CN103936658A - Compound containing pyrazole structural unit, its preparation method and its application - Google Patents
Compound containing pyrazole structural unit, its preparation method and its application Download PDFInfo
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- 0 *c(cc1)cc2c1-c1ccc(*)cc1C21c2ccc3[n]c4ccccc4c3c2-c2ccccc12 Chemical compound *c(cc1)cc2c1-c1ccc(*)cc1C21c2ccc3[n]c4ccccc4c3c2-c2ccccc12 0.000 description 8
- SJLBXGPUMWFOOP-UHFFFAOYSA-N O=C(c1c2)c(cc(cc3)-[n]4c5ccccc5c5c4cccc5)c3-c1ccc2N(c1ccccc1)c1ccccc1 Chemical compound O=C(c1c2)c(cc(cc3)-[n]4c5ccccc5c5c4cccc5)c3-c1ccc2N(c1ccccc1)c1ccccc1 SJLBXGPUMWFOOP-UHFFFAOYSA-N 0.000 description 2
- MZFNMHDPOGTPDS-UHFFFAOYSA-N C=[Br]C1=CC=CC(Cc(cc(cc2)N(C3=CC=CCC3)c3ccccc3)c2-c(c(C2)c3)ccc3N(c3ccccc3)c3ccccc3)C1c1c2cccc1 Chemical compound C=[Br]C1=CC=CC(Cc(cc(cc2)N(C3=CC=CCC3)c3ccccc3)c2-c(c(C2)c3)ccc3N(c3ccccc3)c3ccccc3)C1c1c2cccc1 MZFNMHDPOGTPDS-UHFFFAOYSA-N 0.000 description 1
- JAOFZYQHEJHDCN-UHFFFAOYSA-N CC(C)(C(C)(C)OBc(cccc12)c1-c1ccccc1C21C(C=C(CC2)N(c3ccccc3)c3ccccc3)=C2c(cc2)c1cc2N(c1ccccc1)c1ccccc1)O Chemical compound CC(C)(C(C)(C)OBc(cccc12)c1-c1ccccc1C21C(C=C(CC2)N(c3ccccc3)c3ccccc3)=C2c(cc2)c1cc2N(c1ccccc1)c1ccccc1)O JAOFZYQHEJHDCN-UHFFFAOYSA-N 0.000 description 1
- YJZNEGUZNUOKTE-UHFFFAOYSA-N CC(C1)C=CC2=C1C1C(Br)=CC=CC1C21c2cc(-c3ccccc3)ccc2-c2ccccc12 Chemical compound CC(C1)C=CC2=C1C1C(Br)=CC=CC1C21c2cc(-c3ccccc3)ccc2-c2ccccc12 YJZNEGUZNUOKTE-UHFFFAOYSA-N 0.000 description 1
- RSHWGMWPGBPLHN-UHFFFAOYSA-N CC(C1)C=CC2=C1c1ccccc1C(CCc(cc1)cc(C(c3c4)=O)c1-c3ccc4N(c1ccccc1)c1ccccc1)C2 Chemical compound CC(C1)C=CC2=C1c1ccccc1C(CCc(cc1)cc(C(c3c4)=O)c1-c3ccc4N(c1ccccc1)c1ccccc1)C2 RSHWGMWPGBPLHN-UHFFFAOYSA-N 0.000 description 1
- BSZXAFXFTLXUFV-UHFFFAOYSA-N CC(c1ccccc1)c1ccccc1 Chemical compound CC(c1ccccc1)c1ccccc1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 description 1
- RNNLDSZMPHFWRN-UHFFFAOYSA-N CC1(C)OB(B2OC(C)(C)C(C)(C)C3CC2C3)OC1(C)C Chemical compound CC1(C)OB(B2OC(C)(C)C(C)(C)C3CC2C3)OC1(C)C RNNLDSZMPHFWRN-UHFFFAOYSA-N 0.000 description 1
- PDASDDSVRFSSGL-UHFFFAOYSA-N Cc(cc1C23c4cccc([Br]=C)c4-c4ccccc24)ccc1-c(cc1)c3cc1-[n]1c(cccc2)c2c2c1cccc2 Chemical compound Cc(cc1C23c4cccc([Br]=C)c4-c4ccccc24)ccc1-c(cc1)c3cc1-[n]1c(cccc2)c2c2c1cccc2 PDASDDSVRFSSGL-UHFFFAOYSA-N 0.000 description 1
- IQFMWNQKBVBYKC-UHFFFAOYSA-N Cc(cccc1)c1-c1ccccc1Br Chemical compound Cc(cccc1)c1-c1ccccc1Br IQFMWNQKBVBYKC-UHFFFAOYSA-N 0.000 description 1
- KFCGEQOCLJTOEQ-UHFFFAOYSA-N O=C(c1c2)c(cc(cc3)Br)c3-c1ccc2N(c1ccccc1)c1ccccc1 Chemical compound O=C(c1c2)c(cc(cc3)Br)c3-c1ccc2N(c1ccccc1)c1ccccc1 KFCGEQOCLJTOEQ-UHFFFAOYSA-N 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N c(cc1)cc2c1[nH]c1ccccc21 Chemical compound c(cc1)cc2c1[nH]c1ccccc21 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/96—Spiro-condensed ring systems
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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
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
Abstract
The invention discloses a compound containing a pyrazole structural unit, a preparation method and an application. A structural general formula of the compound containing the spirofluorene structural unit is shown as a formula I. The nuclear magnetic detection of the compound is correct, the compound can be used as an OLED monomer material, and has important application value. The compound has the main advantages that 1) the synthesis is relatively simple; 2) the compound has high efficiency stability and good glass transition temperature; and 3)the device produced by the OLED material has the advantages of low original voltage, high luminescence efficiency and good chromaticity coordinate.
Description
Technical field
The invention belongs to technical field of organic synthesis, relate to a kind of compound that contains carbazole structure unit and preparation method thereof and application.
Background technology
First organic electroluminescent (being called for short OLED) and relevant research have found the electro optical phenomenon of organic compound single-crystal anthracene as far back as people such as pope in 1963.A kind of amorphous membranous type device has been made by the method for evaporation organic molecule by the Kodak of the U.S. in 1987, and driving voltage has been dropped in 20V.This class device owing to thering is ultra-thin, complete solidify, luminous, brightness is high, visual angle is wide, fast response time, driving voltage is low, power consumption is little, bright in luster, contrast gradient is high, technological process is simple, good temp characteristic, can realize the advantages such as softness demonstration, can be widely used in flat-panel monitor and area source, therefore obtain studying widely, develop and used.
Through the development of twenties years, organic OLED material round Realization red, blue, green emitting, Application Areas has also expanded to the field such as polymer and metal complex from small molecules.Recent years, organic electroluminescent technique of display obtained huge progress, and it is luminous to have realized Red, Blue, Green.But at present known with practical value also very limited with materials potentiality, particularly the organic materials of overall target excellence is badly in need of development and exploitation, green and red material develops very fast, substantially can meet the demand of commercialization practicality, and the life-span of blue material is far below other bi-materials, having more problems, still have distance from practical application, is a difficult problem that all the time perplexs OLED technology.Therefore, the molecular designing of stable, high-level efficiency blue light material with become important research contents.
Summary of the invention
The object of this invention is to provide a kind of compound that contains carbazole structure unit and preparation method thereof and application.
The OLED blue light material monomeric compound that contains carbazole structure unit provided by the invention, its general structure is suc as formula shown in I,
In described formula I, R
afor R
1-(Z
1-A
1-Z
2)
x-;
R
bfor-(Z
3-A
2-Z
4)
y-R
2;
R
cfor-(Z
5-A
3-Z
6)
z-R
3;
Wherein, R
1, R
2and R
3all be selected from H ,-F ,-Cl ,-CN ,-CF
3,-OCF
3, any one in the total number of carbon atoms of the total number of carbon atoms alkyl that is 1-15, fluoro alkoxyl group that is 1-15 of alkyl that the total number of carbon atoms is 1-15, alkoxyl group that the total number of carbon atoms is 1-15, normal olefine base that the total number of carbon atoms is 2-15, fluoro and the total number of carbon atoms of fluoro normal olefine base that is 2-15;
Z
1, Z
2, Z
3, Z
4, Z
5and Z
6all be selected from-O-,-S-,-OCO-,-COO-,-CO-,-CH
2o-,-OCH
2-,-CF
2o-,-OCF
2-, at least one in the total number of carbon atoms of straight chained alkyl that the total number of carbon atoms of straight chained alkyl that the total number of carbon atoms is 1-15, normal olefine base that the total number of carbon atoms is 2-15, straight-chain alkynyl that the total number of carbon atoms is 2-15, fluoro is 1-15, fluoro be 2-15 alkylene and carbon-carbon single bond;
A
1, A
2and A
3all be selected from 1,4-cyclohexylidene, 1,4-phenylene, two phenenyl phosphinyl, 2-naphthyl, diphenylamino, N-phenyl napthyl-amido, 2,5-pyrimidyl, 3,9-carbazyl, 2,5-pyridyl, 2,5-tetrahydrochysene-2H-pyranyl, 1,3-diox-2,5-base, 1,2,4-oxadiazole-3, at least one in pyranoid ring two bases of the Isosorbide-5-Nitrae-cyclohexylidene of 5-base, fluoro, the Isosorbide-5-Nitrae-phenylene of fluoro, fluoro, cyclic lactone two bases, five yuan of oxa-ring two bases, pentatomic sulphur heterocycle two bases, penta azacyclo two bases and singly-bounds;
X, y and z are the integer of 0-3;
Described x, y or z are 2 or at 3 o'clock, structural unit Z
1-A
1-Z
2in, Z
1identical or different, A
1identical or different, Z
2identical or different; Structural unit Z
3-A
2-Z
4in, Z
3identical or different, A
2identical or different, Z
4identical or different; Structural unit Z
5-A
3-Z
6in, Z
5identical or different, A
3identical or different, Z
6identical or different.
Concrete, R
afor hydrogen atom,
R
bfor phenyl,
R
cfor
naphthyl,
Shown in described formula I, compound is specially any one in following compound:
Compound shown in described formula I is also for being prepared as follows the compound obtaining.
The method of the described formula I compound of preparation provided by the invention, comprises the steps:
PH value in reaction system is under the condition that exists as catalyzer of 8-14 and tri-butyl phosphine, palladium, by compound and R shown in formula VIII
cx carries out Hartwig linked reaction, obtains after completion of the reaction compound shown in described formula I;
Described R
cin X, X is Br or I;
Described formula VIII and R
cin X, R
a, R
b, R
cdefinition all identical with the definition in aforementioned formula I.
The reaction equation of aforesaid method is as follows:
In aforesaid method, described formula VIII compound and R
cthe mol ratio of X is 1:1～2, specifically can be 1:1.1,1:1.2,1:1.3,1:1.4,1:1.5,1:1.6,1:1.7,1:1.8,1:1.9,1:2.0, preferably 1:1.1;
The molar ratio of formula VIII compound and tri-butyl phosphine is 1:0.002～0.05, specifically can be 1:0.002,1:0.005,1:0.01,1:0.02,1:0.05, preferably 1:0.02;
The mol ratio of formula VIII compound and palladium is 1:0.001～0.01, specifically can be 1:0.001,1:0.002,1:0.003,1:0.004,1:0.005,1:0.006,1:0.007,1:0.008,1:0.009,1:0.01, preferably 1:0.005.
In actually operating, can select sodium tert-butoxide to regulate pH value to 8～14 of reaction system; The mol ratio of described formula VIII compound and sodium tert-butoxide is 1:1～2, specifically can be 1:1.1,1:1.2,1:1.3,1:1.4,1:1.5,1:1.6,1:1.7,1:1.8,1:1.9,1:2.0, preferably 1:1.3;
In described Hartwig linked reaction step, temperature is 60 DEG C～160 DEG C, specifically can be 60 DEG C～80 DEG C, 80 DEG C～100 DEG C, 100 DEG C～120 DEG C, 120 DEG C～140 DEG C, 140 DEG C～160 DEG C, preferably 120 DEG C～140 DEG C;
Reaction times is 4～12 hours, is preferably 8～10 hours.
Described Hartwig linked reaction is carried out in solvent;
Described solvent is specifically selected from least one in toluene, benzene, dimethylbenzene, ethanol, water, tetrahydrofuran (THF), hexane, acetic acid, DMF, orthodichlorobenzene and Isosorbide-5-Nitrae-dioxane.
The reaction atmosphere of described Hartwig linked reaction is inert atmosphere, preferably argon gas atmosphere.
In above-mentioned preparation method, be prepared as follows and obtain as compound shown in the formula VIII of initial reactant:
1) i works as R
a-B (OH)
2time, the pH value in reaction system is 8-14 and Pd (PPh
3)
4under the condition existing as catalyzer, by compound and R shown in formula II
a-B (OH)
2carry out Suzuki cross-coupling reaction, obtain after completion of the reaction compound shown in formula III;
Ii works as R
awhen H, the pH value in reaction system is 8-14 and Pd
2(dba)
3, S-Phos is 2-dicyclohexyl phosphorus-2 ', under the condition that 6 '-dimethoxy-biphenyl exists as catalyzer, by compound and R shown in formula II
ah carries out Hartwig linked reaction, obtains after completion of the reaction compound shown in formula III;
2) i works as R
b-B (OH)
2time, the pH value in reaction system is 8-14 and Pd (PPh
3)
4under the condition existing as catalyzer, by step 1) compound and R shown in the formula III of gained
b-B (OH)
2carry out Suzuki cross-coupling reaction, obtain after completion of the reaction compound shown in formula IV;
Ii works as R
bwhen H, the pH value in reaction system is 8-14 and Pd
2(dba)
3, S-Phos is 2-dicyclohexyl phosphorus-2 ', under the condition that 6 '-dimethoxy-biphenyl exists as catalyzer, by compound and R shown in the formula III of step 1) gained
bh carries out Hartwig linked reaction, obtains after completion of the reaction compound shown in formula IV;
3) the pH value in reaction system is 8-14,2, the two benzene of 2 '-bis-bromines carries out negative ionization with n-Butyl Lithium and reacts, react complete maintenance temperature, adding again step 2) compound shown in the formula IV of gained carries out substitution reaction, react 2 hours at 110 DEG C with hydrochloric acid more after completion of the reaction, obtain compound shown in formula V;
4) the pH value in reaction system is 8-14 and Pd (dppf) Cl
2under the condition existing as catalyzer, compound shown in the formula V of step 3) gained and duplex tetramethyl ethylene ketone boric acid ester are carried out to Suzuki cross-coupling reaction, obtain after completion of the reaction compound shown in formula VI;
5) the pH value in reaction system is 8-14 and Pd (PPh
3)
4under the condition existing as catalyzer, compound shown in the formula VI of step 4) gained and adjacent nitro bromobenzene are carried out to Suzuki cross-coupling reaction, obtain after completion of the reaction compound shown in formula VII;
6) compound shown in the formula VII of step 5) gained and triphenylphosphine are carried out to ring closure reaction, react the complete compound shown in formula VIII that obtains;
In described step 1) i, described formula II compound and R
a-B (OH)
2mol ratio be that 1:1～2 specifically can be 1:1.1,1:1.2,1:1.3,1:1.4,1:1.5,1:1.6,1:1.7,1:1.8,1:1.9,1:2.0, preferably 1:1.2; Formula II compound and Pd (PPh
3)
4molar ratio be 1:0.006～0.15, specifically can be 1:0.006,1:0.015,1:0.03,1:0.05,1:0.15, preferably 1:0.05; Selecting sodium carbonate to regulate reaction system pH is 8～14, and the mol ratio of formula II compound and sodium carbonate is 1:1～4, specifically can be 1:1,1:1.5,1:2,1:2.5,1:3,1:3.5,1:4, preferably 1:4; In described reactions steps, temperature is 60 DEG C～160 DEG C, specifically can be 60 DEG C～80 DEG C, 80 DEG C～100 DEG C, 100 DEG C～120 DEG C, 120 DEG C～140 DEG C, 140 DEG C～160 DEG C, preferably 120 DEG C～140 DEG C; Reaction times is 4～10 hours, is preferably 6～8 hours; Described solvent is selected from least one in ethanol, toluene, water and dimethylbenzene;
In step 1) ii, described formula II ' compound and R
athe mol ratio of H is that 1:1～2 specifically can be 1:1.1,1:1.2,1:1.3,1:1.4,1:1.5,1:1.6,1:1.7,1:1.8,1:1.9,1:2.0, preferably 1:1.1; Formula II ' compound and Pd
2(dba)
3molar ratio be 1:0.005～0.20, specifically can be 1:0.005,1:0.01,1:0.015,1:0.02, preferably 1:0.01; The molar ratio of formula II ' compound and S-phos is 1:0.01～0.06, specifically can be 1:0.01,1:0.02,1:0.03,1:0.04,1:0.05,1:0.06, preferably 1:0.04; Selecting sodium tert-butoxide to regulate reaction system pH is 8～14, and the mol ratio of formula II ' compound and sodium tert-butoxide is 1:1～4, specifically can be 1:1,1:1.5,1:2,1:2.5,1:3,1:3.5,1:4, preferably 1:3; In described reactions steps, temperature is 60 DEG C～160 DEG C, specifically can be 60 DEG C～80 DEG C, 80 DEG C～100 DEG C, 100 DEG C～120 DEG C, 120 DEG C～140 DEG C, 140 DEG C～160 DEG C, preferably 100 DEG C～120 DEG C; Reaction times is 4～10 hours, is preferably 6～8 hours; Described solvent is selected from least one in toluene, benzene and dimethylbenzene;
Described step 2) in i, described formula III compound and R
b-B (OH)
2mol ratio be that 1:1～2 specifically can be 1:1.1,1:1.2,1:1.3,1:1.4,1:1.5,1:1.6,1:1.7,1:1.8,1:1.9,1:2.0, preferably 1:1.2; Formula III compound and Pd (PPh
3)
4molar ratio be 1:0.006～0.15, specifically can be 1:0.006,1:0.015,1:0.03,1:0.05,1:0.15, preferably 1:0.05; Selecting sodium carbonate to regulate reaction system pH is 8～14, and the mol ratio of formula III compound and sodium carbonate is 1:1～4, specifically can be 1:1,1:1.5,1:2,1:2.5,1:3,1:3.5,1:4, preferably 1:4; In described reactions steps, temperature is 60 DEG C～160 DEG C, specifically can be 60 DEG C～80 DEG C, 80 DEG C～100 DEG C, 100 DEG C～120 DEG C, 120 DEG C～140 DEG C, 140 DEG C～160 DEG C, preferably 120 DEG C～140 DEG C; Reaction times is 4～10 hours, is preferably 6～8 hours; Described solvent is selected from least one in ethanol, toluene, water and dimethylbenzene;
Step 2) in ii, described formula III compound and R
bthe mol ratio of H is that 1:1～2 specifically can be 1:1.1,1:1.2,1:1.3,1:1.4,1:1.5,1:1.6,1:1.7,1:1.8,1:1.9,1:2.0, preferably 1:1.1; Formula II compound and Pd
2(dba)
3molar ratio be 1:0.005～0.20, specifically can be 1:0.005,1:0.01,1:0.015,1:0.02, preferably 1:0.01; The molar ratio of formula II compound and S-phos is 1:0.01～0.06, specifically can be 1:0.01,1:0.02,1:0.03,1:0.04,1:0.05,1:0.06, preferably 1:0.04; Selecting sodium tert-butoxide to regulate reaction system pH is 8～14, and the mol ratio of formula II compound and sodium tert-butoxide is 1:1～4, specifically can be 1:1,1:1.5,1:2,1:2.5,1:3,1:3.5,1:4, preferably 1:3; In described reactions steps, temperature is 60 DEG C～160 DEG C, specifically can be 60 DEG C～80 DEG C, 80 DEG C～100 DEG C, 100 DEG C～120 DEG C, 120 DEG C～140 DEG C, 140 DEG C～160 DEG C, preferably 100 DEG C～120 DEG C; Reaction times is 4～10 hours, is preferably 6～8 hours; Described solvent is selected from least one in toluene, benzene and dimethylbenzene;
In described step 3), the mol ratio of described IV compound and n-Butyl Lithium is 1:1～2, specifically can be 1:1.0,1:1.1,1:1.2,1:1.3,1:1.4,1:1.5,1:1.6,1:1.7,1:1.8,1:1.9,1:2.0, preferably 1:1.5; Formula IV compound and 2, the molar ratio of the two benzene of 2 '-bis-bromines is 1:1～2, specifically can be 1:1.0,1:1.1,1:1.2,1:1.3,1:1.4,1:1.5,1:1.6,1:1.7,1:1.8,1:1.9,1:2.0, preferably 1:1.5; In described reactions steps, negative ionization temperature of reaction is-80 DEG C～0 DEG C, specifically can be-80 DEG C～-60 DEG C ,-60 DEG C～-40 DEG C ,-40 DEG C～-20 DEG C ,-20 DEG C～0 DEG C, preferably-80 DEG C～-60 DEG C; Substitution reaction temperature is 0-120 DEG C, specifically can be 0 DEG C～30 DEG C, 30 DEG C～60 DEG C, 60 DEG C～90 DEG C, 90 DEG C～120 DEG C, preferably 90 DEG C～120 DEG C; Reaction times is 4～10 hours, is preferably 6～8 hours; Described solvent is selected from least one in tetrahydrofuran (THF), hexane, acetic acid and dimethylbenzene;
In described step 4), be 1:1～2 suc as formula the mol ratio of the compound shown in V and duplex tetramethyl ethylene ketone boric acid ester, specifically can be 1:1,1:1.1,1:1.3,1:1.5,1:1.7,1:2, preferably 1:1.1; Formula V compound and Pd (dppf) Cl
2molar ratio be 1:0.002～0.05, specifically can be 1:0.002,1:0.005,1:0.01,1:0.02,1:0.05, preferably 1:0.02; Selecting Potassium ethanoate to regulate reaction system pH is 8～14, and the molar ratio of formula V compound and Potassium ethanoate is 1:1～3, specifically can be 1:1,1:1.2,1:1.5,1:2,1:2.5,1:3, preferably 1:1.5; In described reactions steps, temperature is 60 DEG C～110 DEG C, specifically can be 60 DEG C～70 DEG C, 70 DEG C～80 DEG C, 80 DEG C～90 DEG C, 90 DEG C～100 DEG C, 100 DEG C～110 DEG C, preferably 90 DEG C～100 DEG C; Time is 2～8 hours, is preferably 4～6 hours; Described solvent be selected from toluene, benzene and DMF at least one;
In described step 5), the mol ratio of described formula VI compound and adjacent nitro bromobenzene is 1:1～2, specifically can be 1:1.1,1:1.2,1:1.3,1:1.4,1:1.5,1:1.6,1:1.7,1:1.8,1:1.9,1:2.0, preferably 1:1.1; Formula IV compound and Pd (PPh
3)
4molar ratio be 1:0.002～0.05, specifically can be 1:0.002,1:0.005,1:0.01,1:0.02,1:0.05, preferably 1:0.05; Selecting sodium carbonate to regulate reaction system pH is 8～14, and the mol ratio of formula IV compound and sodium carbonate is 1:1～4, specifically can be 1:1,1:1.5,1:2,1:2.5,1:3,1:4, preferably 1:4; In described reactions steps, temperature is 60 DEG C～160 DEG C, specifically can be 60 DEG C～80 DEG C, 80 DEG C～100 DEG C, 100 DEG C～120 DEG C, 120 DEG C～140 DEG C, 140 DEG C～160 DEG C, preferably 80 DEG C～100 DEG C; Reaction times is 4～10 hours, is preferably 6～8 hours; Described solvent is selected from least one in ethanol, toluene, water and dimethylbenzene;
In described step 6), the mol ratio of described formula VII compound and triphenylphosphine is 1:1～3, specifically can be 1:1,1:1.2,1:1.5,1:2,1:2.5,1:3, preferably 1:2.5; In described reactions steps, temperature is 80 DEG C～160 DEG C, specifically can be 80 DEG C～100 DEG C, 100 DEG C～120 DEG C, 120 DEG C～140 DEG C, 140 DEG C～160 DEG C, preferably 140 DEG C～160 DEG C; Time is 2～8 hours, is preferably 4～6 hours; Described solvent is selected from least one in toluene, orthodichlorobenzene and Isosorbide-5-Nitrae-dioxane;
The reaction equation of aforesaid method is as follows:
In addition, shown in the luminescent material that contains compound shown in the formula I that the invention described above provides and this formula I, compound, in the application of preparing in luminescent material, also belongs to protection scope of the present invention; Wherein, the fluorescent emission wavelength of described luminescent material is specially 402-408nm, is more specifically 402,404,406,408 or 404-408nm;
Compound shown in the formula I that the invention described above provides, preparing luminescent material or organic electroluminescence device or being prepared with the application in OLED and the luminescent material that contains compound shown in formula I or organic electroluminescence device or Organic Light Emitting Diode, also belongs to protection scope of the present invention; Wherein, the fluorescent emission wavelength of described luminescent material is specially 402-408nm, is more specifically 402,404,406,408 or 404-408nm;
Described organic electroluminescence device specifically can be following structure:
Formed by transparent substrate, anode, hole injection layer, hole transmission layer, organic luminous layer, electron transfer layer and cathode layer successively from the bottom to top;
Wherein, the material that forms described transparent substrate is glass or flexible substrate, and flexible substrate adopts a kind of material in polyester, polyimide compounds;
The material that forms described anode layer is inorganic materials or organic conductive polymkeric substance; Wherein, described inorganic materials is tin indium oxide (being called for short ITO), zinc oxide, stannic oxide, gold and silver or copper; Described organic conductive polymkeric substance is selected from least one in Polythiophene, polyvinylbenzenesulfonic acid sodium and polyaniline;
The material that forms described hole injection layer is TDATA;
The structural formula of described TDATA is as follows:
The material that forms described hole transmission layer is NPB;
The structural formula of described NPB is as follows:
The material that forms described organic luminous layer is compound shown in aforementioned formula I provided by the invention;
The material that forms described electron transfer layer is Alq3, Gaq3 or BPhen;
Wherein, the structural formula of Alq3, BPhen and Gaq3 is as follows successively:
The material that forms described cathode layer is selected from any one or the alloy of any two kinds of compositions or the fluorochemical of following element in following element: lithium, magnesium, silver, calcium, strontium, aluminium, indium, copper, Jin Heyin.
The thickness of described hole injection layer is 30-50nm, is specially 40nm;
The thickness of described hole transmission layer is 5-15nm, is specially 10nm;
The thickness of described organic luminous layer is 10-100nm, is specially 40nm;
The thickness of described electron transfer layer is 40-60nm, is specially 50nm;
The thickness of described cathode layer is 90-110nm, is specially 100nm.
Compound provided by the invention, nuclear-magnetism detects correct, and the OLED Blue-light emitting host material that can be used as efficient stable uses, and has important using value.Major advantage of the present invention has: 1) synthetic relatively simple; 2) there is efficient stable and good second-order transition temperature; 3) device that uses this OLED material to prepare plays the chromaticity coordinates that point voltage is low, luminous efficiency is higher, good.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described material all can obtain from open commercial sources if no special instructions.
Testing tool and method that following embodiment carries out performance test to OLED material and device are as follows:
Emission wavelength and tristimulus coordinates: use spectrum scanner PhotoResearch PR-655 test;
Current density and a bright voltage: use digital sourcemeter Keithley2420 test;
Power efficiency: use NEWPORT1931-C test.
Following embodiment 1 initial reactant 1e used is prepared as follows and obtains:
Step 1:
synthetic
In 500mL reaction flask, drop into the bromo-9-Fluorenone of 2-of 10.0mmol, the phenylo boric acid of 11.0mmol, the Pd (PPh of 0.5mmol
3)
4, the sodium carbonate of 40.0mmol and the toluene of 100mL, the ethanol of 20mL, the water of 20mL, be then heated to 140 DEG C of back flow reaction 6 hours.Add the ethyl acetate of 30mL and the water of 30mL to system, stir separatory, 30mL ethyl acetate extraction 2 times for water, 30mL saturated common salt washing 2 times for organic phase, merges organic phase, after being spin-dried for, obtains yellow solid.Cross silicagel column, sherwood oil: ethyl acetate=6:1 drip washing obtains yellow solid product, yield: 98%.
Step 2:
synthetic
In 250mL reaction flask, drop into the two benzene of 2,2 '-bis-bromines of 10.0mmol and the tetrahydrofuran (THF) of 80mL, liquid nitrogen ethanol bath is cooled to-78 DEG C.Drip the hexane solution of the n-Butyl Lithium of 10.0mmol, drip off rear maintenance-78 DEG C reaction 1 hour.Drip again the tetrahydrofuran solution 30mL of the step 1 gained compound 1a of 6.7mmol, drip off rear maintenance-78 DEG C reaction 1 hour.Slowly rise to room temperature reaction 1 hour, then add the saturated sodium bicarbonate solution of 30mL, the dichloromethane extraction of use 30mL three times, is spin-dried for to obtain yellow oil.In the round-bottomed bottle of another 250mL, add the yellow oil obtaining, then add the acetic acid stirring and dissolving of 50mL, add the concentrated hydrochloric acid of 5mL, back flow reaction 1 hour.System is cooled to room temperature, and separatory, is repeatedly washed till neutrality with the water of 50mL, and the dichloromethane extraction of 30mL three times, is spin-dried for.Cross silicagel column, sherwood oil: ethyl acetate=20:1 drip washing obtains faint yellow oily matter product, yield: 93%.
Step 3:
synthetic
In 100mL reaction flask, drop into the duplex tetramethyl ethylene ketone boric acid ester of step 2 gained compound 1b, the 11.0mmol of 10.0mmol, the Potassium ethanoate of 15.0mmol, Pd (dppf) Cl of 0.2mmol
2, then drop into the DMF of 80mL, 90 DEG C of reactions 8 hours.Add the ethyl acetate of saturated aqueous common salt and the 20mL of 20mL to system, stir separatory, 20mL ethyl acetate extraction 2 times for water, 20mL saturated common salt washing 2 times for organic phase, merges organic phase, after being spin-dried for, obtains black solid.Cross silicagel column, sherwood oil drip washing obtains faint yellow oily matter product, yield: 69%.
Step 4:
synthetic
In 250mL reaction flask, drop into the adjacent nitro bromobenzene of step 3 gained compound 1c, the 10.0mmol of 12.0mmol, the Pd (PPh of 0.5mmol
3)
4, the sodium carbonate of 40.0mmol and the toluene of 100mL, the ethanol of 20mL, the water of 20mL, be then heated to 140 DEG C of back flow reaction 6 hours.Add the ethyl acetate of 30mL and the water of 30mL to system, stir separatory, 30mL ethyl acetate extraction 2 times for water, 30mL saturated common salt washing 2 times for organic phase, merges organic phase, after being spin-dried for, obtains yellow solid.Cross silicagel column, sherwood oil: ethyl acetate=20:1 drip washing obtains yellow solid product, yield: 95%.
Step 5:
synthetic
In 100mL reaction flask, drop into the step 4 gained compound 1d of 10.0mmol, the triphenylphosphine of 25.0mmol, then drop into the orthodichlorobenzene of 30mL, 140 DEG C are reacted 4 hours.After being drained, system obtains yellow black solid.Cross silicagel column, sherwood oil: ethyl acetate=10:1 drip washing obtains yellow solid product, yield: 79%.
Embodiment 4 initial reactant 4e used is prepared as follows and obtains:
Step 1:
synthetic
In 250mL reaction flask, drop into 2 of 10.0mmol, the pentanoic of the bromo-9-Fluorenone of 7-bis-, 22.0mmol, the Pd of 0.1mmol
2(dba)
3, the S-phos of 0.5mmol, the sodium tert-butoxide of 30mmol, and then add the toluene of 80mL, 110 DEG C of reactions 6 hours.System is spin-dried for, obtains dark oil thing.Cross silicagel column, sherwood oil: methylene dichloride=5:1 drip washing obtains brown oil product, yield: 65%
Step 2:
synthetic
According to the step 2 of aforementioned preparation 1e method, 1a is replaced with to compound 4a, obtain target compound.Yield: 85%.
Step 3:
synthetic
According to the step 3 of aforementioned preparation 1e method, 1b is replaced with to this step 2 gained 4b, obtain target compound.Yield: 68%.
Step 4:
synthetic
According to the step 4 of aforementioned preparation 1e method, 1c is replaced with to this step 3 gained 4c, obtain target compound.Yield: 91%.
Step 5:
synthetic
According to the step 5 of aforementioned preparation 1e method, 1d is replaced with to this step 4 gained 4d, obtain target compound.Yield: 76%.
Following embodiment 5 initial reactant 5e used is prepared as follows and obtains:
Step 1:
synthetic
With the step 1 of aforementioned preparation 4e method
Step 2:
synthetic
According to the step 2 of aforementioned preparation 1e method, 1a is replaced with to this step 1 gained 5a, obtain target compound.Yield: 82%.
Step 3:
synthetic
According to the step 3 of aforementioned preparation 1e method, 1b is replaced with to this step 2 gained 5b, obtain target compound.Yield: 78%.
Step 4:
synthetic
According to the step 4 of aforementioned preparation 1e method, 1c is replaced with to this step 3 gained 5c, obtain target compound.Yield: 88%.
Step 5:
synthetic
According to the step 5 of aforementioned preparation 1e method, 1d is replaced with to this step 4 gained 5d, obtain target compound.Yield: 78%.
Following embodiment 6 initial reactant 6e used is prepared as follows and obtains:
Step 1:
synthetic
According to the step 1 of aforementioned preparation 4e method, pentanoic is replaced with to carbazole, obtain target compound.Yield: 76%.
Step 2:
synthetic
According to the step 2 of aforementioned preparation 1e method, 1a is replaced with to this step 1 gained 6a, obtain target compound.Yield: 87%.
Step 3:
synthetic
According to the step 3 of aforementioned preparation 1e method, 1b is replaced with to this step 2 gained 6b, obtain target compound.Yield: 77%.
Step 4:
synthetic
According to the step 4 of aforementioned preparation 1e method, 1c is replaced with to this step 3 gained 6c, obtain target compound.Yield: 89%.
Step 5:
synthetic
According to the step 5 of aforementioned preparation 1e method, 1d is replaced with to this step 4 gained 6d, obtain target compound.Yield: 75%.
Following embodiment 7 initial reactant 7e used is prepared as follows and obtains:
Step 1:
synthetic
According to the step 1 of aforementioned preparation 4e method, the consumption of pentanoic is reduced to half, obtain target compound.Yield: 70%.
Step 2:
synthetic
According to the step 1 of aforementioned preparation 4e method, bromo-2,7-bis-9-Fluorenone is replaced with to this step 1 gained compound 7a, pentanoic replaces with carbazole and consumption reduces half, obtains target compound.Yield: 74%.
Step 3:
synthetic
According to the step 2 of aforementioned preparation 1e method, 1a is replaced with to this step 2 gained 7b, obtain target compound.Yield: 92%.
Step 4:
synthetic
According to the step 3 of aforementioned preparation 1e method, 1b is replaced with to this step 3 gained 7c, obtain target compound.Yield: 77%.
Step 5:
synthetic
According to the step 4 of aforementioned preparation 1e method, 1c is replaced with to this step 4 gained 7d, obtain target compound.Yield: 88%.
Step 6:
synthetic
According to the step 5 of aforementioned preparation 1e method, 1d is replaced with to this step 5 gained 7e, obtain target compound.Yield: 80%.
Following embodiment 8 initial reactant 8e used is prepared as follows and obtains:
Step 1:
synthetic
According to the step 1 of aforementioned preparation 4e method, pentanoic is replaced with
and consumption reduces half, obtains target compound.Yield: 76%.
Step 2:
synthetic
According to the step 1 of aforementioned preparation 4e method, bromo-2,7-bis-9-Fluorenone is replaced with to this step 1 gained 8a, pentanoic replaces with carbazole and consumption reduces half, obtains target compound.Yield: 69%.
Step 3:
synthetic
According to the step 2 of aforementioned preparation 1e method, 1a is replaced with to this step 2 gained 8b, obtain target compound.Yield: 93%.
Step 4:
synthetic
According to the step 3 of aforementioned preparation 1e method, 1b is replaced with to this step 3 gained 8c, obtain target compound.Yield: 83%.
Step 5:
synthetic
According to the step 4 of aforementioned preparation 1e method, 1c is replaced with to this step 4 gained 8d, obtain target compound.Yield: 90%.
Step 6:
synthetic
According to the step 5 of aforementioned preparation 1e method, 1d is replaced with to this step 5 gained 8e, obtain target compound.Yield: 73%.
Embodiment 1, compound
preparation
In 100mL reaction flask, drop into the para-bromoanisole of step 5 gained compound 1e, the 2.2mmol of 2.0mmol, the sodium tert-butoxide of 2.6mmol, the palladium of 0.01mmol, the tri-butyl phosphine of 0.04mmol, then drop into the dimethylbenzene of 10mL, 140 DEG C were carried out Hartwig linked reaction after 8 hours, add the ethyl acetate of 20mL and the water of 20mL to system, stir separatory, 20mL ethyl acetate extraction 2 times for water, 20mL saturated common salt washing 2 times for organic phase, merge organic phase, after being spin-dried for, obtain brown solid.Cross silicagel column, sherwood oil: ethyl acetate=10:1 drip washing obtains white solid product, yield: 30%.
1H?NMR(CDCl
3,300MHz):δ=8.55(d,1H),8.09(d,1H),7.92-7.94(d,1H),7.75-7.81(m,2H),7.16-7.52(m,19H),6.99-7.01(d,2H),3.83(s,3H)；
Second-order transition temperature Tg:285 DEG C;
Uv-absorbing wavelength: 255nm, 360nm;
Fluorescent emission wavelength: 404nm.
As from the foregoing, this white solid product structure is correct, is compound shown in formula I
Embodiment 2, compound
synthetic
According to the step of embodiment 1, only para-bromoanisole is replaced with to 4-bromo biphenyl, obtain white solid product, yield: 32%.
1H?NMR(CDCl
3,300MHz):δ=8.55(d,1H),8.07-8.09(d,1H),7.92-7.94(d,1H),7.74-7.82(m,4H),7.56-7.68(m,4H),7.40-7.52(m,14H),7.31-7.36(m,2H),7.12-7.28(m,4H)。
Second-order transition temperature Tg:268 DEG C;
Uv-absorbing wavelength: 245nm, 355nm;
Fluorescent emission wavelength: 404nm.
As from the foregoing, this white solid product structure is correct, is compound shown in formula I
Embodiment 3, compound
synthetic
According to the step of embodiment 1, only para-bromoanisole used is replaced with to 2-bromonaphthalene, obtain white solid product, yield: 38%.
1H?NMR(CDCl
3,300MHz):δ=8.55(d,1H),8.09-8.10(d,1H),7.94-8.02(m,4H),7.75-7.86(m,3H),7.16-7.64(m,20H)。
Second-order transition temperature Tg:286 DEG C;
Uv-absorbing wavelength: 245nm, 330nm;
Fluorescent emission wavelength: 404nm.
As from the foregoing, this white solid product structure is correct, is compound shown in formula I
Embodiment 4, compound
synthetic
According to the step of embodiment 1, only 1e is replaced with to 4e, obtain white solid product, yield: 30%.
1H?NMR(CDCl
3,300MHz):δ=8.55(d,1H),8.09-8.12(d,1H),7.92-7.96(d,1H),7.60-7.64(d,1H),7.40-1.55(m,7H),7.15-7.35(m,11H),6.95-7.02(d,2H),6.80-6.82(m,4H),6.50-6.68(m,10H),6.37-6.40(d,2H),3.83(s,3H)。
Second-order transition temperature Tg:288 DEG C;
Uv-absorbing wavelength: 255nm, 335nm;
Fluorescent emission wavelength: 406nm.
As from the foregoing, this white solid product structure is correct, is compound shown in formula I
Embodiment 5,
synthetic
According to the step of embodiment 1, only 1e and para-bromoanisole are replaced with to 5e and 2-bromonaphthalene, obtain white solid product, yield: 36%.
1H?NMR(CDCl
3,300MHz):δ=8.55(d,1H),8.09(d,1H),7.90-8.02(m,4H),7.81-7.83(t,1H),7.58-7.63(m,3H),7.16-7.47(m,17H),6.81(m,4H),6.50-6.65(m,10H),?6.39(m,2H)。
Second-order transition temperature Tg:255 DEG C;
Uv-absorbing wavelength: 235nm, 325nm;
Fluorescent emission wavelength: 410nm.
As from the foregoing, this white solid product structure is correct, is compound shown in formula I
Embodiment 6, compound
synthetic
According to the step of embodiment 1, only 1e and para-bromoanisole are replaced with to 6e and 4-tertiary butyl bromobenzene, obtain white solid product, yield: 39%.
1H?NMR(CDCl
3,300MHz):δ=8.55(m,3H),8.06-8.13(t,3H),7.92-7.95(d,3H),7.75(d,2H),7.61-7.63(m,3H),7.42-7.52(m,7H),7.20-7.35(m,11H),7.14(d,2H),6.97-6.99(m,2H),1.35(s,9H)。
Second-order transition temperature Tg:277 DEG C;
Uv-absorbing wavelength: 255nm, 345nm;
Fluorescent emission wavelength: 402nm.
As from the foregoing, this white solid product structure is correct, is compound shown in formula I
Embodiment 7, compound
synthetic
According to the step of embodiment 1, only 1e is replaced with to 7f, obtain white solid product, yield: 38%.
1H?NMR(CDCl
3,300MHz):δ=8.55(d,2H),8.08-8.14(t,2H),7.94(d,2H),7.75(d,1H),7.60-7.64(t,2H),7.40-7.54(m,7H),7.16-7.38(m,11H),6.98-7.00(m,3H),6.81(m,2H),6.63(m,4H),6.34(s,1H),6.18(m,1H),3.83(s,3H)。
Second-order transition temperature Tg:276 DEG C;
Uv-absorbing wavelength: 245nm, 325nm;
Fluorescent emission wavelength: 406nm.
As from the foregoing, this white solid product structure is correct, is compound shown in formula I
Embodiment 8, compound
synthetic
According to the step of embodiment 1, only 1e and para-bromoanisole are replaced with to 8f and para-bromo toluene, obtain white solid product, yield: 37%.
1H?NMR(CDCl
3,300MHz):δ=8.55(d,2H),7.90-8.12(m,6H),7.75(d,1H),7.10-7.65(m,24H),6.95-6.99(m,2H),6.81(m,1H),6.63(d,2H),6.34(s,1H),6.18(d,1H),2.34(s,3H)。
Second-order transition temperature Tg:254 DEG C;
Uv-absorbing wavelength: 245nm, 335nm;
Fluorescent emission wavelength: 408nm.
As from the foregoing, this white solid product structure is correct, is compound shown in formula I
Embodiment 9, be prepared with organic electroluminescence devices OLED-1, OLED-2, OLED-3
1) by the glass substrate that has been coated with ITO conductive layer supersound process 30 minutes in clean-out system, in deionized water, rinse, in acetone/ethanol mixed solvent ultrasonic 30 minutes, under clean environment, be baked to complete drying, irradiate 10 minutes with UV-light cleaning machine, and with low energy positively charged ion bundle bombarded surface.
2) the above-mentioned ito glass substrate of handling well is placed in vacuum chamber, is evacuated to 1 × 10
-5～9 × 10
-3pa continues difference evaporation compound TDATA as hole injection layer on above-mentioned anode tunic, and evaporation speed is 0.1nm/s, and evaporation thickness is 40nm;
Wherein, the structural formula of TDATA is as follows:
3) on above-mentioned hole injection layer film, continuing evaporation NPB is hole transmission layer, and evaporation speed is 0.1nm/s, and evaporation thickness is 10nm;
Wherein, the structural formula of NPB is as follows:
4) on hole transmission layer, continue that shown in evaporation one laminar I, compound 3f is as the organic luminous layer of device, evaporation speed is 0.1nm/s, and evaporation thickness is 40nm;
5) on organic luminous layer, continue the electron transfer layer of evaporation one deck Alq3 material as device, evaporation speed is 0.1nm/s, and evaporation thickness is 50nm;
Wherein, the structural formula of Alq3 is as follows:
6) on electron transfer layer successively evaporation magnesium/ag alloy layer as the cathode layer of device, wherein the evaporation speed of magnesium/ag alloy layer is 2.0～3.0nm/s, evaporation thickness is 100nm, and magnesium and silver-colored mass ratio are 1:9, obtain device OLED-1 provided by the invention.
According to upper identical step, only compound 3f shown in step 4) compound used therefor formula I is replaced with to 6f, obtain OLED-2 provided by the invention;
According to upper identical step, only compound 3f shown in step 4) compound used therefor formula I is replaced with to 8g, obtain OLED-3 provided by the invention.
Reference examples 1, fabricate devices OLED-4
According to the step of embodiment 9, only the material of step 4) organic luminous layer used is replaced with to Alq3, obtain device OLED-4.
The performance test results of obtained device OLED-1 to OLED-4 is as shown in table 1.
The performance test results of table 1, OLED-1 to OLED-4
As from the foregoing, utilize the organic luminescent device that shown in formula I provided by the invention, compound is made, play bright voltage is low, power efficiency is high, good chromaticity coordinates, and illuminant colour is mazarine, in OLED blue light material, there is important using value.
Although describe the present invention in conjunction with the preferred embodiments, but the present invention is not limited to above-described embodiment, should be appreciated that under the guiding of the present invention's design, those skilled in the art can carry out various amendments and improvement, and claims have been summarized scope of the present invention.
Claims (10)
1. compound shown in formula I:
In described formula I, R
afor R
1-(Z
1-A
1-Z
2)
x-;
R
bfor-(Z
3-A
2-Z
4)
y-R
2;
R
cfor-(Z
5-A
3-Z
6)
z-R
3;
Wherein, R
1, R
2and R
3all be selected from H ,-F ,-Cl ,-CN ,-CF
3,-OCF
3, any one in the total number of carbon atoms of the total number of carbon atoms alkyl that is 1-15, fluoro alkoxyl group that is 1-15 of alkyl that the total number of carbon atoms is 1-15, alkoxyl group that the total number of carbon atoms is 1-15, normal olefine base that the total number of carbon atoms is 2-15, fluoro and the total number of carbon atoms of fluoro normal olefine base that is 2-15;
Z
1, Z
2, Z
3, Z
4, Z
5and Z
6all be selected from-O-,-S-,-OCO-,-COO-,-CO-,-CH
2o-,-OCH
2-,-CF
2o-,-OCF
2-, at least one in the total number of carbon atoms of straight chained alkyl that the total number of carbon atoms of straight chained alkyl that the total number of carbon atoms is 1-15, normal olefine base that the total number of carbon atoms is 2-15, straight-chain alkynyl that the total number of carbon atoms is 2-15, fluoro is 1-15, fluoro be 2-15 alkylene and carbon-carbon single bond;
A
1, A
2and A
3all be selected from 1,4-cyclohexylidene, 1,4-phenylene, two phenenyl phosphinyl, 2-naphthyl, diphenylamino, N-phenyl napthyl-amido, 2,5-pyrimidyl, 3,9-carbazyl, 2,5-pyridyl, 2,5-tetrahydrochysene-2H-pyranyl, 1,3-diox-2,5-base, 1,2,4-oxadiazole-3, at least one in pyranoid ring two bases of the Isosorbide-5-Nitrae-cyclohexylidene of 5-base, fluoro, the Isosorbide-5-Nitrae-phenylene of fluoro, fluoro, cyclic lactone two bases, five yuan of oxa-ring two bases, pentatomic sulphur heterocycle two bases, penta azacyclo two bases and singly-bounds;
X, y and z are the integer of 0-3;
Described x, y or z are 2 or at 3 o'clock, structural unit Z
1-A
1-Z
2in, Z
1identical or different, A
1identical or different, Z
2identical or different; Structural unit Z
3-A
2-Z
4in, Z
3identical or different, A
2identical or different, Z
4identical or different; Structural unit Z
5-A
3-Z
6in, Z
5identical or different, A
3identical or different, Z
6identical or different.
2. compound according to claim 1, is characterized in that: in described formula I, and R
afor hydrogen atom,
R
bfor phenyl,
R
cfor
naphthyl,
Shown in described formula I, compound is specially any one in following compound:
3. a method of preparing compound shown in the arbitrary described formula I of claim 1 or 2, comprises the steps:
PH value in reaction system is under the condition that exists as catalyzer of 8-14 and tri-butyl phosphine, palladium, by compound and R shown in formula VIII
cx carries out Hartwig linked reaction, obtains after completion of the reaction compound shown in described formula I;
Described R
cin X, X is Br or I;
Described formula VIII and R
cin X, R
a, R
b, R
cdefinition all identical with claim 1.
4. method according to claim 3, is characterized in that: described formula VIII compound and R
cthe mol ratio of X is 1:1～2, preferably 1:1.1;
The molar ratio of formula VIII compound and tri-butyl phosphine is 1:0.002～0.05, preferably 1:0.02;
The mol ratio of formula VIII compound and palladium is 1:0.001～0.01, preferably 1:0.005.
5. according to the arbitrary described method of claim 3-4, it is characterized in that: in described Hartwig linked reaction step, temperature is 60 DEG C～160 DEG C, preferably 120 DEG C～140 DEG C;
Reaction times is 4～12 hours, is preferably 8～10 hours.
6. according to the arbitrary described method of claim 3-5, it is characterized in that: described Hartwig linked reaction is carried out in solvent;
Described solvent is specifically selected from least one in toluene, benzene, dimethylbenzene, ethanol, water, tetrahydrofuran (THF), hexane, acetic acid, DMF, orthodichlorobenzene and Isosorbide-5-Nitrae-dioxane.
7. according to the arbitrary described method of claim 3-6, it is characterized in that: the reaction atmosphere of described Hartwig linked reaction is inert atmosphere, preferably argon gas atmosphere.
8. compound shown in the arbitrary described formula I of claim 1 or 2 is preparing luminescent material or organic electroluminescence device or be prepared with the application in OLED;
Wherein, the fluorescent emission wavelength of described luminescent material is specially 402-408nm.
9. contain luminescent material or organic electroluminescence device or the Organic Light Emitting Diode of compound shown in the arbitrary described formula I of claim 1 or 2;
Wherein, the fluorescent emission wavelength of described luminescent material is specially 402-408nm.
10. application according to claim 8 or organic electroluminescence device claimed in claim 9, is characterized in that:
Described organic electroluminescence device is made up of transparent substrate, anode, hole injection layer, hole transmission layer, organic luminous layer, electron transfer layer and cathode layer from the bottom to top successively;
Wherein, the material that forms described transparent substrate is glass or flexible substrate;
The material that forms described anode layer is inorganic materials or organic conductive polymkeric substance; Wherein, described inorganic materials is tin indium oxide, zinc oxide, stannic oxide, gold and silver or copper; Described organic conductive polymkeric substance is selected from least one in Polythiophene, polyvinylbenzenesulfonic acid sodium and polyaniline;
The material that forms described hole injection layer is TDATA;
The structural formula of described TDATA is as follows:
The material that forms described hole transmission layer is NPB;
The structural formula of described NPB is as follows:
The material that forms described organic luminous layer is compound shown in formula I described in claim 1;
The material that forms described electron transfer layer is Alq3, Gaq3 or BPhen;
Wherein, the structural formula of Alq3, BPhen and Gaq3 is as follows successively:
The material that forms described cathode layer is selected from any one or the alloy of any two kinds of compositions or the fluorochemical of following element in following element: lithium, magnesium, silver, calcium, strontium, aluminium, indium, copper, Jin Heyin;
The thickness of described hole injection layer is 30-50nm, is specially 40nm;
The thickness of described hole transmission layer is 5-15nm, is specially 10nm;
The thickness of described organic luminous layer is 10-100nm, is specially 40nm;
The thickness of described electron transfer layer is 40-60nm, is specially 50nm;
The thickness of described cathode layer is 90-110nm, is specially 100nm.
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| US10450269B1 (en) | 2013-11-18 | 2019-10-22 | Global Blood Therapeutics, Inc. | Compounds and uses thereof for the modulation of hemoglobin |
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| CN114805796A (en) * | 2022-03-08 | 2022-07-29 | 武汉大学 | Two-dimensional strong-fluorescence polyaniline material with metal ion detection performance and preparation method thereof |
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