethane. The organic phase was purified by column chromatography, and the organic solvent was removed by rotary evaporation. The mixture was then washed with ethanol to obtain 6,13-dibutoxy-2,3,9,10,18,19,24,25-octabromopentaphenene.

[0022] (5) Preparation of 6,13-dibutoxy-2,3,9,10,18,19,24,25-octa(4'-ethoxycarbonylphenyl)pentaphenene:

[0023] 6,13-Dibutoxy-2,3,9,10,18,19,24,25-octabromopentadiene, (4-(ethoxycarbonyl)phenyl)boronic acid, cesium carbonate, and tetra(triphenylphosphine)palladium were dissolved in dioxane. The reaction mixture was refluxed at 85°C for 72 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled to room temperature, and the organic solvent was removed by rotary evaporation. The resulting mixture was poured into water and extracted with dichloromethane. The organic phase was purified by column chromatography, and the organic solvent was removed by rotary evaporation to obtain 6,13-dibutoxy-2,3,9,10,18,19,24,25-octabromopentadiene.

[0024] (6) Preparation of 6,13-dibutoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentaphenene:

[0025] 6,13-Dibutoxy-2,3,9,10,18,19,24,25-octa(4'-ethoxycarbonylphenyl)pentaphenene was dissolved in tetrahydrofuran, and an aqueous solution of sodium hydroxide was added. The reaction mixture was reacted at 70°C for 10 hours. After the reaction was completed, it was cooled to room temperature, the organic solvent was removed by rotary evaporation, the aqueous phase was acidified with hydrochloric acid to pH = 3, the precipitate was collected by filtration, washed several times with water, and dried to obtain 6,13-dibutoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentaphenene.

[0026] (7) Preparation of 6,13-dimethoxypentadiene:

[0027] 6,13-Dihydroxypentaphenene, potassium carbonate, a catalytic amount of 18-crown-6, and iodomethane were dissolved in acetone. The reaction mixture was refluxed at 65°C for 15 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled to room temperature, and acetone was removed by rotary evaporation. The solid was collected by suction filtration, washed with hot water, and dried to give 6,13-dimethoxypentaphenene.

[0028] (8) Preparation of 6,13-dimethoxy-2,3,9,10,18,19,24,25-octabromopentadiene:

[0029] 6,13-Dimethoxypentaphenene and a catalytic amount of iron powder were dissolved in anhydrous dichloromethane, and then liquid bromine was added. The reaction mixture was refluxed at 45°C for 1.5 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled to room temperature, washed with an aqueous sodium thiosulfate solution, and then extracted with dichloromethane. The organic phase was purified by column chromatography, and the organic solvent was removed by rotary evaporation. After washing with ethanol, 6,13-dimethoxy-2,3,9,10,18,19,24,25-octabromopentaphenene was obtained.

[0030] (9) Preparation of 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-ethoxycarbonylphenyl)pentaphenene:

[0031] 6,13-Dimethoxy-2,3,9,10,18,19,24,25-octabromopentadiene, (4-(ethoxycarbonyl)phenyl)boronic acid, cesium carbonate, and tetra(triphenylphosphine)palladium were dissolved in dioxane. The reaction mixture was refluxed at 85°C for 72 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled to room temperature, and the organic solvent was removed by rotary evaporation. The resulting mixture was poured into water and extracted with dichloromethane. The organic phase was purified by column chromatography, and the organic solvent was removed by rotary evaporation to obtain 6,13-dimethoxy-2,3,9,10,18,19,24,25-octabromopentadiene.

[0032] (10) Preparation of 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentaphenene:

[0033] 6,13-Dimethoxy-2,3,9,10,18,19,24,25-octa(4'-ethoxycarbonylphenyl)pentapterene was dissolved in tetrahydrofuran, and an aqueous solution of sodium hydroxide was added. The reaction mixture was reacted at 70°C for 10 hours. After the reaction was completed, the mixture was cooled to room temperature, and the organic solvent was removed by rotary evaporation. The aqueous phase was acidified to pH = 3 with hydrochloric acid, the precipitate was collected by filtration, washed several times with water, and dried to obtain 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentapterene.

[0034] (11) Preparation of NKM-HOF-1

[0035] 6,13-Dibutoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentadiene, tetrahydrofuran and methyl benzoate were placed in a sample vial and the mixture was heated in an oven at 80 °C for 3 days to obtain colorless lumps NKM-HOF-1.

[0036] (12) Preparation of NKM-HOF-2

[0037] 6,13-Dimethoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentadiene, tetrahydrofuran and methyl benzoate were placed in a sample vial and the mixture was heated in an oven at 80 °C for 3 days to obtain colorless lumps of NKM-HOF-2.

[0038] (13) NKM-HOF-1 Preparation of DPP-0.13 / AnC-3.5

[0039] NKM-HOF-1 was immersed in an acetonitrile solution of DPP and AnC, placed in an oven at 50 °C for 24 hours, then filtered and air-dried.

[0040] (14) NKM-HOF-2 Preparation of DPP-0.12 / AnC-3:

[0041] NKM-HOF-2 was immersed in an acetonitrile solution of DPP and AnC, placed in an oven at 50 °C for 24 hours, then filtered and air-dried.

[0042] The third objective of this invention is to provide a white light emitting pentadiene octacarboxylic acid hydrogen-bonded organic framework composite material of the two isomorphic structures described above for use in white light emitting LED bulbs.

[0043] According to the application described in this invention, two hydrogen-bonded organic framework composite materials based on pentaphenene octacarboxylic acid ligands with white light emission are used in the preparation of white light emitting LED bulbs:

[0044] NKM-HOFs A white light emitting LED bulb can be obtained by coating a DPP / AnC composite material onto a 330 nm ultraviolet LED bulb.

[0045] The advantages of this invention are: the hydrogen-bonded organic framework compound containing pentaphenene octacarboxylic acid has a novel structure and can be directionally constructed, providing a reference for the directional construction of hydrogen-bonded organic framework materials. The white light emitting composite material NKM-HOFs in this invention... The preparation method of DPP / AnC is simple, with mild reaction conditions, high yield, and good reproducibility. Attached Figure Description

[0046] Figure 1 These are the preparation steps of 6,13-dibutoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentadiene (H8PEP-OBu).

[0047] Figure 2 These are the preparation steps of 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentadiene (H8PEP-OMe).

[0048] Figure 3 This is a crystal structure diagram of the NKM-HOF-1 material.

[0049] Figure 4 This is a crystal structure diagram of the NKM-HOF-2 material.

[0050] Figure 5 This is a topological diagram of the NKM-HOF-1 material.

[0051] Figure 6 This is a topological diagram of the NKM-HOF-2 material.

[0052] Figure 7 This is a diagram showing the pore structure of the activated NKM-HOF-1 and NKM-HOF-2 materials.

[0053] Figure 8 These are the X-ray powder diffraction (XRD) patterns of the NKM-HOF-1 and NKM-HOF-2 materials.

[0054] Figure 9 These are the thermogravimetric spectra of the NKM-HOF-1 and NKM-HOF-2 materials.

[0055] Figure 10 It is the NKM-HOF-1 DPP-0.13 / AnC-3.5 and NKM-HOF-2 X-ray powder diffraction (XRD) pattern of DPP-0.12 / AnC-3 material.

[0056] Figure 11 It is the NKM-HOFs Fluorescence spectrum of DPP / AnC material. Detailed Implementation

[0057] Example 1:

[0058] (1) Preparation of pentaphenylene dione:

[0059] Anthracene (10.69 g, 60 mmol), 1,4-benzoquinone (3.24 g, 30 mmol), and p-tetrachlorobenzoquinone (14.75 g, 60 mmol) were dissolved in anhydrous acetic acid (300 mL). The mixture was stirred at 125°C for 16 hours. After the reaction was complete, the mixture was cooled to room temperature and poured into water (300 mL). The precipitate was collected by filtration, washed several times with hot water, and dried under vacuum to give a yellow solid (13.11 g, yield: 95%). 1 ¹H NMR (400 MHz, CDCl₃): δ 7.37 (d, 8H), 6.98 (d, 8H), 5.75 (s, 4H) ppm; indicating that pentaphenylenedione was obtained.

[0060] (2) Preparation of 6,13-dihydroxypentaphenene:

[0061] Pentaterene dione (7.82 g, 17 mmol) was dissolved in anhydrous tetrahydrofuran (200 mL), and then 140 mL of sodium dithionite (35.52 g, 204 mmol) aqueous solution was added. The reaction mixture was stirred at 40°C for 15 hours under a nitrogen atmosphere, and then cooled to room temperature. After removing the tetrahydrofuran by rotary evaporation, the resulting precipitate was filtered and washed successively with hot water and acetone, and dried under vacuum to give a white solid (7.67 g, yield: 98%). 1 ¹H NMR (400 MHz, CDCl₃): δ 7.33 (d, 8H), 6.94 (d, 8H), 5.64 (s, 4H) ppm; indicating the presence of 6,13-dihydroxypentaphene.

[0062] (3) Preparation of 6,13-dibutoxypentadiene:

[0063] 6,13-Dihydroxypentaphenene (7.67 g, 16.60 mmol), potassium carbonate (11.47 g, 83 mmol), a catalytic amount of 18-crown-6 (50 mg), and bromobutane (16.1 mL, 150 mmol) were dissolved in acetone (300 mL). The reaction mixture was refluxed at 65°C for 15 hours under a nitrogen atmosphere. After the reaction was complete, it was cooled to room temperature. Acetone was removed by rotary evaporation, the solid was collected by filtration, washed with hot water, and dried to give a white solid (7.67 g, 95%); 1H NMR (400 MHz, CDCl3): δ7.32 (d, 8H), 6.94 (d, 8H), 5.64 (s, 4H), 3.90 (t, 4H), 1.99 (m, 4H), 1.73 (m, 4H), 1.14 (t, 6H) ppm; indicating the presence of 6,13-dibutoxypentadiene.

[0064] (4) Preparation of 6,13-dibutoxy-2,3,9,10,18,19,24,25-octabromopentadiene:

[0065] 6,13-Dibutoxypentadiene (57.4 mg, 1 mmol) and a catalytic amount of iron powder (160 mg) were dissolved in anhydrous dichloromethane (60 mL), followed by the addition of liquid bromine (0.53 mL, 9.7 mmol). The reaction mixture was refluxed at 45°C for 1.5 h under a nitrogen atmosphere. After the reaction was complete, the mixture was cooled to room temperature, washed with an aqueous solution of sodium thiosulfate, and then extracted with dichloromethane. The organic phase was purified by column chromatography, and the organic solvent was removed by rotary evaporation. The product was then washed with ethanol to obtain a pale yellow solid (890 mg, 74%). ¹H NMR (400 MHz, CDCl₃): δ 7.56 (s, 8H), 5.51 (s, 4H), 3.86 (t, 4H), 1.96 (m, 4H), 1.72 (m, 4H), 1.50 (m, 4H), 1.16 (t, 6H) ppm. This indicates the presence of 6,13-dibutoxy-2,3,9,10,18,19,24,25-octabromopentadiene.

[0066] (5) Preparation of 6,13-dibutoxy-2,3,9,10,18,19,24,25-octa(4'-ethoxycarbonylphenyl)pentaphenene:

[0067] 6,13-Dibutoxy-2,3,9,10,18,19,24,25-octabromopentadiene (2.55 g, 2 mmol), (4-(ethoxycarbonyl)phenyl)boronic acid (4.66 g, 24 mmol), cesium carbonate (10.43 g, 32 mmol), and tetra(triphenylphosphine)palladium (0.46 g, 0.4 mmol) were dissolved in dioxane (250 mL), and the reaction mixture was refluxed at 85°C for 72 hours under a nitrogen atmosphere. After the reaction was completed and cooled to room temperature, the organic solvent was removed by rotary evaporation. The resulting mixture was poured into water and extracted with dichloromethane. The organic phase was purified by column chromatography, and after removing the organic solvent by rotary evaporation, a pale yellow solid (1.66 g, 45%) was obtained. ¹H NMR (400 MHz, CDCl₃): δ 7.85 (d, 16H), 7.48 (s, 8H), 7.08 (d, 16H), 5.89 (s, 4H), 4.35 (q, 16H), 3.75 (t, 4H), 2.02 (m, 4H), 1.72 (m, 4H), 1.36 (t, 24H), 1.25 (t, 6H) ppm; it is known that 6,13-dibutoxy-2,3,9,10,18,19,24,25-octa(4'-ethoxycarbonylphenyl)pentaphenene was obtained;

[0068] (6) Preparation of 6,13-dibutoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentaphenene:

[0069] 6,13-Dibutoxy-2,3,9,10,18,19,24,25-octa(4'-ethoxycarbonylphenyl)pentapterene (1.66 g, 0.9 mmol) was dissolved in tetrahydrofuran (40 mL), and 40 mL of aqueous sodium hydroxide (2.16 g, 54 mmol) solution was added. The reaction mixture was reacted at 70°C for 10 hours. After the reaction was completed, the mixture was cooled to room temperature, the organic solvent was removed by rotary evaporation, and the aqueous phase was acidified with hydrochloric acid to pH = 3. The precipitate was collected by filtration, washed several times with water, and dried to obtain a white solid (1.33 g, 96%); 1H NMR (400 MHz, DMSO-d6): δ 12.92 (s, 8H), 7.75 (d, 16H), 7.57 (s, 8H), 7.15 (d, 16H), 6.06 (s, 4H), 4.03 (t, 4H), 1.97 (m, 4H), 1.68 (m, 4H), 1.01 (t, 6H) ppm; indicating the presence of 6,13-dibutoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentapterene;

[0070] Please also refer to the appendix for the above steps. Figure 1 .

[0071] (7) Preparation of 6,13-dimethoxypentadiene:

[0072] 6,13-Dihydroxypentaphenene (0.93 g, 2 mmol), potassium carbonate (1.38 g, 10 mmol), a catalytic amount of 18-crown-6 (6 mg), and methyl iodoforme (1.1 mL, 18 mmol) were dissolved in acetone (35 mL). The reaction mixture was refluxed at 65°C for 15 hours under a nitrogen atmosphere. After the reaction was complete, the mixture was cooled to room temperature. Acetone was removed by rotary evaporation, the solid was collected by filtration, washed with hot water, and dried to give a white solid (0.75 g, 76%). ¹H NMR (400 MHz, CDCl₃): δ 7.35 (d, 8H), 6.96 (d, 8H), 5.68 (s, 4H), 3.88 (s, 6H) ppm; indicating that 6,13-dimethoxypentaphenene was obtained.

[0073] (8) Preparation of 6,13-dimethoxy-2,3,9,10,18,19,24,25-octabromopentadiene:

[0074] 6,13-Dimethoxypentaphenene (490 mg, 2 mmol) and a catalytic amount of iron powder (160 mg) were dissolved in 60 mL of anhydrous dichloromethane, and then liquid bromine (0.53 mL, 9.7 mmol) was added. The reaction mixture was refluxed at 45°C for 1.5 h under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled to room temperature, washed with an aqueous sodium thiosulfate solution, and then extracted with dichloromethane. The organic phase was purified by column chromatography, and the organic solvent was removed by rotary evaporation. The mixture was washed with ethanol to give a yellow solid (835 mg, 75%); 1H NMR (400 MHz, CDCl3): δ 7.58 (s, 8H), 5.54 (s, 4H), 3.86 (s, 6H) ppm; indicating that 6,13-dimethoxy-2,3,9,10,18,19,24,25-octabromopentaphenene was obtained.

[0075] (9) Preparation of 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-ethoxycarbonylphenyl)pentaphenene:

[0076] 6,13-Dimethoxy-2,3,9,10,18,19,24,25-octabromopentadiene (2.24 g, 2 mmol), (4-(ethoxycarbonyl)phenyl)boronic acid (4.66 g, 24 mmol), cesium carbonate (10.43 g, 32 mmol), and tetra(triphenylphosphine)palladium (0.46 g, 0.4 mol) were dissolved in 250 mL of dioxane. The reaction mixture was refluxed at 85°C for 72 hours under a nitrogen atmosphere. After the reaction was completed and cooled to room temperature, the organic solvent was removed by rotary evaporation. The resulting mixture was poured into water and extracted with dichloromethane. The organic phase was purified by column chromatography. After removing the organic solvent by rotary evaporation, a pale yellow solid (2.48 g, 74%) was obtained. ¹H NMR (400 MHz, CDCl₃): δ 7.85 (d, 16H), 7.51 (s, 8H), 7.09 (d, 16H), 5.91 (s, 4H), 4.34 (q, 16H), 3.98 (s, 6H), 1.39 (t, 24H) ppm; it was identified as 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-ethoxycarbonylphenyl)pentapterene.

[0077] (10) Preparation of 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentaphenene:

[0078] 6,13-Dimethoxy-2,3,9,10,18,19,24,25-octa(4'-ethoxycarbonylphenyl)pentapterene (2.48 g, 1.5 mmol) was dissolved in 40 mL of tetrahydrofuran, and 40 mL of aqueous sodium hydroxide (3.6 g, 90 mmol) solution was added. The reaction mixture was reacted at 70°C for 10 hours. After the reaction was complete, the mixture was cooled to room temperature, the organic solvent was removed by rotary evaporation, and the aqueous phase was acidified to pH = 3 with hydrochloric acid. The precipitate was collected by filtration, washed several times with water, and dried to give a white solid (2.07 g, 95%). ¹H NMR (400 MHz, DMSO-d) 6 ): δ 7.75 (d, 16H), 7.61 (s, 8H), 7.15 (d, 16H), 6.11 (s, 4H), 3.94 (s, 6H) ppm; it is known that 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentaphenene was obtained;

[0079] Please also refer to the appendix for the above steps. Figure 2 .

[0080] (11) Preparation of NKM-HOF-1

[0081] 15 mg of 6,13-dibutoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentadiene, 6 mL of tetrahydrofuran, and 3 mL of methyl benzoate were placed in a 20 mL sample vial. The mixture was heated in an oven at 80 °C for 3 days to obtain colorless granular NKM-HOF-1.

[0082] (12) Preparation of NKM-HOF-2

[0083] 15 mg of 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentadiene, 6 mL of tetrahydrofuran, and 3 mL of methyl benzoate were placed in a 20 mL sample vial. The mixture was heated in an oven at 80 °C for 3 days to obtain colorless granular NKM-HOF-2.

[0084] (13) NKM-HOF-1 Preparation of DPP-0.13 / AnC-3.5

[0085] 15 mg NKM-HOF-1 was soaked in 4 mL of acetonitrile solution of DPP (0.13 mmol / L) and AnC (3.5 mmol / L), placed in an oven at 50 °C for 24 hours, then filtered and air-dried.

[0086] (14) NKM-HOF-2 Preparation of DPP-0.12 / AnC-3:

[0087] 15 mg NKM-HOF-2 was soaked in 4 mL of acetonitrile solution of DPP (0.12 mmol / L) and AnC (3.0 mmol / L), placed in an oven at 50 °C for 24 hours, then filtered and air-dried.

[0088] (15) Fabrication of white light emitting LED bulbs:

[0089] NKM-HOFs A white light emitting LED bulb can be obtained by coating a DPP / AnC composite material onto a 330 nm ultraviolet LED bulb.

[0090] The present invention uses the following instruments or methods to characterize and test the properties of materials.

[0091] Single-crystal X-ray diffraction (XRD) tests were performed on NKM-HOF-1 and NKM-HOF-2 materials, respectively. Crystals were removed from the mother liquor, transferred to oil, and mounted on a loop ring for single-crystal XRD analysis. Diffraction data were obtained at 100 K using a Rigaku XtalAB Pro MM007 DW diffractometer equipped with Cu-Kα (λ = 1.54184 Å). Data collection and reconstruction were performed using the CrystAlisPro program. The crystal structure of NKM-HOF-1 is shown below. Figure 3 As shown (drawn using Dianond software). The crystal structure of NKM-HOF-2 is as follows. Figure 4 As shown (drawn using Dianond software).

[0092] The topology of NKM-HOF-1 was calculated using ToposPro software. The topology of NKM-HOF-1 is as follows: Figure 5 As shown (drawn using Dianond software).

[0093] The topology of NKM-HOF-2 was calculated using ToposPro software. The topology of NKM-HOF-2 is as follows: Figure 6 As shown (drawn using Dianond software).

[0094] The pore structures of activated NKM-HOF-1 and NKM-HOF-2 are as follows: Figure 7 As shown (drawn using Mercury software).

[0095] The powder X-ray diffraction (PXRD) patterns of the NKM-HOF-1 and NKM-HOF-2 materials prepared in this invention were collected on a Rigaku MiniFlex 600 diffractometer equipped with a copper target. The X-ray powder diffraction patterns are shown below. Figure 8 As shown (drawn using Origin software, simulated using Mercury software).

[0096] Thermogravimetric analysis (TGA) chromatograms of this invention were collected using a Rigaku Thermo Plus EVO2 8182 thermal analyzer, see [link / reference]. Figure 9 (Drawn using Origin software).

[0097] The NKM-HOF-1 prepared in this invention DPP-0.13 / AnC-3.5 and NKM-HOF-2 Powder X-ray diffraction (PXRD) patterns of the DPP-0.12 / AnC-3 material were collected on a Rigaku MiniFlex 600 diffractometer equipped with a copper target. The X-ray powder diffraction patterns are shown below. Figure 10As shown (drawn using Origin software, simulated using Mercury software).

[0098] NKM-HOFs prepared in this invention The fluorescence spectrum of the DPP / AnC composite material was measured using an Ediburgh Instruments FS5 spectrophotometer. Figure 11 The diagram shows the usage (plotted using Origin software). By keeping the concentration of the 3,6-bis(2-thienyl)dione-pyrrolopyrrole acetonitrile solution constant at 0.13 mmol / L, the concentration of the 9-anthraaldehyde acetonitrile solution was varied within the range of 0.50–4.00 mmol / L. NKM-HOF-1 The first emission band of DPP / AnC remained almost unchanged, while the second and third emission bands increased with increasing 9-anthraaldehyde concentration. The corresponding CIE coordinates changed sequentially from (0.24, 0.20) to (0.29, 0.36). When the concentration of the 3,6-bis(2-thienyl)dione-pyrrolopyrrole acetonitrile solution was 0.13 mmol / L and the concentration of the 9-anthraaldehyde acetonitrile solution was 3.5 mmol / L, the CIE coordinates of the complex were (0.29, 0.33), indicating that white light emission was achieved. Similar results were obtained for NKM-HOF-2, where the optimal concentrations of 3,6-bis(2-thienyl)dione-pyrrolopyrrole and 9-anthraaldehyde were 0.12 mmol / L and 3.00 mmol / L, respectively, with corresponding CIE coordinates of (0.32, 0.34).

Claims

1. A composite material of two isomorphic pentaphenene octacarboxylic acid-based hydrogen-bonded organic frameworks exhibiting white light emission, characterized by: The composite material is a complex of two pentaphyllum octacarboxylic acid hydrogen-bonded organic frameworks (HOFs) and organic dyes 3,6-bis(2-thienyl)dione-pyrrolopyrrole (DPP) and 9-anthraaldehyde (AnC).

2. The two isomorphic pentaphenene octacarboxylic acid hydrogen-bonded organic framework composite materials with white light emission as described in claim 1, characterized in that: Two pentapeptide octacarboxylic acid-bonded organic frameworks (HOFs) are NKM-HOF-1 and NKM-HOF-2, with chemical formulas (H8PEP-OBu)(MB)3 and (H8PEP-OMe)(MB)3, respectively. H8PEP-OBu is 6,13-dibutoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentapeptide, MB is methyl benzoate, and H8PEP-OMe is 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentapeptide. The HOFs are crystallized in the orthorhombic crystal system Pnma space group. The unit cell parameters of NKM-HOF-1 are a = 18.3338(5), b = 25.9671(7), c = 37.9645(8), α = β. =γ = 90°, the cell parameters of NKM-HOF-2 are a = 18.3974(3), b = 26.3784(3), c = 37.7312(4), α = β = γ = 90°.

3. The two isomorphic pentaphenene octacarboxylic acid hydrogen-bonded organic framework composite materials with white light emission as described in claim 2, characterized in that: NK The crystal structure of M-HOF-1 is as follows: Each tetragonal prism-shaped H8PEP-OBu molecule is connected by eight pairs of intermolecular -COOH groups. ... The HOOC-hydrogen bond is linked to eight adjacent H8PEP-OBu molecules, O … H distance, O … O distance and OH … The angular ranges of O are 1.737–1.807 Å, 2.573–2.637 Å, and 166.8–173.3°, all within the range of strong hydrogen bonds. This allows for the formation of a three-dimensional hydrogen-bonded framework. Topologically, if the H8PEP-OBu molecule is considered as an eight-connector node, NKM-HOF-1 possesses a double-interpenetrating bcu topology. Activated NKM-HOF-1 is designated NKM-HOF-1a, which has irregular two-dimensional channels of 7.8 × 11.6 Å. 2 The porosity is 64.5%.

4. The two isomorphic pentaphenene octacarboxylic acid hydrogen-bonded organic framework composite materials with white light emission as described in claim 2, characterized in that: NK The crystal structure of M-HOF-2 is as follows: each prismatic H8PEP-OMe molecule is connected by eight pairs of -COOH groups between molecules. ... The HOOC-hydrogen bond is linked to eight adjacent H8PEP-OMe molecules, O … H distance, O … O distance and OH … The angular ranges of O are 1.760–1.806 Å, 2.578–2.634 Å, and 158.3–176.7°, all within the range of strong hydrogen bonding. This allows for the formation of a three-dimensional hydrogen-bonded framework. Topologically, if the H8PEP-OMe molecule is considered as an eight-connected node, NKM-HOF-2 possesses a double-interpenetrating bcu topology. After activation, NKM-HOF-2 is designated NKM-HOF-2a, exhibiting irregular two-dimensional channels of 8.4 × 16.2 Å. 2 The porosity is 68.6%.

5. The two isomorphic pentaphenene octacarboxylic acid hydrogen-bonded organic framework composite materials with white light emission as described in claim 2, characterized in that: NK The large pore size of M-HOF-1 and NKM-HOF-2 endows them with excellent guest molecule encapsulation capabilities, successfully introducing the yellow-emitting 3,6-bis(2-thienyl)dione-pyrrolopyrrole (DPP) and the yellow-green-emitting 9-anthraaldehyde (AnC) as guest molecules into HOFs to achieve white light emission. By fine-tuning the content of the two dyes, two white-emitting composite materials were obtained. The composite material with NKM-HOF-1 as the host and DPP and AnC as guests is denoted as NKM-HOF-1. DPP-0.13 / AnC-3.5, a composite material with NKM-HOF-2 as the main component and DPP and AnC as the auxiliary components, is designated as NKM-HOF-2. The CIE coordinates of the two white-light-emitting composite materials, DPP-0.12 / AnC-3, are 0.29, 0.33 and 0.32, 0.34, respectively, with corresponding color temperatures of 7815 K and 6073 K.

6. A method for preparing two isomorphic pentaphenene octacarboxylic acid-based hydrogen-bonded organic framework composite materials with white light emission as described in any one of claims 1-5, comprising the following steps: (1) Preparation of pentaphenylene dione: Anthracene, 1,4-benzoquinone and p-tetrachlorobenzoquinone were dissolved in anhydrous acetic acid, and the mixture was stirred at 125°C for 16 hours. After the reaction was completed, the mixture was cooled to room temperature, poured into water, filtered to collect the precipitate, washed several times with hot water, and dried under vacuum to obtain pentaphenylene dione. (2) Preparation of 6,13-dihydroxypentaphenene: Pentylenedione was dissolved in anhydrous tetrahydrofuran, and then an aqueous solution of sodium dithionite was added. The reaction mixture was stirred at 40°C for 15 hours under a nitrogen atmosphere, then cooled to room temperature. The tetrahydrofuran was removed by rotary evaporation, and the resulting precipitate was filtered and washed successively with hot water and acetone. After vacuum drying, 6,13-dihydroxypentylene was obtained. (3) Preparation of 6,13-dibutoxypentadiene: 6,13-Dihydroxypentaphenene, potassium carbonate, a catalytic amount of 18-crown-6, and bromobutane were dissolved in acetone. The reaction mixture was refluxed at 65°C for 15 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled to room temperature, and acetone was removed by rotary evaporation. The solid was collected by suction filtration, washed with hot water, and dried to obtain 6,13-dibutoxypentaphenene. (4) Preparation of 6,13-dibutoxy-2,3,9,10,18,19,24,25-octabromopentadiene: 6,13-Dibutoxypentaphenene and a catalytic amount of iron powder were dissolved in anhydrous dichloromethane, and then liquid bromine was added. The reaction mixture was refluxed at 45°C for 1.5 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled to room temperature, washed with an aqueous sodium thiosulfate solution, and then extracted with dichloromethane. The organic phase was purified by column chromatography, and the organic solvent was removed by rotary evaporation. The mixture was then washed with ethanol to obtain 6,13-dibutoxy-2,3,9,10,18,19,24,25-octabromopentaphenene. (5) Preparation of 6,13-dibutoxy-2,3,9,10,18,19,24,25-octa(4'-ethoxycarbonylphenyl)pentaphenene: 6,13-Dibutoxy-2,3,9,10,18,19,24,25-octabromopentadiene, (4-(ethoxycarbonyl)phenyl)boronic acid, cesium carbonate, and tetra(triphenylphosphine)palladium were dissolved in dioxane. The reaction mixture was refluxed at 85°C for 72 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled to room temperature, and the organic solvent was removed by rotary evaporation. The resulting mixture was poured into water and extracted with dichloromethane. The organic phase was purified by column chromatography, and the organic solvent was removed by rotary evaporation to obtain 6,13-dibutoxy-2,3,9,10,18,19,24,25-octabromopentadiene. (6) Preparation of 6,13-dibutoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentaphenene: 6,13-Dibutoxy-2,3,9,10,18,19,24,25-octa(4'-ethoxycarbonylphenyl)pentapterene was dissolved in tetrahydrofuran, and an aqueous solution of sodium hydroxide was added. The reaction mixture was reacted at 70°C for 10 hours. After the reaction was completed, the mixture was cooled to room temperature, and the organic solvent was removed by rotary evaporation. The aqueous phase was acidified to pH = 3 with hydrochloric acid, the precipitate was collected by filtration, washed several times with water, and dried to obtain 6,13-dibutoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentapterene. (7) Preparation of 6,13-dimethoxypentadiene: 6,13-Dihydroxypentaphenene, potassium carbonate, a catalytic amount of 18-crown-6, and iodomethane were dissolved in acetone. The reaction mixture was refluxed at 65°C for 15 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled to room temperature, and acetone was removed by rotary evaporation. The solid was collected by suction filtration, washed with hot water, and dried to obtain 6,13-dimethoxypentaphenene. (8) Preparation of 6,13-dimethoxy-2,3,9,10,18,19,24,25-octabromopentadiene: 6,13-Dimethoxypentaphenene and a catalytic amount of iron powder were dissolved in anhydrous dichloromethane, and then liquid bromine was added. The reaction mixture was refluxed at 45°C for 1.5 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled to room temperature, washed with an aqueous sodium thiosulfate solution, and then extracted with dichloromethane. The organic phase was purified by column chromatography, and the organic solvent was removed by rotary evaporation. After washing with ethanol, 6,13-dimethoxy-2,3,9,10,18,19,24,25-octabromopentaphenene was obtained. (9) Preparation of 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-ethoxycarbonylphenyl)pentaphenene: 6,13-Dimethoxy-2,3,9,10,18,19,24,25-octabromopentadiene, (4-(ethoxycarbonyl)phenyl)boronic acid, cesium carbonate, and tetra(triphenylphosphine)palladium were dissolved in dioxane. The reaction mixture was refluxed at 85°C for 72 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled to room temperature, and the organic solvent was removed by rotary evaporation. The resulting mixture was poured into water and extracted with dichloromethane. The organic phase was purified by column chromatography, and the organic solvent was removed by rotary evaporation to obtain 6,13-dimethoxy-2,3,9,10,18,19,24,25-octabromopentadiene. (10) Preparation of 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentaphenene: 6,13-Dimethoxy-2,3,9,10,18,19,24,25-octa(4'-ethoxycarbonylphenyl)pentapterene was dissolved in tetrahydrofuran, and an aqueous solution of sodium hydroxide was added. The reaction mixture was reacted at 70°C for 10 hours. After the reaction was completed, the mixture was cooled to room temperature, and the organic solvent was removed by rotary evaporation. The aqueous phase was acidified to pH = 3 with hydrochloric acid, the precipitate was collected by filtration, washed several times with water, and dried to obtain 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentapterene. (11) Preparation of NKM-HOF-1 6,13-Dibutoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentadiene, tetrahydrofuran and methyl benzoate were placed in a sample vial and the mixture was heated in an oven at 80 °C for 3 days to obtain colorless lumps NKM-HOF-1. (12) Preparation of NKM-HOF-2 6,13-Dimethoxy-2,3,9,10,18,19,24,25-octa(4'-carboxyphenyl)pentadiene, tetrahydrofuran and methyl benzoate were placed in a sample vial and the mixture was heated in an oven at 80 °C for 3 days to obtain colorless lumps of NKM-HOF-2. (13) NKM-HOF-1 Preparation of DPP-0.13 / AnC-3.5 NKM-HOF-1 was immersed in an acetonitrile solution of DPP and AnC, placed in an oven at 50 °C for 24 hours, then filtered and air-dried. (14) NKM-HOF-2 Preparation of DPP-0.12 / AnC-3: NKM-HOF-2 was immersed in an acetonitrile solution of DPP and AnC, placed in an oven at 50 °C for 24 hours, then filtered and air-dried.

7. The application of the two isomorphic pentaphenene octacarboxylic acid hydrogen-bonded organic framework composite materials with white light emission as described in any one of claims 1-5 in white light emitting LED bulbs.

8. The application as described in claim 7, characterized in that, The method for manufacturing white light emitting LED bulbs is as follows: The two white-light-emitting composite materials NKM-HOF-1 described in claim 5 DPP-0.13 / AnC-3.5 and NKM-HOF-2 DPP-0.12 / AnC-3 were coated onto a 330 nm ultraviolet LED bulb to obtain a white light emitting LED bulb.

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