CN101225298A - Hole-transporting type blue luminescent material as well as preparation and uses thereof - Google Patents
Hole-transporting type blue luminescent material as well as preparation and uses thereof Download PDFInfo
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- CN101225298A CN101225298A CNA2007100628330A CN200710062833A CN101225298A CN 101225298 A CN101225298 A CN 101225298A CN A2007100628330 A CNA2007100628330 A CN A2007100628330A CN 200710062833 A CN200710062833 A CN 200710062833A CN 101225298 A CN101225298 A CN 101225298A
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Abstract
The invention relates to a hole-transporting blue color compound, which is a fluorine derivative based on 9, 9-bi-(4-(bi-p-methypheny) aminophenyl). The preparation method is to first mix 9, 9-bi-[4-(N, N-bi-p-toluidine) phenyl]-2-dibromofluorine and boric acid pinacol ester of conjugate radicle, or to mix 9, 9-bi-[4-(N, N-bi-p-tolyl-amino) phenyl] fluorine -2, 7-bi-boric acid pinacol ester and bromide of conjugate radicle; and then add in toluene, potash solution, aliquat336 and catalyst tetrakis (triphenylphosphine) palladium, and heat and reflow for 10 to 30 hours in nitrogen environment; when the reaction is done, decompress, remove the solution and get the target product, the derivative based on 9, 9-bi-(4-(bi-p-methypheny) aminophenyl) fluorine substituted by unilateral conjugate radical. The compound can be used as the hole-transporting layer and the luminescent layer as well in electroluminescent devices.
Description
Technical field
The present invention relates to a kind of hole-transporting type blue luminescent material.
The invention still further relates to the preparation method of above-mentioned luminescent material.
The invention still further relates to of the application of above-mentioned luminescent material in the electroluminescent field.
Background technology
Organic Light Emitting Diode (OLEDs) has been obtained swift and violent development so far since 1987 report (C.W.Tang, S.A.VanSlyke, Appl.Phys.Lett.1987,51,913).Need the redgreenblue luminescent material as demonstration and illumination, wherein blue light material is particularly important, because the light of other color can be converted to by the following of blue light.The green glow of excellent property and red light material are by wide coverage, but the blue light material of excellent property still remains to be developed.The energy gap width of blue light material is bigger, need be doped to blue light material when the preparation blue luminescent device usually and improve the shortcoming that its current carrier injects and transmission is poor in some material of main parts, but can make preparation of devices complicated like this.In order to simplify preparation process, press for the blue luminescent device that uses the blue light material of being convenient to current carrier injection and transmission to prepare non-doping type.Trianilino group has good hole and injects and transmittability, and fluorene group also has good cavity transmission ability (Inada, H.Shirota, Y.J.Mater.Chem.1993,3,319; Pei, Q.Yang, Y.J.Am.Chem.Soc.1996,118,7416.), we have prepared a class by the change substituting group based on above-mentioned factor has better hole to inject and the transmittability blue emitting material.
Summary of the invention
The object of the present invention is to provide a kind of hole-transporting type blue luminescent material.
Another purpose of the present invention is to provide a kind of method for preparing above-mentioned luminescent material.
For achieving the above object, hole-transporting type blue light compound provided by the invention, for based on 9, the derivative of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes, its structure as shown in Equation 1:
Formula 1
Wherein R, R ' group are hydrogen atom or the conjugation group with big conjugation degree, and R, R ' group can be the same or different;
When a group is arranged among R ' and the R for-H, be referred to as that monolateral conjugation group replaces 9, the derivative of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes; When R ' and R be-during H, be referred to as 9 of bilateral conjugation group replacement, the derivative of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes.
Described hole-transporting type blue light compound, wherein the conjugation group is phenyl, anthryl, pyrenyl, aromatic amino or their combination.
Monolateral conjugation group replaces in the above-mentioned hole-transporting type blue light of the preparation provided by the invention compound 9, the method for the derivative of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes:
With 9,9-two [4-(N, N-two para-totuidine bases) phenyl]-boric acid of 2-bromine fluorenes and conjugation group any ester in molar ratio 1～2 frequently: 1 mixes, add toluene 50～100mL, concentration is aliquat336, the catalyzer tetrakis triphenylphosphine palladium of solution of potassium carbonate 10～30mL, the 0.05～0.5mL of 2.0M, under nitrogen atmosphere reflux 10-30 hour; After reaction finished, removal of solvent under reduced pressure obtained 9 of the monolateral conjugation group replacement of target product, the derivative of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes.
Described method, wherein where ester is the boric acid of conjugation group frequently: pyrene boric acid is which ester, 10-benzene anthracene-which ester of 9-boric acid frequency or 10-(4-hexichol aminocarbonyl phenyl) anthracene-which ester of 9-boric acid frequency frequently.
Described method, wherein, the target product methylene dichloride: sherwood oil=make eluant at 1: 9, silica gel column chromatography is purified.
Bilateral conjugation group replaces in the above-mentioned hole-transporting type blue light of the preparation provided by the invention compound 9, the method for the derivative of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes:
With 9,9-two [4-(N, N-two para-totuidine bases) phenyl] fluorenes-2, the 7-hypoboric acid is the bromide in molar ratio 2～3 of which ester and conjugation group frequently: 1 mixes, add toluene 50～100mL, concentration is aliquat336, the catalyzer tetrakis triphenylphosphine palladium of solution of potassium carbonate 5～30mL, the 0.05～0.5mL of 2.0M, under nitrogen atmosphere reflux 10-30 hour; After reaction finished, removal of solvent under reduced pressure obtained 9 of the bilateral conjugation group replacement of target product, 9-two (4-(two-p-methylphenyl) aminophenyl) fluorene derivatives.
Described method, wherein, the bromide of conjugation group is: bromo pyrene, 9-bromo-10-benzene anthracene, or 4-(10-bromine anthracene-9-yl)-N, N-phenylbenzene aniline.
Described method, wherein, target product adds the methylene dichloride dissolving, remove inorganic salt with saturated NaCl solution extraction, the organic phase anhydrous magnesium sulfate drying, filtrate filtered is removed with rotary evaporation and is desolvated, use methylene dichloride: sherwood oil=make eluant at 1: 9, silica gel column chromatography is purified.
The application of hole-transporting type blue light compound provided by the invention in the preparation luminescent device prepares luminescent device by following structure:
ITO/ compound/TNS/Alq
3/ LiF/Al
Wherein anode is with tin indium oxide (ITO) glass, and negative electrode is with aluminium (Al), and compound is meant 9 of claim 1, and the derivative of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes, TNS are meant that β-four naphthyl silane is as hole blocking layer, Alq
3Be meant oxine aluminium as electron transfer layer, lithium fluoride (LiF) is used for modifying negative electrode.
Described application, wherein compound is with the method film forming of vacuum evaporation or solution spin coating, and other material is all used the method film forming of vacuum evaporation.
Among the preparation method of the present invention, two kinds of precursors that adopted: 9,9-two [4-(N, N-two para-totuidine bases) phenyl]-2-bromine fluorenes, and 9,9-two [4-(N, N-two para-totuidine bases) phenyl] fluorenes-2, the 7-hypoboric acid is which ester frequently, and its preparation method is as follows:
A) precursor 9, the preparation of 9-two [4-(N, N-two para-totuidine bases) phenyl]-2-bromine fluorenes:
2-bromine Fluorenone and 4,4 '-dimethyl triphenylamine mixing (mol ratio 1: 3～5), under nitrogen atmosphere, heat, after mixture melts fully, drip catalyzer trifluoromethane sulfonic acid (0.75mL).After reaction finishes, add methylene dichloride and dissolve all unreacted raw materials and other impurity, filtering and obtaining white solid is 9,9-two [4-(N, N-two para-totuidine bases) phenyl]-2-bromine fluorenes.
B) precursor 9,9-two [4-(N, N-two para-totuidine bases) phenyl] fluorenes-2, and the 7-hypoboric acid is the preparation of which ester frequently:
2,7-dibromo fluorenone and 4,4 '-dimethyl triphenylamine mixing (mol ratio 1: 3～5), under nitrogen atmosphere, heat, after mixture melts fully, drip catalyzer trifluoromethane sulfonic acid (1mL).Reaction is dissolved crude product after finishing with methylene dichloride, after partial solvent is removed in decompression, pour precipitating in a large amount of acetone into, and obtaining white solid after the filtration is 9,9-two [4-(N, N-two para-totuidine bases) phenyl]-2,7-dibromo fluorenes.
With 9,9-two [4-(N, N-two para-totuidine bases) phenyl]-2,7-dibromo fluorenes is dissolved in the tetrahydrofuran (THF), and low temperature adds n-Butyl Lithium down under the nitrogen atmosphere, adds isopropoxy boric acid which ester frequently, is warming up to room temperature.After reaction finished, removal of solvent under reduced pressure was made eluant with methylene dichloride/sherwood oil, and silica gel column chromatography obtains white solid product 9,9-two [4-(N, N-two para-totuidine bases) phenyl] fluorenes-2, and the 7-hypoboric acid is which ester frequently.
The substituted radical that adopts among the preparation method of the present invention:
I) bromide of the bromide of the bromide of phenyl, anthryl, pyrenyl, and the bromide of triphen amido buy by commodity.
Ii) the boric acid of phenyl frequently any ester, anthryl boric acid frequently any ester, pyrenyl boric acid frequently any ester, and the boric acid of triphen amido frequently any ester with any the ester reaction frequently of isopropoxy boric acid make under low temperature, catalyst action by the corresponding bromide of conjugation group.
Iii) the preparation of the bromide of the combination of conjugation group can generate corresponding boric acid frequently behind which ester through low temperature, catalyst action reaction by the bromide of conjugation group, dibromide reaction with another kind of conjugation group makes again, as: substituted radical is the bromide [4-(10-bromine anthracene-9-yl)-N of the combination of triphenylamine and anthryl, N-phenylbenzene aniline] time, it is to generate 4-hexichol amido phenylo boric acid frequently behind which ester by 4-bromine triphenylamine adding which the ester reaction frequently of isopropoxy boric acid under low temperature, the n-Butyl Lithium catalysis, makes again with after the dibromide reaction of anthracene.
Iv) the boric acid of the combination of conjugation group frequently any ester be that corresponding bromide by the combination of conjugation group with which the ester reaction frequently of isopropoxy boric acid makes under low temperature, catalyst action.
The above is a known technology, and is not the emphasis that the present invention discusses, and is not described in detail at this.
The compound of the present invention's preparation can prepare luminescent device by following structure:
ITO/ compound/TNS/Alq
3/ LiF/Al
Wherein anode is with tin indium oxide (ITO) glass, and negative electrode is with aluminium (Al), and it is provided by the invention 9 that compound is meant, the derivative of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes, TNS are meant that β-four naphthyl silane is as hole blocking layer, Alq
3Be meant oxine aluminium as electron transfer layer, lithium fluoride (LiF) is used for modifying negative electrode.The method film forming of compound vacuum available evaporation or solution spin coating, other material are all used the method film forming of vacuum evaporation.
The present invention has following feature:
1) compound is all with 9, and 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes is nuclear, and this nuclear contains and has triphen amido and fluorenyl, is convenient to the injection and the transmission in hole.
2) with 9,9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes is nuclear, can carry out monolateral or bilateral conjugation group and replace on 2 and 7 of fluorene group, by adjustable its photoelectric properties of substituting group.
3) as substituent conjugation group bigger conjugated degree is arranged, can be by the conjugated degree of π-π or the pi-conjugated enhancing compound molecule of p-, the glow color of regulating compound obtains blue emission (glow color of nuclear is a purple).
When 4) being applied to this compounds in the electroluminescent device, they are as the hole transmission layer luminescent layer of holding concurrently.
The present invention has the following advantages:
1) this compounds is luminous all in blue region, and very high fluorescence quantum yield is arranged.
2) this compounds has good thermostability, and its decomposition temperature and second-order transition temperature are all very high.
3) this compounds has electron donation preferably, the reversible redox property, and lower oxidation potentiality, higher highest occupied molecular orbital (HOMO) energy level is convenient to the injection and the transmission in hole.
4) this compounds has good prospects for application aspect OLED.
Description of drawings
Fig. 1 is the fluorescence emission spectrum of compd A-E in toluene solution.
Fig. 2 is the fluorescence emission spectrum of compd A-E in film.
Fig. 3 is the cyclic voltammetry curve of compd A-E.
Fig. 4 is the electroluminescent spectrum of compd A-E, and device architecture is ITO/HIL/EML (40nm)/TNS (25nm)/Alq
3(20nm)/and LiF (1nm)/Al (100nm), wherein EML is a compd A, B, C, D or E; For EML is compd A, B, and D, or during E, HIL is PEDOT:PSS (30nm); HTL is F when being Compound C for EML
16CuPc (5nm).
Fig. 5 is based on the voltage-to-current of the blue-light device of this compounds (A-E)-brightness characteristics curve, a) current density-voltage curve; B) brightness-voltage curve.Device architecture is ITO/HIL/EML (40nm)/TNS (25nm)/Alq
3(20nm)/and LiF (1nm)/Al (100nm), wherein EML is a compd A, B, C, D or E; For EML is compd A, B, and D, or during E, HIL is PEDOT:PSS (30nm); HTL is F when being Compound C for EML
16CuPc (5nm).
Fig. 6 is the luminous efficiency curve based on the blue-light device of this compounds (A-E).Device architecture is ITO/HIL/EML (40nm)/TNS (25nm)/Alq
3(20nm)/and LiF (1nm)/Al (100nm), wherein EML is a compd A, B, C, D or E; For EML is compd A, B, and D, or during E, HIL is PEDOT:PSS (30nm); HTL is F when being Compound C for EML
16CuPc (5nm).
Embodiment
The present invention is described in detail below in conjunction with accompanying drawing/table and example.
Showed precursor 9 in the formula 2,9-two [4-(N, N-two para-totuidine bases) phenyl]-2-bromine fluorenes and 9,9-two [4-(N, N-two para-totuidine bases) phenyl] fluorenes-2, the 7-hypoboric acid is the synthetic method of which ester frequently.
(formula 2)
Showed 9 of each conjugation group replacement in the formula 3, the derivative synthetic route of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes.
Embodiment 1:
Precursor 9,9-two [4-(N, N-two para-totuidine bases) phenyl]-2-bromine fluorenes (compound 3) synthetic.
2-bromine Fluorenone (4g, 15.4mmol) with 4,4 '-(15g 55mmol) mixes the dimethyl triphenylamine, is heated to 120 ℃ under nitrogen atmosphere, after mixture melts fully, drips catalyzer trifluoromethane sulfonic acid 1mL, keeps heated overnight.After reaction finishes, add methylene dichloride and dissolve all unreacted raw materials and other impurity, filtering and obtaining white solid is 9,9-two [4-(N, N-two para-totuidine bases) phenyl]-2-bromine fluorenes (formula 3) 11.0g, productive rate 90%.Mass spectrum: m/z 786.7 (M
++ 1); Ultimate analysis (%) C
53H
43BrN
2: theoretical value C 80.80, and H 5.50, and N 3.56; Measured value C 80.05, H 5.64, N3.57.
Embodiment 2:
Precursor 9,9-two [4-(N, N-two para-totuidine bases) phenyl] fluorenes-2,7-hypoboric acid be synthesizing of which ester (compound 2) frequently.
2, the 7-dibromo fluorenone (4g, 12mmol) with 4,4 '-(15g 55mmol) mixes the dimethyl triphenylamine, is heated to 120 ℃ under nitrogen atmosphere, after mixture melts fully, drips catalyzer trifluoromethane sulfonic acid 0.75mL, keeps heated overnight.Reaction is dissolved crude product after finishing with methylene dichloride, after partial solvent is removed in decompression, pour precipitating in a large amount of acetone into, obtaining white solid after the filtration is 9,9-two [4-(N, N-two para-totuidine bases) phenyl]-2,7-dibromo fluorenes (compound 1) 8.7g, productive rate 83%.
Mass spectrum: m/z 864.9 (M
++ 1); Nucleus magnetic hydrogen spectrum [
1H NMR (CDCl
3, 300MHz)]: δ=7.57 (d, 2H), 7.49 (s, 2H), 7.47 (d, 2H), 7.06-6.92 (m, 20H), 6.86 (d, 2H), 2.29 (s, 12H); Ultimate analysis (%) C
53H
42Br
2N
2: theoretical value C 73.45, and H 4.88, and N 3.23; Measured value C 73.39, H 4.86, and N 3.28.
(6.067g 7mmol) is dissolved in the tetrahydrofuran (THF) (150mL), is cooled to-78 ℃ under the nitrogen atmosphere with compound 1, (6.72mL 16.8mmol), kept low temperature about 1 hour to add n-Butyl Lithium, (3.43mL 16.8mmol), is warming up to stirred overnight at room temperature to add which ester of isopropoxy boric acid frequency.After reaction finished, removal of solvent under reduced pressure was made eluant with methylene dichloride/sherwood oil (1: 4), silica gel column chromatography obtains white solid product 9,9-two [4-(N, N-two para-totuidine bases) phenyl] fluorenes-2, the 7-hypoboric acid is which ester (compound 2) 1.7g frequently, productive rate 25%.
Mass spectrum: m/z 959.9 (M
++ 1); Ultimate analysis (%) C
65H
66B
2N
2O
4: theoretical value C 81.25, and H 6.92, and N 2.92; Measured value C 81.59, H 7.47, and N 2.71.
Embodiment 3:
The bromide of the combination of conjugation group: 4-(10-bromine anthracene-9-yl)-N, N-phenylbenzene aniline (compound 8) synthetic.
(3.24g 10mmol) is dissolved in the tetrahydrofuran (THF) (30mL) 4-bromine triphenylamine, is cooled to-78 ℃ under the nitrogen atmosphere, (4.8mL 12mmol), kept low temperature about 1 hour to add n-Butyl Lithium, (2.45mL 12mmol), is warming up to stirred overnight at room temperature to add which ester of isopropoxy boric acid frequency.After reaction finished, rotary evaporation removed and desolvates, and makes eluant with sherwood oil, and silica gel column chromatography obtains white solid product 4-hexichol amido phenylo boric acid which ester (compound 7) 2.2g frequently, productive rate 59%.Mass spectrum: m/z371 (M
++ 1); Ultimate analysis (%) C
24H
26BNO
2: theoretical value C 77.64, and H 7.06, and N 3.77; Measured value C 77.42, H 7.18, and N 3.75.
Compound 7 (1.86g, 5mmol), 9,10-dibromoanthracene (5.04g, 15mmol), tetrahydrofuran (THF) (100mL), wet chemical (2.0M, 30mL), several aliquat336, catalyzer tetrakis triphenylphosphine palladiums (174mg) add in the there-necked flask, was warming up to 80 ℃ of reflux 48 hours under nitrogen atmosphere.After reaction finishes, remove by filter the excessive raw material of part 9,10-dibromoanthracene and other impurity, filtrate is removed part 9 again with the tetrahydrofuran (THF) recrystallization, 10-dibromoanthracene, residue mother liquor removal of solvent under reduced pressure, make eluant with sherwood oil, silica gel column chromatography obtains yellow-green colour solid 4-(10-bromine anthracene-9-yl)-N, N-phenylbenzene aniline (compound 8) 2.1g, productive rate 84%.Mass spectrum: m/z 499.4 (M
++ 1); Nucleus magnetic hydrogen spectrum [
1HNMR (CDCl
3, 300MHz)]: δ=8.54 (d, 2H), 7.78-7.68 (m, 4H), 7.57 (t, 2H), 7.40 (t, 4H), 7.32 (d, 2H), 7.27-7.08 (m, 8H); Ultimate analysis (%) C
32H
22BrN: theoretical value C 76.80, H 4.43, and N 2.80; Measured value C 76.77, H 4.54, and N 3.13.
Embodiment 4:
The boric acid of conjugation group is which ester frequently: pyrene boric acid is the preparation of which ester (compound 4) frequently.
(1.41g 5mmol) is dissolved in the tetrahydrofuran (THF) (30mL) 1-bromine pyrene, is cooled to-78 ℃ under the nitrogen atmosphere, (2.4mL 6mmol), kept low temperature about 1 hour to add n-Butyl Lithium, (1.22mL 6mmol), is warming up to stirred overnight at room temperature to add which ester of isopropoxy boric acid frequency.After reaction finished, rotary evaporation removed and desolvates, and makes eluant with sherwood oil, and silica gel column chromatography obtains yellow solid product pyrene boric acid which ester (compound 4) 0.55g frequently, productive rate 33%.
Mass spectrum: m/z 328 (M
++ 1); Nucleus magnetic hydrogen spectrum [
1H NMR (CDCl
3, 300MHz)]: δ=9.09 (d, 1H), 8.55 (d, 1H), 7.47 (d, 2H), 8.21-8.12 (m, 4H), 8.08-7.96 (m, 3H), 1.48 (s, 12H); Ultimate analysis (%) C
22H
21BO
2: theoretical value C 80.51, and H 6.45; Measured value C80.31, H 6.62.
Embodiment 5:
The boric acid of conjugation group is which ester frequently: 10-benzene anthracene-9-boric acid is the preparation of which ester (compound 6) frequently.
(1.5g 5.9mmol) is dissolved in the acetic acid (80mL) 9-benzene anthracene, is heated to 65 ℃ of backflows, and (0.34mL 6.5mmol) is dissolved in the 20mL acetic acid, drips gradually with bromine.After bromine drips, reduce to room temperature, to filter and obtain glossiness yellow solid, filtrate is removed under reduced pressure and is desolvated, and obtains yellow solid, purifies with the acetic acid recrystallization.Two portions solid merges, and is 9-bromo-10-benzene anthracene (compound 5) 1.8g, productive rate 93%.Mass spectrum: m/z 334 (M
++ 1); Nucleus magnetic hydrogen spectrum [
1H NMR (CDCl
3, 400MHz)]: δ=8.65 (d, 2H), 7.68 (d, 2H), 7.63 (s, 1H), 7.60 (d, 4H), 7.44-7.38 (m, 4H); Ultimate analysis (%) C
20H
13Br: theoretical value C 72.09, H 3.93; Measured value C 71.95, H 3.99.
(1g 3mmol) is dissolved in the tetrahydrofuran (THF) (30mL) compound 5, is cooled to-78 ℃ under the nitrogen atmosphere, (1.5mL 3.6mmol), kept low temperature about 1 hour to add n-Butyl Lithium, (0.74mL 3.6mmol), is warming up to stirred overnight at room temperature to add which ester of isopropoxy boric acid frequency.After reaction finished, rotary evaporation removed and desolvates, and makes eluant with sherwood oil, and silica gel column chromatography obtains faint yellow solid product 10-benzene anthracene-9-boric acid which ester (compound 6) 0.67g frequently, productive rate 59%.Mass spectrum: m/z 380 (M
++ 1); Nucleus magnetic hydrogen spectrum [
1H NMR (CDCl
3, 300MHz)]: δ=8.45 (d, 2H), 7.63 (d, 2H), 7.57-7.52 (m, 3H), 7.47 (t, 2H), 7.40 (d, 2H), 7.31 (t, 2H), 1.60 (s, 12H); Ultimate analysis (%) C
26H
25BO
2: theoretical value C 82.12, and H 6.63; Measured value C 82.00, H 6.75.
Embodiment 6:
Monolateral conjugation group replace 9, the derivative of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes: 9,9-two [4-(N, N-two para-totuidine bases) phenyl]-2-pyrenyl fluorenes (compd A) synthetic.
At first according to the method synthetic compound 3 of embodiment 1, the method synthetic compound 4 of embodiment 4.Compound 4 (656mg, 2mmol), compound 3 (1.887g, 2.4mmol) be mixed in the there-necked flask, add toluene (100mL), solution of potassium carbonate (2.0M, 20mL), several aliquat336, catalyzer tetrakis triphenylphosphine palladium (100mg), 115 ℃ of reflux are 48 hours under nitrogen atmosphere.After reaction finished, removal of solvent under reduced pressure was made eluant with methylene dichloride/sherwood oil (1: 9), and silica gel column chromatography obtains oyster solid 9,9-two [4-(N, N-two para-totuidine bases) phenyl]-2-pyrenyl fluorenes (compd A) 1.22g, productive rate 67%.
Mass spectrum: m/z 908.8 (M
++ 1); Nucleus magnetic hydrogen spectrum [
1H NMR (CDCl
3, 300MHz)]: δ=8.20 (t, 2H), 8.13-8.09 (m, 4H), 8.04 (d, 2H), 7.94 (d, 2H), 7.85 (d, 1H), 7.73 (s, 1H), 7.66 (d, 1H), 7.50 (d, 1H), 7.41 (t, 1H), 7.33 (t, 1H), 7.12 (d, 4H), 7.02-6.93 (m, 16H), 6.89 (d, 4H), 2.27 (s, 12H); Ultimate analysis (%) C
69H
52N
2: theoretical value C 91.15, and H 5.76, and N 3.08; Measured value C 90.79, H 5.75, and N 3.34.
Embodiment 7:
Monolateral conjugation group replace 9, the derivative of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes: 9,9-two [4-(N, N-two para-totuidine bases) phenyl]-2-(10-phenylanthracene-9-yl) fluorenes (Compound C) synthetic.
At first according to the method synthetic compound 3 of embodiment 1, the method synthetic compound 6 of embodiment 5.Compound 6 (456mg, 1.2mmol), compound 3 (1.13g, 1.44mmol) be mixed in the there-necked flask, add toluene (80mL), solution of potassium carbonate (2.0M, 10mL), several aliquat336, catalyzer tetrakis triphenylphosphine palladium (70mg), 115 ℃ of reflux are 48 hours under nitrogen atmosphere.After reaction finished, removal of solvent under reduced pressure was made eluant with methylene dichloride/sherwood oil (1: 5), silica gel column chromatography obtains yellow solid 9,9-two [4-(N, N-two para-totuidine bases) phenyl]-2-(10-phenylanthracene-9-yl) fluorenes (Compound C) 0.68g, productive rate 59%.Mass spectrum: m/z 960.5 (M
++ 1); Nucleus magnetic hydrogen spectrum [
1H NMR (CDCl
3, 300MHz)]: δ=7.99 (d, 1H), 7.88 (d, 1H), 7.75-7.66 (m, 4H), 7.61-7.57 (m, 4H), 7.56-7.39 (m, 5H), 7.38-7.29 (m, 4H), 7.13 (d, 4H), 7.05-6.88 (m, 17H), 6.85 (d, 4H), 2.27 (s, 12H); Ultimate analysis (%) C
73H
56N
2: theoretical value C 91.21, and H 5.87, and N 2.91; Measured value C 90.80, H 5.86, and N 3.34.
Embodiment 8:
Bilateral conjugation group replace 9, the derivative of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes: 9,9-two [4-(N, N-two para-totuidine bases) phenyl]-2,7-two pyrenyl fluorenes (compd B) synthetic.
At first according to the method synthetic compound 2 of embodiment 2.1-bromine pyrene (478mg, 1.7mmol), compound 2 (672mg, 0.7mmol) be mixed in the there-necked flask, add toluene (50mL), solution of potassium carbonate (2.0M, 5mL), several aliquat336, catalyzer tetrakis triphenylphosphine palladium (30mg), 115 ℃ of reflux are 36 hours under nitrogen atmosphere.After reaction finishes, removal of solvent under reduced pressure adds the methylene dichloride dissolving, removes inorganic salt with the NaCl solution extraction, the organic phase anhydrous magnesium sulfate drying, filtrate filtered is removed with rotary evaporation and is desolvated, and makes eluant with methylene dichloride/sherwood oil (1: 5), and silica gel column chromatography obtains yellow solid product 9,9-two [4-(N, N-two para-totuidine bases) phenyl]-2,7-two pyrenyl fluorenes (compd B) 0.57g, productive rate 73%.Mass spectrum: m/z 1108.8 (M
++ 1); Nucleus magnetic hydrogen spectrum [
1HNMR (CDCl
3, 300MHz)]: δ=8.26-7.97 (m, 20H), 7.80 (s, 2H), 7.73 (d, 2H), 7.21 (d, 4H), 7.03-6.89 (m, 20H); Ultimate analysis (%) C
85H
60N
2: theoretical value C 92.02, H5.45, and N 2.53; Measured value C 91.22, H 5.74, and N 2.52.
Embodiment 9:
9 of bilateral conjugation group replacement, the derivative of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes: 9,9-two [4-(N, N-two para-totuidine bases) phenyl]-2,7-two (10-phenylanthracene-9-yl) fluorenes (Compound D).
At first according to the method synthetic compound 5 of embodiment 5, the method synthetic compound 2 of embodiment 2.Compound 5 (766mg, 2.3mmol), compound 2 (960mg, 1mmol) add in the there-necked flask, add toluene (50mL), solution of potassium carbonate (2.0M again, 10mL), several aliquat336, catalyzer tetrakis triphenylphosphine palladium (70mg), 115 ℃ of reflux are 48 hours under nitrogen atmosphere.After reaction finished, removal of solvent under reduced pressure was made eluant with methylene dichloride/sherwood oil (1: 8), silica gel column chromatography obtains light yellow solid 9,9-two [4-(N, N-two para-totuidine bases) phenyl]-2,7-two (10-phenylanthracene-9-yl) fluorenes (Compound D) 0.66g, productive rate 54%.Mass spectrum: m/z 1212.4 (M
++ 1); Nucleus magnetic hydrogen spectrum [
1HNMR (CDCl
3, 300MHz)]: δ=8.12 (d, 2H), 7.88-7.76 (br, 4H), 7.76-7.42 (m, 18H), 7.41-7.38 (br, 8H), 7.20 (d, 4H), 7.03-6.78 (m, 20H), 2.25 (s, 12H); Ultimate analysis (%) C
93H
68N
2: theoretical value C 92.04, and H 5.65, and N 2.31; Measured value C 92.04, H 5.65, and N 2.79.
Embodiment 10:
9 of bilateral conjugation group replacement, the derivative of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes: 9,9-two [4-(N, N-two para-totuidine bases) phenyl]-2,7-two [10-(4-hexichol aminocarbonyl phenyl) anthracene-9-yl] fluorenes (compd E).
At first according to the method synthetic compound 2 of embodiment 2, the method synthetic compound 8 of embodiment 3.Compound 8 (1g, 2mmol), compound 2 (769mg, 0.8mmol), tetrahydrofuran (THF) (100mL), wet chemical (2.0M, 30mL), several aliquat336, catalyzer tetrakis triphenylphosphine palladiums (85mg) add in the there-necked flask, was warming up to 80 ℃ of reflux 48 hours under nitrogen atmosphere.After reaction finishes, removal of solvent under reduced pressure, make eluant with methylene dichloride/sherwood oil (1: 5), the silica gel column chromatography preliminary purification is dissolved in methylene dichloride with mixture then, be added drop-wise to precipitating in the sherwood oil, filtration obtains yellow-green colour solid 9,9-two [4-(N, N-two para-totuidine bases) phenyl]-2,7-two [10-(4-hexichol aminocarbonyl phenyl) anthracene-9-yl] fluorenes (compd E) 0.79g, productive rate 64%.Mass spectrum: m/z 1548.0 (M
++ 1).
Embodiment 11:
Preparation and performance test based on the electroluminescent device of compd A.
Ito glass passes through washing composition successively, deionized water, and acetone is dried after the washing with alcohol.After the ito glass of wash clean is handled 10 minutes through UVO (40W), spin coating PEDOT:PSS aqueous solution (Baytron P4083) on it, get rid of film thickness monitoring be 30nm.The ito glass that scribbles PEDOT:PSS is placed baking oven, and 100 ℃ were toasted 2 hours down.To be cooled to room temperature, toluene solution of spin coating compd A on it, the control thickness is 40nm, as the hole transport luminescent layer of holding concurrently.Again in vacuum chamber, 5 * 10
-4Evaporation TNS (25nm) on it successively under the Pa vacuum tightness, Alq
3(20nm), LiF (1nm), Al (100nm).
Above-mentioned device is tested under room temperature, atmospheric environment: current-voltage curve is recorded by the HP4140B semi-conductor test instrument; Luminous power is recorded by the NewPort2835C light power meter, can obtain light emission luminance value through conversion; Chromaticity coordinates is recorded by the PR-650 colourimeter, and electroluminescent spectrum is recorded by the Hitachi-F4500 spectrograph.
Embodiment 12:
Preparation and performance test based on the electroluminescent device of compd B.
Press method fabricate devices and the test component of embodiment 11, hole transport that different the is luminescent material compd B of holding concurrently.
Embodiment 13:
Preparation and performance test based on the electroluminescent device of Compound C.
Ito glass passes through washing composition successively, deionized water, and acetone is dried after the washing with alcohol.The ito glass of wash clean is placed vacuum chamber, in 5 * 10
-4CuPc (the F that replaces to evaporation skim perfluor on it earlier under the Pa vacuum tightness
16CuPc 5nm) is used for modifying ito anode.Then hole transport of vacuum evaporation Compound C formation 40nm luminescent layer of holding concurrently on to it.Again in vacuum chamber, 5 * 10
-4Evaporation TNS (25nm) on it successively under the Pa vacuum tightness, Alq
3(20nm), LiF (1nm), Al (100nm).
The means of testing of prepared device is identical with embodiment 11.
Embodiment 14:
Preparation and performance test based on the electroluminescent device of Compound D.
Press method fabricate devices and the test component of embodiment 11, hole transport that different the is luminescent material Compound D of holding concurrently.
Embodiment 15:
Preparation and performance test based on the electroluminescent device of compd E.
Press method fabricate devices and the test component of embodiment 11, hole transport that different the is luminescent material compd E of holding concurrently.
9 of synthetic conjugation group replacement, title and the mutually deserved substituted radical of the derivative A-E of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes are summarized in the table 1.
The synthetic route of compd A-E as shown in Figure 2.
9 of institute's synthetic conjugation group replacement, the derivative A-E of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes, the emission peak in toluene solution is 406-456nm, all in blue region (as shown in Figure 3).The fluorescence emission peak of compd A-E under filminess be also all in blue region, but with respect to their emission peaks in solution some red shift (see figure 4)s have been arranged.Wherein the emission peak of compd A under filminess has 53nm than its emission peak red shift amount maximum in toluene solution; The emission peak of compd E under filminess has 13nm than its emission peak red shift amount minimum in toluene solution.Based on the electroluminescence spectrum of the OLED device of compd A-E and the fluorescence spectrum basically identical under its filminess separately, luminous as shown in Figure 6 all in blue region, its electroluminescent peak position and chromaticity coordinates are listed in the table 3.The calorifics of compd A-E and electrochemical data are summarized in the table 2, can find out that these compounds have good thermostability from table, and its decomposition temperature and second-order transition temperature are all very high.These compounds have higher H OMO energy level, and reversible redox processes (see figure 5), show that these compounds are beneficial to the injection and the transmission in hole.
Fig. 7, Fig. 8 have showed the performance based on the electroluminescent device of compd A-E.They all have higher luminosity and efficient.Wherein the device based on Compound C has the highest brightness 3150cd/m
2(when 14.5V) has the highest luminous efficiency 3.1cd/A (at 2.33mA/cm based on the device of compd E
2The time).
Table 1.
Table 2
| Compound | T g (℃) | T d(℃) | E 1/2(V) | E onset (V) | E HOMO (eV) | E LUMO (eV) |
| A | / | 453 | 0.88 | 0.78 | -5.18 | -2.02 |
| B | 165 | 535 | 0.92 | 0.81 | -5.22 | -2.14 |
| C | 159 | 487 | 0.88 | 0.76 | -5.18 | -2.20 |
| D | / | 496 | 0.94 | 0.79 | -5.24 | -2.29 |
| E | / | / | 0.93 | 0.76 | -5.23 | -2.34 |
Table 3.
| Compound | The CIE coordinate (x, y) | Electroluminescent peak position (nm) |
| A | (0.18，0.20) | 455 |
| B | (0.15，0.16) | 457 |
| C | (0.18，0.20) | 454 |
| D | (0.19，0.22) | 449 |
| E | (0.15，0.24) | 471 |
Claims (10)
1. hole-transporting type blue light compound, for based on 9, the derivative of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes, its structure as shown in Equation 1:
Formula 1
Wherein R, R ' group are hydrogen atom or the conjugation group with big conjugation degree, and R, R ' group can be the same or different;
When a group is arranged among R ' and the R for-H, be referred to as that monolateral conjugation group replaces 9, the derivative of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes; When R ' and R be-during H, be referred to as 9 of bilateral conjugation group replacement, the derivative of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes.
2. hole-transporting type blue light compound as claimed in claim 1, wherein the conjugation group is phenyl, anthryl, pyrenyl, aromatic amino or their combination.
One kind prepare that monolateral conjugation group replaces in the described hole-transporting type blue light of claim 1 compound 9, the synthetic method of the derivative of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes:
With 9,9-two [4-(N, N-two para-totuidine bases) phenyl]-boric acid of 2-bromine fluorenes and conjugation group any ester in molar ratio 1～2 frequently: 1 mixes, add toluene 50～100mL, the aliquat336 of concentration 2.0M solution of potassium carbonate 10～30mL, 0.05～0.5mL, catalyzer tetrakis triphenylphosphine palladium, under nitrogen atmosphere reflux 10-30 hour; After reaction finished, removal of solvent under reduced pressure obtained 9 of the monolateral conjugation group replacement of target product, the derivative of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes.
4. method as claimed in claim 3, wherein where ester is the boric acid of conjugation group frequently: pyrene boric acid is which ester, 10-benzene anthracene-which ester of 9-boric acid frequency or 10-(4-hexichol aminocarbonyl phenyl) anthracene-which ester of 9-boric acid frequency frequently.
5. method as claimed in claim 3, wherein, the target product methylene dichloride: sherwood oil=make eluant at 1: 9, silica gel column chromatography is purified.
One kind prepare that bilateral conjugation group replaces in the described hole-transporting type blue light of claim 1 compound 9, the synthetic method of the derivative of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes:
With 9,9-two [4-(N, N-two para-totuidine bases) phenyl] fluorenes-2, the 7-hypoboric acid is the bromide in molar ratio 2～3 of which ester and conjugation group frequently: 1 mixes, add toluene 50～100mL, concentration 2.0M solution of potassium carbonate 5～30mL, 0.05～0.5mLaliquat336, catalyzer tetrakis triphenylphosphine palladium, under nitrogen atmosphere reflux 10-30 hour; After reaction finished, removal of solvent under reduced pressure obtained 9 of the bilateral conjugation group replacement of target product, 9-two (4-(two-p-methylphenyl) aminophenyl) fluorene derivatives.
7. method as claimed in claim 6, wherein, the bromide of conjugation group is: bromo pyrene, 9-bromo-10-benzene anthracene, or 4-(10-bromine anthracene-9-yl)-N, N-phenylbenzene aniline.
8. method as claimed in claim 6, wherein, target product adds the methylene dichloride dissolving, remove inorganic salt with saturated NaCl solution extraction, the organic phase anhydrous magnesium sulfate drying, filtrate filtered is removed with rotary evaporation and desolvated, and uses methylene dichloride: sherwood oil=make eluant at 1: 9, silica gel column chromatography is purified.
9. the application of the described hole-transporting type blue light of claim 1 compound in the preparation luminescent device prepares luminescent device by following structure:
ITO/ compound/TNS/Alq
3/ LiF/Al
Wherein anode is with tin indium oxide (ITO) glass, and negative electrode is with aluminium (Al), and compound is meant 9 of claim 1, and the derivative of 9-two (4-(two-p-methylphenyl) aminophenyl) fluorenes, TNS are meant that β-four naphthyl silane is as hole blocking layer, Alq
3Be meant oxine aluminium as electron transfer layer, lithium fluoride (LiF) is used for modifying negative electrode.
10. application as claimed in claim 9, wherein compound is with the method film forming of vacuum evaporation or solution spin coating, and other material is all used the method film forming of vacuum evaporation.
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