CN113105484A - Green light material and preparation method and application thereof - Google Patents
Green light material and preparation method and application thereof Download PDFInfo
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- CN113105484A CN113105484A CN202110263241.5A CN202110263241A CN113105484A CN 113105484 A CN113105484 A CN 113105484A CN 202110263241 A CN202110263241 A CN 202110263241A CN 113105484 A CN113105484 A CN 113105484A
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 8
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical group C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 28
- 239000011701 zinc Substances 0.000 claims description 14
- -1 5-styryl-8-hydroxyquinoline Chemical compound 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 150000004795 grignard reagents Chemical class 0.000 claims description 9
- JGOBHUWKRDXZEY-UHFFFAOYSA-N 5-(chloromethyl)quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=C(CCl)C2=C1 JGOBHUWKRDXZEY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007818 Grignard reagent Substances 0.000 claims description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229960003540 oxyquinoline Drugs 0.000 claims description 7
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229920002866 paraformaldehyde Polymers 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 230000005284 excitation Effects 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 238000010464 Blanc reaction Methods 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 abstract description 7
- 125000005504 styryl group Chemical group 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 230000021615 conjugation Effects 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- DLJHXMRDIWMMGO-UHFFFAOYSA-N quinolin-8-ol;zinc Chemical compound [Zn].C1=CN=C2C(O)=CC=CC2=C1.C1=CN=C2C(O)=CC=CC2=C1 DLJHXMRDIWMMGO-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YYSAQRFXEUTRAR-UHFFFAOYSA-N 5-ethenylquinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=C(C=C)C2=C1 YYSAQRFXEUTRAR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- GNHGQOQUCKGFCV-UHFFFAOYSA-N quinolin-8-ol;zinc Chemical compound [Zn].C1=CN=C2C(O)=CC=CC2=C1 GNHGQOQUCKGFCV-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
- C07D215/24—Oxygen atoms attached in position 8
- C07D215/26—Alcohols; Ethers thereof
- C07D215/30—Metal salts; Chelates
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- C—CHEMISTRY; METALLURGY
- 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
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
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- C—CHEMISTRY; METALLURGY
- 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
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
Abstract
The invention belongs to the technical field of luminescent materials, and discloses a green light material, and a preparation method and application thereof. The green light material has the following structural formula:
according to the invention, 5-bit of the 8-hydroxyquinoline structure is modified, a styryl structure is introduced, and the introduced styryl group can generate pi-pi conjugation with the 8-hydroxyquinoline structure, so that the electron cloud density of the 8-hydroxyquinoline structure is reduced; simultaneously, Zn is selected by selecting metal ions2+WherebyCompared with the traditional 8-hydroxyquinoline aluminum, the obtained new green light material has stronger electron transmission performance, red shift of emission wavelength and wavelength adjustment, and can further meet the requirements of color display. Moreover, the green light material provided by the invention has good thermal stability and high color purity, and is a novel high-quality green light material.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a green light material, and a preparation method and application thereof.
Background
The research on organic electroluminescent devices using organic light emitting materials as the material of the emission layer has attracted more and more attention. 8-hydroxyquinoline aluminum is an important substance used as a material of a light-emitting layer in an electroluminescent device, and 8-hydroxyquinoline aluminum has the advantages of high glass transition temperature, good electron transport property, capability of obtaining a flawless film by a vacuum evaporation method and the like, and is always widely regarded by the academic and industrial fields of research on organic electroluminescent devices. The 8-hydroxyquinoline aluminum can almost meet the requirements of organic devices on materials, and is an uncommon electroluminescent material. However, the electroluminescent wavelength range of 8-hydroxyquinoline aluminum is still limited, and the requirement of color display cannot be completely met.
Therefore, it is desirable to provide a new green material with different emission wavelengths.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a green light material which can adjust the wavelength and further meet the requirements of color display.
Specifically, the green light material has a structural formula shown in formula (1):
preferably, the green material has an emission wavelength of 522nm at an excitation wavelength of 286 nm.
The invention also provides a preparation method of the green light material, which comprises the following steps:
8-hydroxyquinoline and paraformaldehyde are taken as raw materials, 5-styryl-8-hydroxyquinoline ligand is synthesized through Blanc chloromethylation reaction and nucleophilic addition reaction of aldehyde group, and then the 5-styryl-8-hydroxyquinoline ligand and Zn are reacted2+And (4) coordinating to obtain the green light material.
Specifically, the preparation method of the green light material comprises the following steps:
(1) mixing 8-hydroxyquinoline, paraformaldehyde and hydrochloric acid, carrying out a first heating reaction, and filtering to obtain a precipitate to obtain 5-chloromethyl-8-hydroxyquinoline;
(2) adding magnesium into the 5-chloromethyl-8-hydroxyquinoline prepared in the step (1) to prepare a Grignard reagent;
(3) weighing the Grignard reagent prepared in the step (2), benzaldehyde and K2CO3Mixing with a solvent A, carrying out a second heating reaction, and filtering to obtain a precipitate to obtain 5-styryl-8-hydroxyquinoline;
(4) adding a solvent B into the 5-styryl-8-hydroxyquinoline prepared in the step (3), dissolving, and then adding Zn2+The solution is heated for the third time for reaction, the pH value is adjusted, and the precipitate is obtained by filtration, thus obtaining the green light material.
Preferably, the temperature of the first heating reaction in the step (1) is 70-90 ℃, and the time of the first heating reaction is 6-10 h; further preferably, the temperature of the first heating reaction in the step (1) is 75-85 ℃, and the time of the first heating reaction is 6-10 h.
Preferably, the concentration of the hydrochloric acid in the step (1) is 36-38%.
Preferably, the solvent a in step (3) is an organic solvent, and more preferably, the solvent a in step (2) is Dimethylformamide (DMF).
Preferably, the temperature of the second heating reaction in the step (3) is 110-; further preferably, the temperature of the second heating reaction in the step (3) is 120-130 ℃, and the time of the second heating reaction is 25-30 h.
Preferably, the solvent B in step (4) is a mixed solution of alcohol and water; further preferably, the alcohol is ethanol.
Preferably, the Zn is contained in the step (4)2+The solution of (a) is at least one selected from a zinc acetate solution, a zinc chloride solvent, a zinc nitrate solution or a zinc sulfate solution; further preferably, the Zn is contained in the step (4)2+The solution of (a) is a zinc acetate solution.
Preferably, the temperature of the third heating reaction in the step (4) is 40-60 ℃, and the time of the third heating reaction is 20-60 min; further preferably, the temperature of the third heating reaction in the step (4) is 45-55 ℃, and the time of the third heating reaction is 30-45 min.
Preferably, the pH value in step (4) is 4 to 6, and more preferably, the pH value in step (4) is 5 to 6.
More specifically, the preparation method of the green light material comprises the following steps:
(1) weighing 8-hydroxyquinoline, paraformaldehyde and hydrochloric acid, adding into a three-necked flask, heating to 70-90 ℃, reacting for 6-10h under magnetic stirring, stopping reaction, standing, cooling, performing suction filtration, washing with acetone for 3-4 times, and vacuum drying at 60-90 ℃ to obtain yellow powdery solid, thus obtaining 5-chloromethyl-8-hydroxyquinoline;
(2) adding anhydrous ether into the 5-chloromethyl-8-hydroxyquinoline, dissolving, and adding magnesium to prepare a Grignard reagent;
(3) weighing a Grignard reagent, benzaldehyde and K2CO3, adding into a three-neck flask, adding a solvent, magnetically stirring, heating by an electrothermal sleeve, refluxing, and reacting at the temperature of 110-; after reaction, standing and cooling; carrying out vacuum drying on the green product obtained by suction filtration; obtaining green solid, and recrystallizing with 95% ethanol to obtain green powder 5-styryl-8-hydroxyquinoline;
(4) dissolving 5-styryl-8-hydroxyquinoline in mixed solution of ethanol and water, and dropwise adding Zn-containing solution2+Heating the solution to 40-60 ℃, stirring for 20-60min, adjusting the pH value to 4-6, separating out a light yellow precipitate, performing suction filtration, washing with water, and recrystallizing with 95% ethanol to obtain the green-light material.
The invention also provides a light-emitting layer comprising the green light material.
The invention also provides a light emitter comprising the green light material or the light emitting layer.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, 5-bit of the 8-hydroxyquinoline structure is modified, a styryl structure is introduced, and the introduced styryl group can generate pi-pi conjugation with the 8-hydroxyquinoline structure, so that the electron cloud density of the 8-hydroxyquinoline structure is reduced; by simultaneous selection of metal ionsSelecting Zn2+Compared with the traditional 8-hydroxyquinoline aluminum, the obtained new green light material has stronger electron transmission performance, red shift of emission wavelength, wavelength adjustment and capability of further meeting the requirements of color display. Moreover, the green light material provided by the invention has good thermal stability and high color purity, and is a novel high-quality green light material.
Drawings
FIG. 1 is a diagram showing a process for preparing a green emitting material in example 1;
FIG. 2 is a fluorescence spectrum of the green light material obtained in example 1;
FIG. 3 is a graph showing the thermal performance test of the green material prepared in example 1.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1
A green light material has the following structural formula:
a method for preparing green light material comprises the following steps (preparation steps are shown in figure 1):
(1) installing an electromagnetic stirrer and a water bath heating device, weighing 8.00g of 8-hydroxyquinoline, 1.6g of paraformaldehyde and 16ml of concentrated hydrochloric acid (36%) in a 250ml three-neck flask, heating to 80 ℃, reacting for 8 hours under magnetic stirring, stopping reaction, standing, cooling, performing suction filtration, washing for 3-4 times with acetone, and performing vacuum drying at 80 ℃ to obtain a yellow powdery solid which is recorded as an intermediate CMQ (5-chloromethyl-8-hydroxyquinoline). It was weighed to a mass of 5.61g, yield 87% and its melting point was determined to be 92 ℃.
Of intermediate CMQ1HNMR data are as follows:1HNMR(300MHz，DMSO-d6) (ii) a δ — 9.30(d, 1H, J ═ 7.5Hz), 9.0(d, 1H, J ═ 8Hz), 8.5(m, 2H), 7.05(m, 2H), 7.75(d, 1H, J ═ 7.8Hz), 7.51(d, 1H, J ═ 6Hz), 3.98(s, 1H), 4.93(s, 2H); elemental analysis (%): c, 62.01; h, 4.18; and N, 7.26. Calculated value (C)10H8ClNO，％)：C，62.03；H，4.16；N，7.23；EI/MS(m/z)193(M+)。
(2) Taking 5g of 5-chloromethyl-8-hydroxyquinoline, adding 20mL of anhydrous ether, dissolving, adding 1g of magnesium, and reacting to obtain a Grignard reagent (CMGQ);
(3) 3g of Grignard reagent (CMGQ), 2.7g of benzaldehyde, 1.78g K were weighed out2CO3Charging into a 150ml three-neck flask, adding 50ml DMF, magnetically stirring, heating with an electrothermal sleeve, refluxing, and reacting for 26h while maintaining the temperature at 125 ℃. After the reaction, the mixture is kept stand and cooled. And carrying out vacuum drying on the green product obtained by suction filtration. The green solid was obtained and recrystallized from 95% ethanol to give 5-styryl-8-hydroxyquinoline as a green powder, which was noted as intermediate SQ and the melting point was determined to be 119 ℃.
Of intermediate SQ1HNMR data are as follows:1HNMR(300MHz，CDCl3): δ — 9.03(d, 1H, J ═ 9Hz), 9.12(d, 1H, J ═ 9Hz), 8.13-8.05(m, 1H), 7.75(d, 1H, J ═ 9Hz), 7.51(m, 1H, J ═ 5.6Hz), 6.78(m, 1H, J ═ 7.6Hz), 5.53(s, 1H); elemental analysis (%): c, 82.57; h, 5.29; n, 5.68; calculated value (C)17H13NO)：C，82.57；H，5.30；N，5.66；EI MS(m/z)247(M+)。
(4) Dissolving 2g of 5-vinyl-8-hydroxyquinoline (intermediate SQ) in 16ml of a mixed solution of ethanol and water in a 50ml beaker, dropwise adding a zinc acetate aqueous solution, heating to 50 ℃, stirring for 40 minutes, adjusting the pH to 5-6 with a 10% sodium carbonate solution, precipitating a light yellow precipitate, carrying out suction filtration, washing with water, recrystallizing with 95% ethanol to obtain a powdery green-light material (5-vinyl-8-hydroxyquinoline zinc complex) recorded as Zn (SQ)2The melting point was measured to be 201 ℃.
Zn(SQ)2Is/are as follows1HNMR data are as follows:1HNMR(300MHz，CDCl3): δ is 8.83(d, 1H, J is 7.7Hz), 8.32(d, 1H, J is 8.1Hz), 7.52(m, 1H), 8.18(d, 1H, J is 8.5Hz), 7.71(d, 1H, J is 5.1Hz), 7.38(m, 1H, J is 7.4Hz), 7.23(m, 1H); 6.78(d, 1H, J ═ 5.0 Hz); 6.56(d, 1H, J ═ 4.8 Hz); elemental analysis (%): c, 73.17; h, 4.36; n, 5.05; calculated value (C)51H36AlN3O3)：C，73.19；H，4.34；N，5.02；EI MS(m/z)558(M+)。
Product effectiveness testing
(1) Wavelength determination
The green light material (Zn (SQ)) prepared in the present invention was measured at an excitation wavelength of 286nm using a fluorescence spectrophotometer2) At a wavelength of (2) and as a zinc 8-hydroxyquinoline complex (ZnQ)2) As a comparison, as can be seen from FIG. 2, the green material provided by the invention has an emission wavelength of 522nm, which is comparable to that of 8-hydroxyquinoline zinc complex (ZnQ)2) The emission wavelength of 518nm needs to be red-shifted by 4nm, and compared with the emission wavelength of 6nm of the classical 8-hydroxyquinoline aluminum complex (516nm), the emission wavelength of the red-shifted aluminum complex achieves the purpose of adjusting the wavelength and can further meet the requirements of color display.
Meanwhile, as can be seen from FIG. 2, the green light material (Zn (SQ))2) And 8-hydroxyquinoline zinc complex (ZnQ)2) All emit better green light, but the green light material (Zn (SQ))2) Compared with the 8-hydroxyquinoline zinc complex, the green light material (Zn (SQ))2) Can adjust the wavelength of 8-hydroxyquinoline, has good luminous chromaticity and narrow half-peak width, and is a high-quality novel green light material.
(2) Thermal performance testing
For the green material (Zn (SQ) prepared by the invention2) Thermogravimetric analysis was carried out, and it can be seen from FIG. 3 that a downward slope of a curve appears around 200 ℃ and the green-emitting material (Zn (SQ))2) The temperature at about 10% weight loss was 201 ℃. The green light material has better thermal stability.
Claims (10)
1. A green light material is characterized in that the structural formula of the green light material is shown as formula (1):
2. the green material of claim 1, wherein the green material has an emission wavelength of 522nm at an excitation wavelength of 286 nm.
3. The method for preparing a green-emitting material according to claim 1 or 2, comprising the steps of:
8-hydroxyquinoline and paraformaldehyde are taken as raw materials, 5-styryl-8-hydroxyquinoline ligand is synthesized through Blanc chloromethylation reaction and nucleophilic addition reaction of aldehyde group, and then the 5-styryl-8-hydroxyquinoline ligand and Zn are reacted2+And (4) coordinating to prepare the green light material.
4. The method of claim 3, comprising the steps of:
(1) mixing 8-hydroxyquinoline, paraformaldehyde and hydrochloric acid, carrying out a first heating reaction, and filtering to obtain a precipitate to obtain 5-chloromethyl-8-hydroxyquinoline;
(2) adding magnesium into the 5-chloromethyl-8-hydroxyquinoline prepared in the step (1) to prepare a Grignard reagent;
(3) weighing the Grignard reagent prepared in the step (2), benzaldehyde and K2CO3Mixing with a solvent A, carrying out a second heating reaction, and filtering to obtain a precipitate to obtain 5-styryl-8-hydroxyquinoline;
(4) adding a solvent B into the 5-styryl-8-hydroxyquinoline prepared in the step (3), dissolving, and then adding Zn2+The solution is heated for the third time for reaction, the pH value is adjusted, and the precipitate is obtained by filtration, thus obtaining the green light material.
5. The method according to claim 4, wherein the temperature of the first heating reaction in the step (1) is 70 to 90 ℃ and the time of the first heating reaction is 6 to 10 hours.
6. The method as claimed in claim 4, wherein the temperature of the second heating reaction in step (3) is 110-130 ℃, and the time of the second heating reaction is 20-30 h.
7. The production method according to claim 4, wherein the Zn is contained in the step (4)2+The solution of (a) is selected from at least one of a zinc acetate solution, a zinc chloride solvent, a zinc nitrate solution or a zinc sulfate solution.
8. The method according to claim 4, wherein the temperature of the third heating reaction in the step (4) is 40 to 60 ℃ and the time of the third heating reaction is 20 to 60 min.
9. A light-emitting layer comprising the green light-emitting material according to claim 1 or 2.
10. A light-emitting device comprising the green light-emitting material according to claim 1 or the light-emitting layer according to claim 9.
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| JPH1053759A (en) * | 1996-08-12 | 1998-02-24 | Toyo Ink Mfg Co Ltd | Organic electroluminescent element material and organic electroluminescent element prepared therefrom |
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| JPH1053759A (en) * | 1996-08-12 | 1998-02-24 | Toyo Ink Mfg Co Ltd | Organic electroluminescent element material and organic electroluminescent element prepared therefrom |
| CN107721921A (en) * | 2017-11-13 | 2018-02-23 | 广州工程技术职业学院 | A kind of new 8 hydroxyquinoline aluminum green light material of Wavelength tunable and preparation method thereof |
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