CN114956973B - Organic porous material based on tetraphenyl ethylene and preparation method and application thereof - Google Patents
Organic porous material based on tetraphenyl ethylene and preparation method and application thereof Download PDFInfo
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- 239000011148 porous material Substances 0.000 title claims abstract description 55
- 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 19
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 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 15
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 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 6
- 239000000463 material Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 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 9
- 238000000034 method Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000005284 excitation Effects 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000010257 thawing Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 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 description 3
- 150000003949 imides Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 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 27
- 102000016726 Coat Protein Complex I Human genes 0.000 abstract description 26
- 108010092897 Coat Protein Complex I Proteins 0.000 abstract description 26
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 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
- 238000001179 sorption measurement Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000003795 desorption Methods 0.000 description 5
- 238000006862 quantum yield reaction Methods 0.000 description 5
- 238000012360 testing method 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
- 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
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000001228 spectrum Methods 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
- 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
- 238000004566 IR spectroscopy Methods 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
- 238000004458 analytical method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 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
- 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
- 238000003763 carbonization Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect 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
- 230000002349 favourable effect Effects 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
- 238000005286 illumination Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003446 ligand 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
- 238000011056 performance test Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229920000642 polymer Polymers 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
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic 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
Classifications
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- C—CHEMISTRY; METALLURGY
- 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
-
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G73/02—Polyamines
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1425—Non-condensed systems
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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Abstract
The invention discloses an organic porous material based on tetraphenyl ethylene, 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 solvents, reacting for 5 days in an anaerobic atmosphere at 100 ℃, filtering to obtain a yellow solid, and washing with tetrahydrofuran, methanol and ethanol for one day to obtain a target product COP-1. 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 an organic porous material based on tetraphenyl ethylene, a preparation method and application thereof.
Background
In recent years, porous materials have been widely used in various fields such as ion exchange, adsorption and separation, and guest chemistry. Therefore, the research of the porous material has basic and application research values. Porous materials are classified into three forms of porous materials, i.e., inorganic-organic hybrid and organic, according to the elemental composition of the porous material and the bonding manner. Compared with the research of inorganic porous materials and inorganic-organic porous materials, the research time of the 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 structure, light weight and the like because the organic elements consisting of the light elements are connected through covalent bonds to form the porous material.
At present, white light is realized by a white light LED light source, and the following three methods are mainly adopted: (1) white light is generated by adopting light emitting diodes with three colors of red, green and blue; (2) the blue LED is coated with yellow fluorescent powder to obtain white light; (3) and adopting near ultraviolet and ultraviolet LEDs to excite red, green and blue fluorescent powder, and mixing the three-color light to obtain white light. The first method has the greatest disadvantage of high price, which is unfavorable for commercialization development; in the third method, ultraviolet excitation is adopted, so that the energy consumption is high, the environment is not protected, and serious harm to human eyes can be caused; with these aspects in mind, the second approach has potential advantages. Most of the phosphors used in commercial use under the eyes are oxides or nitrides of rare earth metals such as europium, terbium, yttrium and the like, rare earth is extremely precious as a non-renewable resource and the price has been rising in recent years, so that it is very important to find available organic matters with better chemical stability as raw materials to prepare the phosphors.
Disclosure of Invention
The invention aims to: the invention aims to solve the technical problem of providing a novel organic porous material synthesized by a light-emitting group based on tetraphenyl ethylene, namely a novel light-emitting group-based compound (TPE-Ph-CHO), and the novel organic porous material is constructed by taking hydrazine hydrate as a connecting unit, is a high-molecular polymer, has stable chemical property and can be subjected to long-time illumination. Further expanding the breadth and depth of the luminescent material.
The invention also solves the technical problem of providing a synthetic method of the organic porous material with the tetraphenyl ethylene as the luminous core.
The invention also solves the technical problem of providing the application of the organic porous material in the aspect of emitting white LED light.
The invention selects the low-cost and easily-obtained tetraphenyl ethylene with excellent aggregation-induced emission (AIE) effect, and synthesizes the organic porous material (COP-1) with excellent luminous performance through the reaction of aldehyde group and amino group on hydrazine hydrate under the solvothermal condition, and the material has a layered three-dimensional network structure and is linked through rotatable imide chemical bonds, 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 method 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 being dependent on the amount of monomer involved in the reaction.
The invention provides TPE-Ph-CHO, which has 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
COP-1 structure is as follows:
wherein n represents a positive integer.
Wherein the synthesized organic porous material (COP-1) based on tetraphenyl ethylene as luminous core has the maximum excitation wavelength E x 470-490nm, maximum emission wavelength E m The absolute quantum yield is 13.45% at 570-590nm.
The invention also discloses a preparation method of the organic porous material (COP-1) with the tetraphenyl ethylene as the luminous core, which comprises the following steps: TPE-Ph-CHO was weighed in order, hydrazine hydrate was added to a glass tube, dioxane and o-dichlorobenzene were added as solvents to slightly dissolve them, oxygen was removed, and the mixture was heated to 100℃under a sealed condition and reacted for 5 days. After cooling to room temperature, the product was obtained as a pale yellow solid by filtration.
Wherein, the mol ratio of TPE-Ph-CHO to hydrazine hydrate is 1: the yield was highest at 2.
The invention also comprises 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 invention selects the tetrastyrene group with AIE effect, has stable structure, is an important hole conduction molecule, and has higher fluorescence performance and photoluminescence efficiency. TPE-Ph-CHO with tetraphenyl ethylene group as core is used as main ligand, and hydrazine hydrate is synthesized by solvothermal method to obtain organic porous fluorescent powder material with good blue light excitation yellow light, and the material can be found to basically meet the technical requirement of preparing white light LED by comparing with commercial YAG (Ce) material.
The beneficial effects are that: compared with the luminescent white LED reported in the prior art, the COP-1 has the following advantages:
1. the whole synthesis process does not contain heavy metal, and is linked by virtue of covalent bonds, so that the structure is firm, and the chemical property is stable.
2. The invention prepares a yellow fluorescent material by self-assembling a tetraphenyl ethylene organic ligand and hydrazine hydrate. The defects of expensive price, environment hazard rare earth metals and the like in the white light material are overcome. The synthesis method of the compound is simple, has good reproducibility, is simple and safe to operate, and provides reference for purposefully synthesizing the functional material with good fluorescence performance in future. The fluorescence performance 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 the infrared spectra of examples 3 and examples and 1;
FIG. 2 is a Thermogravimetric (TG) plot of COP-1 of example 3;
FIG. 3 is a pore size distribution diagram of example 3;
FIG. 4 is a graph of Adsorption (ADS) Desorption (DES) for nitrogen of example 3;
FIG. 5 is a solid state fluorescence spectrum of COP-1 of example 3;
FIG. 6 is a graph of the LED device prepared in example 4;
fig. 7 is a chromaticity diagram (CIE) of example 3.
The specific embodiment is as follows:
the following describes specific embodiments of the experiment, but is not meant to limit the invention.
All reagents used were purchased from the national reagent company, hydrazine hydrate was purchased from the national reagent company, and the solvents dioxane and o-dichlorobenzene were purchased from the company Ala Ding Shiji. In addition, the following description is needed:
TG/DTA test conditions: under the protection of nitrogen, the temperature rising interval is from room temperature to 700 ℃, and the temperature rising rate is 10 ℃ min -1 The method comprises the steps of carrying out a first treatment on the surface of the Fluorescence analysis testing used a spectrofluorometer FS5 fluorescence spectrometer.
EXAMPLE 1 Synthesis of the Compound TPE-Ph-CHO
Tetrakis (4-bromophenyl) ethylene (0.001 mol) and 4-formylphenylboronic acid (0.006 mol) were reacted with 1:6 in 80mL of toluene, 1.66g of potassium carbonate was dissolved in 20mL of water, and the two were thoroughly mixed. After 24h of reaction under nitrogen atmosphere, TPE-Ph-CHO complex is obtained.
Hydrogen spectrum data of the TPE-Ph-CHO complex obtained by synthesis:
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 (0.001 mol) and 4-formylphenylboronic acid (0.004 mol) were reacted with 1:4 in 80mL of toluene, 1.66g of potassium carbonate was dissolved in 20mL of water, and the two were thoroughly mixed. After 24h of reaction under nitrogen atmosphere, TPE-Ph-CHO complex is obtained.
The hydrogen spectrum data are substantially the same as those of example 1.
EXAMPLE 3 Synthesis of organic porous Material COP-1
TPE-Ph-CHO (0.1 mmol) complex and hydrazine hydrate (0.1 mmol) were combined in an amount of 1:1 was dissolved in dioxane (4 mL), added to a Pyrex glass tube, and the organic porous material was obtained by filtration under 373K and anaerobic conditions after three liquid nitrogen cooling-vacuum-thawing cycles using acetic acid (2 mL) as a catalyst.
TPE-Ph-CHO (0.1 mmol) complex and hydrazine hydrate (0.1 mmol) were combined in an amount of 1:1 is dissolved in mesitylene (4 mL), added into a Pyrex glass tube, and subjected to three liquid nitrogen cooling, vacuumizing and thawing cycles by using acetic acid (2 mL), and then reacted for 3 days under 373K and anaerobic conditions, 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
TPE-Ph-CHO (0.05 mmol) complex and hydrazine hydrate (0.1 mmol) were dissolved in mesitylene (4 mL) at a ratio of 1:2, and then added into a Pyrex glass tube, and after three liquid nitrogen cooling-vacuumizing-thawing cycles with acetic acid (2 mL) as a catalyst, the organic porous material was obtained by reacting for 5 days under 373K and anaerobic conditions and filtering, and the yield of the organic porous material COP-1 was 63.2%.
EXAMPLE 5 Synthesis of organic porous Material COP-1
TPE-Ph-CHO (0.05 mmol) complex and hydrazine hydrate (0.1 mmol) were combined in an amount of 1:2 was dissolved in dioxane (4 mL), and then added to a Pyrex glass tube, followed by three liquid nitrogen cooling-vacuum-thawing cycles using acetic acid (2 mL) as a catalyst, and then reacted under 373K and anaerobic conditions for 5 days to obtain the organic porous material by filtration, wherein the yield of the organic porous material COP-1 was 74.6%.
Example 6 Infrared Spectrometry
The COP-1 obtained in example 5 was analyzed by infrared spectrum analysis, and the obtained infrared spectrum is shown in FIG. 1, curve A shows that the infrared absorption spectrum of the monomer TPE-Ph-CHO prepared in example 1 was 1700cm -1 Characteristic peaks of aldehyde groups appear at the positions, and curve B is that COP-1 is at 1360cm -1 Characteristic peaks of amide bonds appear at the positions, but characteristic peaks of two monomers do not appear, which indicates that the two monomers participate in the reaction to form a novel COP-1 material with amide bond connection.
Example 7 Infrared Spectrometry
Thermogravimetric analysis of COP-1 obtained in example 5 revealed no weight loss at 300 ℃, initial collapse of the structure between 300 and 420 ℃, complete carbonization after 420 ℃, structural failure, 80% weight loss. This shows that the COF-1 material also has a better thermal stability under an 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 and desorption test, and as shown in fig. 4, the pore size distribution of the material was shown in fig. 3, and the material had a uniform pore size, and the pore size distribution was about 1.4nm, and was a microporous material. Fig. 4 is an isothermal adsorption-desorption curve of the material, the origin represents an adsorption curve thereof, and the square line represents an analysis curve thereof. Is typical of adsorption and desorption curve characteristics of microporous materials. This also happens to coincide with the feature of COP-1 material having a uniform pore size.
Example 9 fluorescence Quantum yield of organic porous materials
In order to obtain PLQY of COP-1, the absolute quantum yield of fluorescence of the organic porous material prepared in example 5 was measured by the integrating sphere method to be 13.45%.
Example 10 use of organic porous Material
The organic porous material COP-1 prepared in example 5 was subjected to fluorescence property test as follows:
FIG. 5 is a graph of fluorescence performance test of organic porous material COP-1, excitation wavelength of 480nm, and maximum emission wavelength of 600nm.
FIG. 6 is a graph of COP-1 uniformly coated on a blue-emitting LED device, energized under light and dark conditions, respectively, and left graph of blue light emitted from an energized blue LED lamp without a coating material. The right graph shows that the electrified blue LED lamp emits white light after being coated with the COP-1 organic porous material.
FIG. 7 is a CIE spectrum of COP-1. The COP-1 emission can be seen in the yellow region, which can be excited with a common blue LED lamp to emit white light.
Claims (6)
1. An organic porous material based on tetraphenyl ethylene, characterized in that it is synthesized from a compound of tetraphenyl ethylene having the following structure:
the structural formula of the organic porous material is as follows:wherein n represents a positive integer, the material has a layered three-dimensional network structure, and is linked by a rotatable imide chemical bond.
2. The organic porous material based on tetraphenyl ethylene according to claim 1, wherein the organic porous material has a maximum excitation wavelength Ex of 470-490nm and a maximum emission wavelength Em of 570-590nm.
3. The method for producing a tetraphenyl ethylene-based organic porous material according to claim 1 or 2, which comprisesAnd hydrazine hydrate is dissolved in dioxane or mesitylene, then added into a glass tube, and acetic acid is used as a catalyst, and after three liquid nitrogen cooling, vacuumizing and thawing cycles, the organic porous material is obtained after the reaction for 3 to 5 days under 373 to 393K and anaerobic conditions and filtration.
4. The method for preparing a tetraphenyl ethylene-based organic porous material according to claim 3, wherein the molar ratio of the tetraphenyl ethylene-based compound to the hydrazine hydrate is 1:1-2.
5. Use of the organic porous material based on tetraphenyl ethylene according to claim 1 for preparing white LED materials.
6. A white LED material, characterized in that it comprises the tetraphenyl ethylene-based organic porous material according to claim 1.
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