CN114956973A - Organic porous material based on tetraphenylethylene, and preparation method and application thereof - Google Patents
Organic porous material based on tetraphenylethylene, and preparation method and application thereof Download PDFInfo
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- 239000011148 porous material Substances 0.000 title claims abstract description 49
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 25
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 13
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 13
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 6
- 230000005284 excitation Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000010257 thawing Methods 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- -1 tetraphenylethylene compound Chemical class 0.000 claims 1
- YLOCGHYTXIINAI-XKUOMLDTSA-N (2s)-2-amino-3-(4-hydroxyphenyl)propanoic acid;(2s)-2-aminopentanedioic acid;(2s)-2-aminopropanoic acid;(2s)-2,6-diaminohexanoic acid Chemical compound C[C@H](N)C(O)=O.NCCCC[C@H](N)C(O)=O.OC(=O)[C@@H](N)CCC(O)=O.OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 YLOCGHYTXIINAI-XKUOMLDTSA-N 0.000 abstract description 28
- 102000016726 Coat Protein Complex I Human genes 0.000 abstract description 27
- 108010092897 Coat Protein Complex I Proteins 0.000 abstract description 27
- 238000006862 quantum yield reaction Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001228 spectrum Methods 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000012298 atmosphere Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000005297 pyrex Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000004566 IR spectroscopy Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)C=C1 VXWBQOJISHAKKM-UHFFFAOYSA-N 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 2
- BIRLDGKMJJEZRI-UHFFFAOYSA-N 1-bromo-4-[1,2,2-tris(4-bromophenyl)ethenyl]benzene Chemical group C1=CC(Br)=CC=C1C(C=1C=CC(Br)=CC=1)=C(C=1C=CC(Br)=CC=1)C1=CC=C(Br)C=C1 BIRLDGKMJJEZRI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 239000013474 COF-1 Substances 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 241000083879 Polyommatus icarus Species 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
- C07C47/548—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings having unsaturation outside the six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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Abstract
The invention discloses a tetraphenylethylene-based organic porous material, and a preparation method and application thereof. The organic porous material COP-1 is prepared by adding TPE-Ph-CHO and hydrazine hydrate into o-DCB and 1,4-Dioxane solvent, reacting for 5 days at 100 ℃ in an oxygen-free atmosphere, filtering to obtain a yellow solid, washing for one day with tetrahydrofuran, methanol and ethanol to obtain a target product COP-1, and the material is simple to synthesize, firm in structure and stable in chemical property, and emits yellow light through a fluorescent CIE (circular element interference element) spectrum, wherein the absolute quantum yield is 13.45%. Has potential application value in the field of white light LEDs.
Description
Technical Field
The invention belongs to the field of organic porous materials, and particularly relates to a tetraphenylethylene-based organic porous material, and a preparation method and application thereof.
Background
In recent years, porous materials have been widely used in many fields such as ion exchange, adsorption and separation, and host-guest chemistry. Therefore, the research on the porous material has both basic and application research values. Porous materials are classified into three forms, inorganic-organic hybrid and organic, according to their elemental compositions and bonding methods. Compared with the research on inorganic porous materials and inorganic-organic porous materials, the research time on the aspect of organic porous materials is shorter. The organic porous material has the advantages of rich skeleton composition, strong modification, good chemical stability, high specific surface area, adjustable pore channel structure, light weight and the like.
At present, white light is realized by a white light LED light source, and the following three methods are mainly adopted: firstly, adopting red, green and blue LEDs to generate white light; coating yellow fluorescent powder on the blue LED to obtain white light; and thirdly, adopting near ultraviolet and ultraviolet LEDs to excite red, green and blue fluorescent powder, and mixing the three colors of light to obtain white light. The biggest disadvantage of the first method is that the price is high, which is not favorable for commercialization development; the third method adopts ultraviolet excitation, not only has higher energy consumption, but also is not beneficial to environmental protection, and especially can cause serious harm to human eyes; in view of these aspects, the second approach has potential advantages. Most of the commercial fluorescent powder under the eyes is oxide or nitride of rare earth metals such as europium, terbium, yttrium and the like, and the rare earth is used as a non-renewable resource, which is extremely precious and the price rises all the way in recent years, so that the search for available organic matters with better chemical stability as raw materials for preparing the fluorescent powder is of great significance.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of synthesizing an organic porous material by using a tetraphenylethylene-based luminescent group. The breadth and depth of the luminescent material are further expanded.
The invention also aims to solve the technical problem of providing a method for synthesizing an organic porous material with tetraphenylethylene as a luminescent core.
The invention also aims to solve the technical problem of providing the application of the organic porous material in the aspect of emitting white LED light.
The organic porous material (COP-1) with excellent luminescence property is synthesized by selecting cheap and easily available tetraphenylethylene with excellent Aggregation Induced Emission (AIE) effect through the reaction of aldehyde group and amino group on hydrazine hydrate under the condition of solvothermal, the material has a layered three-dimensional network structure and is linked through a rotatable imide chemical bond, thereby effectively avoiding aggregation induced quenching caused by structure accumulation, maintaining higher fluorescence quantum yield, and the absolute quantum yield is 13.45%. Therefore, the LED has wide prospect in the direction of light-emitting components.
The synthetic route is as follows:
the value of n is a positive integer, the actual value depending on the amount of monomers involved in the reaction.
The invention provides TPE-Ph-CHO with a chemical formula of C 54 H 36 O 4 The structural formula is as follows:
the structure of hydrazine hydrate is as follows: 2 HN-NH 2 ·H 2 O
the COP-1 structure is as follows:
wherein n represents a positive integer.
Wherein the maximum excitation wavelength E of the synthesized organic porous material (COP-1) based on tetraphenylethylene as a luminescent core x 470-490nm, maximum emission wavelength E m The absolute quantum yield was 13.45% at 570-590 nm.
The invention also discloses a preparation method of the organic porous material (COP-1) taking tetraphenylethylene as a luminescent core, which comprises the following steps: TPE-Ph-CHO and hydrazine hydrate are weighed in sequence and added into a glass tube, dioxane and o-dichlorobenzene are added as solvents to slightly dissolve the materials, oxygen is removed, and the materials are heated to 100 ℃ under sealed conditions and reacted for 5 days. After cooling to room temperature, the product was filtered to give a yellowish solid.
Wherein the mol ratio of TPE-Ph-CHO to hydrazine hydrate is 1: the highest yield was obtained at 2.
The invention also discloses the application of the yellow fluorescent material in preparing white light LED materials.
The invention also discloses a white light LED material which is prepared from the yellow fluorescent material.
The tetraphenylethylene group with AIE effect is selected, has stable structure, is an important hole conducting molecule, and has higher fluorescence property and photoluminescence efficiency. TPE-Ph-CHO taking tetraphenylethylene group as core is taken as main ligand, and hydrazine hydrate is synthesized to obtain the organic porous fluorescent powder material with good blue light excited yellow light by a solvothermal method, and the material can be found to basically meet the technical requirements for preparing white light LED by comparing with commercial YAG (Ce) material.
Has the advantages that: compared with the luminous white LED reported by the prior art, the COP-1 has the following advantages:
1. the whole synthesis process does not contain heavy metal, depends on covalent bond linkage, and has firm structure and stable chemical property.
2. The invention self-assembles tetraphenyl ethylene organic ligand and hydrazine hydrate to prepare a yellow fluorescent material. Overcomes the defects that the white light material mainly adopts rare earth metals with high price and environmental hazard and the like. The compound has the advantages of simple synthesis method, good reproducibility, simple and safe operation, and provides reference for purposefully synthesizing functional materials with good fluorescence property in the future. The fluorescence property shows that the compound can emit yellow light under the excitation of blue light, and has wide application prospect in the aspect of white light LED materials.
Description of the drawings:
FIG. 1 is a graph of the infrared spectra of example 3 and examples and 1;
FIG. 2 is a Thermogravimetric (TG) plot of COP-1 of example 3;
FIG. 3 is an aperture distribution diagram of example 3;
FIG. 4 is the adsorption on Nitrogen (ADS) desorption on Nitrogen (DES) graph of example 3;
FIG. 5 is a solid state fluorescence spectrum of COP-1 of example 3;
FIG. 6 is a diagram of an LED device prepared according to example 4;
fig. 7 is the chromaticity diagram (CIE) of example 3.
The specific implementation mode is as follows:
specific embodiments of the experiments are described below, but do not represent a limitation of the present invention.
All reagents used were purchased from national reagents GmbH, solvents dioxan and o-dichlorobenzene were purchased from Aladdin reagents. It should be further noted that:
TG/DTA test conditions: under the protection of nitrogen, the temperature rise interval is from room temperature to 700 ℃, and the temperature rise rate is 10 ℃ min -1 (ii) a Fluorescence analysis test A spectrofluorometer FS5 fluorescence spectrometer was used.
EXAMPLE 1 Synthesis of TPE-Ph-CHO Compound
Tetrakis (4-bromophenyl) ethylene (0.001mol) and 4-formylphenylboronic acid (0.006mol) were reacted in the presence of palladium (0.05g) as a catalyst in a ratio of 1: 6 was dissolved in 80mL of toluene, and 1.66g of potassium carbonate was dissolved in 20mL of water, and the two were mixed well. And reacting for 24 hours under the nitrogen atmosphere to obtain the TPE-Ph-CHO complex.
The hydrogen spectrum data of the synthesized TPE-Ph-CHO complex are as follows:
1H NMR(DMSO-d6,400MHz)δ:10.03(s,1H),7.97-7.95(d,J＝8.0Hz,2H),7. 92-7.89(d,J＝12.0Hz,2H),7.70-7.68(d,J＝8.0Hz,2H),7.25-7.23(d,J＝8.0Hz,2H ).
example 2
Tetrakis (4-bromophenyl) ethylene (0.001mol) and 4-formylphenylboronic acid (0.004mol) were reacted in the presence of palladium (0.02g) as a catalyst in a ratio of 1: 4 in 80mL of toluene, and 1.66g of potassium carbonate in 20mL of water, and the two were mixed well. And reacting for 24 hours under the nitrogen atmosphere to obtain the TPE-Ph-CHO complex.
The hydrogen spectrum data thereof was substantially the same as in example 1.
Example 3 Synthesis of organic porous Material COP-1
TPE-Ph-CHO (0.1mmol) complex and hydrazine hydrate (0.1mmol) were mixed at a ratio of 1: 1 is dissolved in dioxane (4mL), added into a Pyrex glass tube, and reacted for 3 days under 373K and oxygen-free conditions after three cycles of liquid nitrogen cooling, vacuumizing and thawing by using acetic acid (2mL) as a catalyst, and filtered to obtain the organic porous material.
TPE-Ph-CHO (0.1mmol) complex and hydrazine hydrate (0.1mmol) were mixed at a ratio of 1: 1 is dissolved in benzotrifluoride (4mL), added into a Pyrex glass tube, and reacted for 3 days under 373K and oxygen-free conditions after three cycles of liquid nitrogen cooling, vacuumizing and unfreezing by using acetic acid (2mL) as a catalyst, and filtered to obtain the organic porous material, wherein the yield of the organic porous material COP-1 is 41.6%.
Example 4 Synthesis of organic porous Material COP-1
Dissolving TPE-Ph-CHO (0.05mmol) complex and hydrazine hydrate (0.1mmol) in benzotrifluoride (4mL) at a ratio of 1:2, adding the solution into a Pyrex glass tube, using acetic acid (2mL) as a catalyst, reacting for 5 days under 373K and oxygen-free conditions after three cycles of liquid nitrogen cooling, vacuumizing and unfreezing, and filtering to obtain the organic porous material, wherein the yield of COP-1 of the organic porous material is 63.2%.
Example 5 Synthesis of organic porous Material COP-1
TPE-Ph-CHO (0.05mmol) complex and hydrazine hydrate (0.1mmol) were mixed at a ratio of 1:2 is dissolved in dioxane (4mL), added into a Pyrex glass tube, and reacted for 5 days under 373K and oxygen-free conditions after three cycles of liquid nitrogen cooling, vacuumizing and unfreezing by using acetic acid (2mL) as a catalyst, and filtered to obtain the organic porous material, wherein the yield of COP-1 of the organic porous material is 74.6%.
Example 6 Infrared Spectroscopy
Infrared spectroscopy of COP-1 obtained in example 5 gave an infrared spectrum as shown in FIG. 1, curve A showing the infrared absorption spectrum at 1700cm for the monomeric TPE-Ph-CHO monomer prepared in example 1 -1 The characteristic peak of aldehyde group appears, and the curve B is that COP-1 is 1360cm -1 The characteristic peak of amido bond appears, but the characteristic peaks of two monomers do not appear, which shows that the two monomers participate in the reaction to form a novel COP-1 material connected by the amido bond.
Example 7 Infrared Spectroscopy
Thermogravimetric analysis of COP-1 obtained in example 5 revealed no weight loss at 300 ℃ and the structure began to collapse between 300 ℃ and 420 ℃ and after 420 ℃ it was fully carbonized with a structural failure and a weight loss of 80%. This indicates that the COF-1 material also has better thermal stability in air atmosphere, which provides favorable conditions for its application.
Example 8 adsorption and desorption test of Nitrogen
The organic porous material obtained in example 5 was subjected to a nitrogen adsorption/desorption test, and fig. 4 is a pore size distribution diagram of the material, and as can be seen from fig. 3, the material had a uniform pore size and a pore size distribution of about 1.4nm, and was a microporous material. Fig. 4 is an isothermal adsorption-desorption curve of the material, the origin represents the adsorption curve, and the square line represents the analytical curve. Is the characteristic of the adsorption and desorption curve of the typical microporous material. This also exactly matches the feature of COP-1 material with uniform pore size.
Example 9 fluorescence quantum yield of organic porous Material
In order to obtain PLQY of COP-1, the absolute quantum yield of fluorescence of COP-1, the organic porous material prepared in example 5, was measured by the integrating sphere method to be 13.45%.
Example 10 application of organic porous Material
The fluorescence property test was performed on the organic porous material COP-1 prepared in example 5 as follows:
FIG. 5 is a fluorescence property test spectrum of an organic porous material COP-1, wherein the excitation wavelength is 480nm, and the maximum emission wavelength is 600 nm.
Fig. 6 shows an LED device with COP-1 uniformly coated on it and capable of emitting blue light, which is energized under light and dark conditions, respectively, and the left side shows an energized blue LED lamp without coating material emitting blue light. The right picture shows that the blue LED lamp which is electrified after being coated with COP-1 organic porous material emits white light.
FIG. 7 is a CIE spectrum of COP-1. It can be seen that the COP-1 luminescence is in the yellow region and can be excited by a common blue LED lamp to produce white light.
Claims (7)
1. A tetraphenylethylene-based compound having the formula C 54 H 36 O 4 The structural formula is as follows:
2. a tetraphenylethylene-based organic porous material synthesized from the tetraphenylethylene compound of claim 1, characterized by the structural formula:
3. The tetraphenylethylene-based organic porous material of claim 2, characterized in that the maximum excitation wavelength Ex of the organic porous material is 470-490nm and the maximum emission wavelength Em is 570-590 nm.
4. The method for preparing the tetraphenylethylene-based organic porous material of claim 2 or 3, comprising dissolving the tetraphenylethylene-based compound of claim 1 and hydrazine hydrate in dioxane or mesitylene, adding into a glass tube, using acetic acid as a catalyst, reacting for 3-5 days under 373-393K and oxygen-free conditions after three liquid nitrogen cooling-vacuumizing-thawing cycles, and filtering to obtain the organic porous material.
5. The method for preparing the tetraphenylethylene-based organic porous material according to claim 4, wherein the molar ratio of the tetraphenylethylene-based compound to the hydrazine hydrate is 1: 1 to 2.
6. Use of the tetraphenylethylene-based compound of claim 1 or the tetraphenylethylene-based organic porous material of claim 2 for the preparation of white light LED materials.
7. A white LED material, characterized in that the white LED material is made of the tetraphenylethylene-based compound of claim 1 or the tetraphenylethylene-based organic porous material of claim 2.
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