CN101126020B - 1, 3, 6, 8-tetraaryl-9-alkyl substituted carbazole derivative and application thereof in luminescent diode - Google Patents
1, 3, 6, 8-tetraaryl-9-alkyl substituted carbazole derivative and application thereof in luminescent diode Download PDFInfo
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Abstract
The invention discloses an electroluminescent material from near-ultraviolet to deep blue containing 9-alkly-1, 3, 6, 8-aryl used as substitute for carbazole derivative and a preparation method thereof. The structure of the invention can be expressed by element analysis, nuclear magnetic resonance spectrum and mass spectrum; the optical physic properties of the invention are studied by ultraviolet absorption spectrum and fluorescence spectrum; the application of the invention in organic light-emitting diodes is also studied. The experiment indicates that the compound has good dissolve performance and good heat stability; the light of near-ultraviolet or deep blue given out by solid powder and film has good color purity; the maximum wavelength of light is 390-440nm.
Description
Technical field:
The present invention relates to one type and contain the 9-alkyl and replace-1,3,6,8-four aryl carbazole derivative and preparation method thereof and as the application of electroluminescent material in organic flat panel display device and white-light illuminating device thereof.
Background technology:
The Eastern Kodak C.W.Tang of company in 1987 etc. are at document (C.W.Tang; S.A.Vanslyke Appl.Phys.Lett.1987; 51; 913) and invented the device of sandwich structure among the patent US4356429; Adopt fluorescence efficiency very high, electron transport property is arranged and can process the high-quality thin film of even compact with the oxine aluminium (Alq3) of vacuum plating and the aromatic diamine (diamine) with hole transport characteristic, and process organic EL device, just make the epoch of the research work entering practicality of electroluminescent organic material and device.The breadboard Friend of the nineteen ninety Cavendish of univ cambridge uk etc. has reported the phenomenon of high molecule electroluminescent under low voltage, has opened the frontier of polymer FPD research; The Heeger of Pennsylvania State Univ-Univ Park USA in 1992 etc. has invented with plastics as substrate preparation deformable flexible indicating meter first, and the one side that organic elctroluminescent device is the most charming is presented in face of the people.The Forrest of Princeton university in 1997 etc. find the phosphorescence electro optical phenomenon, have broken through the electroluminescent organic material quantum yield and have been lower than 25% restriction, make a new development of the research entering period of organic elctroluminescent device.
Carbazole (carbazole) and verivate thereof are typical blue emitting materials, have very high fluorescence quantum efficiency, and well light, heat and chemicalstability are considered to one of best luminescent material.Nearly all contain carbazole group in the chemical structure of phosphorescence main light emission material commonly used at present, and the verivate of carbazole group all have characteristic [(1) D.M.Pai, J.E.Yanus, the M.Stolka of hole transport
J.Phys.Chem., 1984,88,4714; (2) X.Gong, M.R.Robinson, J.C.Ostrowski, D.Moses, G.C.Bazan, A.J.Heeger
Adv.Mater., 2001,14,581].The main body luminescent material that the most often is used is 4,4 '-two (9-carbazyl-) biphenyl (CBP), and CBP is in the news and has character [H.Kanai, S.Ichinosawa, the Y.Sato of quadripole transmission
Synth.Met., 1997,71,195], use the internal quantum of green, yellow and the red phosphorescent device of CBP can reach 60～80% [
J.Am.Chem.Soc., 123,4304 (2001);
Jpn.J Appl.Phys.Part2,38, L1502 (1999);
Org.Electron., 2,37 (2001);
Nature (London), 403,750 (2000);
Appl.Phys.Lett., 79,1045 (2001);
Synth.Met., 122,203 (2001)], external quantum efficiency can be higher than 10%.But the triplet excited state energy of CBP has only 2.56eV; Have high triple excited energies (> 2.65eV if mix) the blue phosphorescent material time; Can take place energy is returned the phenomenon to the main light emission material; The external quantum efficiency of device is reduced to had only (5.7 ± 0.3) % [Appl.Phys.Lett., 79,2082 (2001)].Developed the various main body luminescent materials that contain the verivate of carbazole group as the phosphorescence device afterwards successively, more famous has 4,4 ', 4 "-Tris (9-carbazoyl) triphenyl (TCTA) [
Appl.Phys.Lett., 79,156 (2001)], adopt hole mobile material TCTA as the main light emission material, utilize starlike C60F42 (CF-X) as hole and exciton barrier-layer again, doping Ir (ppy)
3Device, under the driving voltage of 3.52V, external quantum efficiency can rise to 19.2%.
Improve the efficient of blue phosphorescent device, just must use the main light emission material of high triple excited energies, developed N for this reason, N '-dicarbazolyl-2,5-benzene (mCP) [
New J.Chem., 26,1171 (2002);
Appl.Phys.Lett.; 82,2422 (2003)], this material is the conjugate system shortening with famous main light emission material C BP; With the meta-substituent of two carbazole groups as phenyl ring; Make the triplet excited state energy of mCP rise to 2.9eV, two carbazoles are substituent sterically hinderedly to make whole planes of molecules be distorted, and can reduce to produce concentration quenching under high doping because the object luminescent material piles up.With the triplet excited state energy be 2.65eV Iridium bis (4,6-difluorophenyl)-pyidinato-N, C
2 ') picolinate (FIrpic) blue phosphorescent guest materials is doped among the mCP, the external quantum efficiency of device can be promoted to (7.8 ± 0.8) %.
S.Tokito etc. introduce 4 of methyl substituents on 2 and 2 ' of CBP xenyl, 4 '-Bis (9-carbazolyl)-2,2 '-dimethyl-biphneyl (CDBP) [
Appl.Phys.Lett., 83,569 (2003)], make two overlapping reducing of phenyl ring planar molecular orbital(MO), shorten the conjugate system of molecule, to improve the energy of triplet excited state, also can avoid the concentration quenching under high doping of hotchpotch simultaneously.Through experiment measuring, the energy of the triplet excited state of CDBP rises to 3.0eV, can reach 10.4% with the external quantum efficiency of the blue-light device of FIrpic.
Design philosophy of the present invention is with carbazole with good electric electroluminescent properties, high fluorescence quantum efficiency and the hole transport performance center as molecule, in the high reaction activity position 1,3 of carbazole ring; Connect the higher relatively substituting groups such as aromatic nucleus of unreactiveness on 6,8, not only can avoid other active specy and luminescence center generation chemical reaction; And 6; Aromatic substituent on 8 shortens the conjugation chain length of molecule owing to receive 9 distortions of going up the extruding generation planes of molecules of group, increases the triplet excited state energy; Avoid the formation of exciplex, improve the luminous efficiency of material.
Summary of the invention:
The object of the present invention is to provide one type to contain the 9-alkyl and replace-1,3,6,8-four aryl carbazole derivative and preparation method thereof and as the application of electroluminescent material in organic flat panel display device and white-light illuminating device thereof.
The present invention utilizes the center of carbazole as molecule, uses the Suzuki reaction aryl or alkane substituting group are connected 1,3 of carbazole ring; On 6,8,9; Prepared a series of can be with 9-alkyl-1 evaporation film-forming, brand-new, that have near ultraviolet or mazarine electroluminescent and hole transport performance; 3,6,8-four aryl substituted carbazole verivates.
One type of novel near ultraviolet provided by the invention or mazarine electroluminescent material have following structure:
R is a hydrogen; Methyl; Ethyl; N-propyl; Normal-butyl; N-pentyl; N-hexyl; N-heptyl; N-octyl; The 2-ethylhexyl; N-nonyl; Positive certain herbaceous plants with big flowers base; Benzyl.
Ar is a phenyl; The 2-tolyl; The 3-tolyl; The 4-tolyl; The 4-tert-butyl-phenyl; The 4-xenyl; The 1-naphthyl; The 2-naphthyl; 9,9-dimethyl fluorene-2-base; 9,9-dibutyl fluorenes-2-base; 9,9-dihexyl fluorenes-2-base; 9,9-two (2 '-ethylhexyl) fluorenes-2-base; 9-methyl carbazole-3-base; 9-ethyl carbazole-3-base; 9-butyl carbazole-3-base; 9-hexyl carbazole-3-base; 9-(2-ethylhexyl) carbazole-3-base; Contain substituent conjugation or its structure of unconjugated phenyl is:
(wherein D is conjugation or unconjugated aryl structural unit, n=0,1,2); Contain substituent conjugation or its structure of unconjugated naphthyl is:
(wherein D is conjugation or unconjugated aryl structural unit, n=0,1,2); Contain substituent conjugation or its structure of unconjugated fluorenyl is:
(wherein D is conjugation or unconjugated aryl repeated structural unit, n=0,1,2); Contain substituent conjugation or its structure of unconjugated carbazyl is:
(wherein D is conjugation or unconjugated aryl repeated structural unit, n=0,1,2).Contain substituent conjugation or unconjugated thiophene phenyl and and phenyl, its structure is:
(wherein D is conjugation or unconjugated aryl repeated structural unit, n=0,1,2).
Major advantage of the present invention is:
1. prepared with known bromination reaction and Suzuki reaction synthetic route and contained 9-alkyl-1,3,6, the substituted carbazole derivative of 8-four aryl.
2. synthetic 9-alkyl-1,3,6, the substituted carbazole derivative solvability of 8-four aryl is good, and is at chloroform and methylene dichloride, solvable in the organic solvents such as toluene.
3. compound is near ultraviolet or the mazarine fluorescence material and the electroluminescent material of excellent property; When 9-alkyl-1; 3,6, when the aryl of the substituted carbazole derivative of 8-four aryl is little conjugation aromatic base such as phenyl, thienyl, Alpha-Naphthyl; The peak width at half of light fluorescence or electroluminescent spectrum is narrow band near ultraviolet or the mazarine fluorescence material and the electroluminescent material of one type of high color purity less than 50nm.The maximum optical emission wavelength is between 390nm～440nm.Near ultraviolet electroluminescent fluorescent ballistic device structure is: ITO/CuPc (30nm)/9-Methyl-1,3,6,8-tetraphenyl-9H-carbazole (30nm)/BCP (20nm)/AlQ
3(30nm)/and Li (0.5nm)/Al (100nm), the maximum optical emission wavelength lambda
Max=401nm; Maximum external quantum efficiency is 1.2%, and high-high brightness is 104 ℃ of d/m
2, playing bright voltage is V
On=3.5V.
4. the device architecture as the hole material is: ITO/9-Methyl-1,3,6,8-tetraphenyl-9H-carbazole (30nm)/AlQ
3(30nm)/Li (0.5nm)/Al (100nm).The maximum optical emission wavelength lambda
Max=516nm; Maximum external quantum efficiency and brightness are respectively 1.1%, 3.3cd/A, 1800 ℃ of d/m
2, playing bright voltage is V
On=2.4V.
Description of drawings:
Fig. 1 is a 9-alkyl-1,3,6, the substituted carbazole derivative synthetic route of 8-four aryl;
Fig. 2 is a 9-alkyl-1,3,6, the fluorescence spectrum of the substituted carbazole derivative pressed powder of 8-tetraphenyl.
Fig. 3 is ITO/CuPc (30nm)/9-Methyl-1,3,6, and 8-tetraphenyl-9H-
Carbazole (30nm)/BCP (20nm)/AlQ
3(30nm)/electroluminescent spectrum of Li (0.5nm)/Al (100nm) device.
Embodiment:
Synthetic route is as shown in Figure 1.
(1) 9-methyl carbazole
Add (10mmol) carbazole in the 50mL there-necked flask, inflated with nitrogen 30min injects methyl-sulfate (12mmol); 10ml DMSO, 85% Pottasium Hydroxide (30mmol), 30mg chlorination triethyl Bian ammonium (TEBA); Under nitrogen atmosphere, stir after 6 hours, reaction solution is poured in the 100mL zero(ppm) water, cross and filter white powder; With 95% ethyl alcohol recrystallization get white squamous crystal (1.72g, yields:95%)
(2) 9-butyl carbazole
Add (10mmol) carbazole, inflated with nitrogen 30min, 10mLDMSO in the 50mL there-necked flask; 85% Pottasium Hydroxide (30mmol), 30mg chlorination triethyl Bian ammonium (TEBA), n-butyl bromide (15mmoB; Potassiumiodide (30mmol) stirs after 8 hours under nitrogen atmosphere, and reaction solution is poured in the 100mL zero(ppm) water; Cross and filter white powder, with ethyl alcohol recrystallization get white needle-like crystals (2.05g, yields:92%)
(3) 9-methyl isophthalic acid, 3,6,8-tetrabromo carbazole
Get the 100ml there-necked flask, add 9-butyl carbazole (15mmol) and 60ml glacial acetic acid, stirring at room 20min makes it whole dissolvings.Get the 68mmol bromine again and be dissolved in the 40ml glacial acetic acid, slowly splash in the flask, drip off the back and be heated to 90 ℃ to reaction system, keep 10hrs, place a night; Filter, solid is with washing, and drying is used the toluene recrystallization; Washing, and dry white needle-like crystals (6.6g, yields:88%), mp:192.7 ℃;
1H NMR (CDCl
3, 500Hz) δ: 4.48 (3H, s); 7.79～7.80 (2H, d); 8.04～8.05 (2H, d).
(4) 9-butyl-1,3,6,8-tetrabromo carbazole
Get the 100ml there-necked flask, add 9-butyl carbazole (15mmol) and 60ml glacial acetic acid, stirring at room 20min makes it whole dissolvings.Get the 68mmol bromine again and be dissolved in the 40ml glacial acetic acid, slowly splash in the flask, drip off the back and be heated to 90 ℃ to reaction system, keep 10hrs; Place a night, filter, solid is with washing, drying; Use the toluene recrystallization, washing, dry white needle-like crystals (6.8g, yields:84%); Mp:170.5 ℃, MS (EI, m/z):
1H NMR (CDCl
3, 500Hz) δ: 0.96～0.99 (3H, t); 1.35～1.40 (2H, q); 1.76～1.82 (2H, m); 5.15～5.18 (2H, t); 7.81～7.82 (2H, d); 8.08～8.08 (2H, d).
(5) 9-methyl isophthalic acid, 3,6,8-tetraphenyl carbazole
Get the 100ml there-necked flask and add 9-butyl-1,3,6,8-tetrabromo carbazole (2mmol); Sodium tetraphenylborate (2.5mmol), Tetrabutyl amonium bromide (TBAB) (0.4mmol), Palladous chloride (0.04mmol); 2M sodium carbonate solution 12ml, acetone 36ml is at nitrogen atmosphere refluxed 10hrs.Boil off acetone, water layer is used dichloromethane extraction, and anhydrous magnesium sulfate drying is used in extracting solution washing back, by silica gel column chromatography separate white needle-like crystals (0.78g, yields:79%), mp:236.2 ℃; MS-EI (m/e): 485 (100.00%), 486 (30%), 243 (15%); Elemental analysis:Calculate (%) for C
37H
27N:C 91.51, and H 5.60, and N 2.88; Found:C 91.20, H5.56, and N 2.68;
1H NMR (CDCl
3, 500Hz) δ: 2.94 (3H, s); 7.38～7.42 (4H, m); 7.47～7.52 (8H, q); 7.60～7.65 (2H, m); 7.80～7.81 (4H, t); 8.42～8.42 (2H, d).
(6) 9-butyl-1,3,6,8-tetraphenyl carbazole
Get the 100ml there-necked flask and add 9-butyl-1,3,6,8-tetrabromo carbazole (2mmol); Sodium tetraphenylborate (2.5mmol), Tetrabutyl amonium bromide (TBAB) (0.4mmol), Palladous chloride (0.04mmol); 2M sodium carbonate solution 12ml, acetone 36ml is at nitrogen atmosphere refluxed 10hrs.Boil off acetone, water layer is used dichloromethane extraction, and anhydrous magnesium sulfate drying is used in extracting solution washing back, by silica gel column chromatography separate white needle-like crystals (yields:71%).mp：171.5℃，MS—EI(m/e)：484(100.00％)，527(80％)，485(30％)，528(25％)；Elementalanalysis：Calculate(％)for?C
40H
33N：C?91.04，H?6.30；N?2.65；Found：C?89.20，H?6.00，N?2.50；
1H?NMR(CDCl
3，500Hz)δ：0.30～0.37(5H，m)；0.88～0.91(2H，t)；3.44～3.47(2H，d)；7.36～7.43(4H，m)；7.46～7.52(8H，m)；7.58～7.60(6H，q)；7.79～7.81(4H，d)；8.43～8.43(2H，d)。
(7) 9-methyl isophthalic acid, 3,6,8-four (4 '-t-butyl-phenyl) carbazole
Get the 100ml there-necked flask and add 9-butyl-1,3,6,8-tetrabromo carbazole (2mmol); 4 '-tert-butylbenzene ylboronic acid (8.8mmol), Tetrabutyl amonium bromide (TBAB) (0.4mmol), Palladous chloride (0.04mmol); The aqueous solution 20ml of yellow soda ash (24mmol), acetone 60ml is at nitrogen atmosphere refluxed 8hrs.Boil off acetone, water layer is used dichloromethane extraction, and anhydrous magnesium sulfate drying is used in extracting solution washing back, by silica gel column chromatography separate the white needles powder (0.97g, yields:68%).mp：296.9℃；MS(EI，m/z)：
1H?NMR(CDCl
3，500Hz)δ：3.89(3H，s)；7.30～7.32(2H，t)；7.44～7.46(2H，d)；7.53～7.56(2H，m)；8.16～8.17(2H，t)。
(8) 9-butyl-1,3,6,8-four (4 '-t-butyl-phenyl) carbazole
Get the 100ml there-necked flask and add 9-butyl-1,3,6,8-tetrabromo carbazole (2mmol); 4 '-tert-butylbenzene ylboronic acid (8.8mmol), Tetrabutyl amonium bromide (TBAB) (0.4mmol), Palladous chloride (0.04mmol); The aqueous solution 20ml of yellow soda ash (24mmol), acetone 60ml is at nitrogen atmosphere refluxed 8hrs.Boil off acetone, water layer is used dichloromethane extraction, and anhydrous magnesium sulfate drying is used in extracting solution washing back, by silica gel column chromatography separate white needles powder (yields:70%).mp：277.7℃；MS—EI(m/e)：751(100.00％)，361(55％)，752(50％)，368(30％)；Elemental?analysis：Calculate(％)for?C
53H
35N：C?92.81，H5.14，N?2.04，Found：C?92.46，H?5.40，N?1.97；
1H?NMR(CDCl
3，500Hz)δ：0.28～0.29(3H，d)；0.90～0.92(2H，d)；1.38～1.43(36H，q)；3.50～3.53(2H，t)；7.44～7.55(14H，m)；7.71～7.73(4H，d)；8.40～8.40(2H，d)。
(9) 9-methyl isophthalic acid, 3,6,8-four (1 '-naphthyl) carbazole
Get the 250ml there-necked flask and add 9-butyl-1,3,6,8-tetrabromo carbazole (2mmol); 1-naphthyl boric acid (8.8mmol), Tetrabutyl amonium bromide (TBAB) (0.4mmol), Palladous chloride (0.04mmol); The aqueous solution 40ml of yellow soda ash (24mmol), acetone 120ml is at nitrogen atmosphere refluxed 40hrs.Boil off acetone, water layer is used dichloromethane extraction, and anhydrous magnesium sulfate drying is used in extracting solution washing back, by silica gel column chromatography separate slightly yellowy white glass shape solid (yields:50%).
(10) 9-butyl-1,3,6,8-four (1 '-naphthyl) carbazole
Get the 250ml there-necked flask and add 9-butyl-1,3,6,8-tetrabromo carbazole (2mmol); 1-naphthyl boric acid (8.8mmol), Tetrabutyl amonium bromide (TBAB) (0.4mmol), Palladous chloride (0.04mmol); The aqueous solution 40ml of yellow soda ash (24mmol), acetone 120ml is at nitrogen atmosphere refluxed 40hrs.Boil off acetone, water layer is used dichloromethane extraction, and anhydrous magnesium sulfate drying is used in extracting solution washing back, by silica gel column chromatography separate white glass shape solid (yields:48%).
(11) 9-methyl isophthalic acid, 3,6,8-four (2 '-naphthyl) carbazole
Get the 250ml there-necked flask and add 9-butyl-1,3,6,8-tetrabromo carbazole (2mmol); 2-naphthyl boric acid (8.8mmol), Tetrabutyl amonium bromide (TBAB) (0.4mmol), Palladous chloride (0.04mmol); The aqueous solution 40ml of yellow soda ash (24mmol), acetone 120ml is at nitrogen atmosphere refluxed 40hrs.Boil off acetone, water layer is used dichloromethane extraction, and anhydrous magnesium sulfate drying is used in extracting solution washing back, separates to such an extent that have a little yellowish white powder (yields:38%) by silica gel column chromatography.
(12) 9-butyl-1,3,6,8-four (2 '-naphthyl) carbazole
Get the 250ml there-necked flask and add 9-butyl-1,3,6; 8-tetrabromo carbazole (2mmol), 2-naphthyl boric acid (8.8mmol), Tetrabutyl amonium bromide (TBAB) is (0.4mmol); Palladous chloride (0.007g, 0.04mmol), the aqueous solution 40ml of yellow soda ash (24mmol); Acetone 120ml is at nitrogen atmosphere refluxed 40hrs.Boil off acetone, water layer is used dichloromethane extraction, and anhydrous magnesium sulfate drying is used in extracting solution washing back, by silica gel column chromatography separate white powder (yields:30%).
(13) 9-methyl isophthalic acid, 3,6, the 8-four (carbazole of 9 ', 9 '-dibutyl fluorenes-2 '-yl)
Get the 100ml there-necked flask and add 9-butyl-1,3,6; 8-tetrabromo carbazole (2mmol), 9 ', 9 '-dibutyl fluorenes-2 '-ylboronic acid (8.8mmol); Tetrabutyl amonium bromide (TBAB) (0.4mmol), Palladous chloride (0.04mmol), the aqueous solution 30ml of yellow soda ash (24mmol); Acetone 90ml is at nitrogen atmosphere refluxed 30hrs.Boil off acetone, water layer is used dichloromethane extraction, and anhydrous magnesium sulfate drying is used in extracting solution washing back, by silica gel column chromatography separate white needles powder (yields:56%).
(14) 9-butyl-1,3,6, the 8-four (carbazole of 9 ', 9 '-dibutyl fluorenes-2 '-yl)
Get the 100ml there-necked flask and add 9-butyl-1,3,6; 8-tetrabromo carbazole (2mmol), 9 ', 9 '-dibutyl fluorenes-2 '-ylboronic acid (8.8mmol); Tetrabutyl amonium bromide (TBAB) (0.4mmol), Palladous chloride (0.04mmol), the aqueous solution 30ml of yellow soda ash (24mmol); Acetone 90ml is at nitrogen atmosphere refluxed 30hrs.Boil off acetone, water layer is used dichloromethane extraction, and anhydrous magnesium sulfate drying is used in extracting solution washing back, by silica gel column chromatography separate white needles powder (yields:45%).
(15) 9-methyl isophthalic acid, 3,6,8-four (4 '-xenyl) carbazole
Get the 100ml there-necked flask and add 9-butyl-1,3,6,8-tetrabromo carbazole (2mmol); 4 '-xenyl boric acid (9mmol), Tetrabutyl amonium bromide (TBAB) (0.4mmol), Palladous chloride (0.04mmol); 2M sodium carbonate solution 12ml, acetone 36ml is at nitrogen atmosphere refluxed 10hrs.Boil off acetone, water layer is used dichloromethane extraction, and anhydrous magnesium sulfate drying is used in extracting solution washing back, by silica gel column chromatography separate white needles powder (yields:76%).
(16) 9-butyl-1,3,6,8-four (4 '-xenyl) carbazole
Get the 100ml there-necked flask and add 9-butyl-1,3,6,8-tetrabromo carbazole (2mmol); 4 '-xenyl boric acid (2.5mmol), Tetrabutyl amonium bromide (TBAB) (0.4mmol), Palladous chloride (0.04mmol); 2M sodium carbonate solution 12ml, acetone 36ml is at nitrogen atmosphere refluxed 10hrs.Boil off acetone, water layer is used dichloromethane extraction, and anhydrous magnesium sulfate drying is used in extracting solution washing back, by silica gel column chromatography separate white needles powder (yields:79%).
(17) 9-methyl isophthalic acid, 3,6,8-four (9 '-ethyl-carbazole-2-yl) carbazole
Get the 100ml there-necked flask and add 9-methyl isophthalic acid, 3,6,8-tetrabromo carbazole (2mmol); 9 '-ethyl-carbazole-2-ylboronic acid (8mmol), Tetrabutyl amonium bromide (TBAB) (0.4mmol), Palladous chloride (0.04mmol); 2M sodium carbonate solution 12ml, acetone 36ml is at nitrogen atmosphere refluxed 10hrs.Boil off acetone, water layer is used dichloromethane extraction, and anhydrous magnesium sulfate drying is used in extracting solution washing back, by silica gel column chromatography separate white needles powder (yields:59%).
(18) 9-butyl-1,3,6,8-four (9 '-ethyl-carbazole-2-yl) carbazole
Get the 100ml there-necked flask and add 9-butyl-1,3,6,8-tetrabromo carbazole (2mmol); 9 '-ethyl-carbazole-2-ylboronic acid (8mmol), Tetrabutyl amonium bromide (TBAB) (0.4mmol), Palladous chloride (0.04mmol); 2M sodium carbonate solution 12ml, acetone 36ml is at nitrogen atmosphere refluxed 10hrs.Boil off acetone, water layer is used dichloromethane extraction, and anhydrous magnesium sulfate drying is used in extracting solution washing back, by silica gel column chromatography separate white needles powder (yields:40%).
(19) 9-butyl-1,3,6,8-four (3 ', 5 '-phenylbenzene-phenyl) carbazole
Get the 100ml there-necked flask and add 9-butyl-1,3,6,8-tetrabromo carbazole (2mmol); 3 ', 5 '-phenylbenzene-phenyl-boron dihydroxide (9mmol), Tetrabutyl amonium bromide (TBAB) (0.4mmol), Palladous chloride (0.04mmol); 2M sodium carbonate solution 12ml, acetone 36ml is at nitrogen atmosphere refluxed 10hrs.Boil off acetone, water layer is used dichloromethane extraction, and anhydrous magnesium sulfate drying is used in extracting solution washing back, by silica gel column chromatography separate white needles powder (yields:63%).
(20) 9-butyl-1,3,6,8-four (thiophene-2-yl) carbazole
Get the 100ml there-necked flask and add 9-butyl-1,3,6,8-tetrabromo carbazole (2mmol); Thiophene-2-base (12mmol), Tetrabutyl amonium bromide (TBAB) (0.4mmol), Palladous chloride (0.04mmol); 2M sodium carbonate solution 12ml, acetone 36ml is at nitrogen atmosphere refluxed 20hrs.Boil off acetone, water layer is used dichloromethane extraction, and anhydrous magnesium sulfate drying is used in extracting solution washing back, by silica gel column chromatography separate white needles powder (yields:33%).
Claims (4)
1. one kind contains 9-alkyl-1,3,6, and 8-four aryl substituted carbazole derivative blue electroluminescent materials is characterized in that having following structure:
R is a methyl; Ethyl; N-propyl; Normal-butyl; N-pentyl; N-hexyl; N-heptyl; N-octyl;
The 2-ethylhexyl; N-nonyl; Positive decyl; Benzyl;
Ar is a phenyl; The 2-tolyl; The 3-tolyl; The 4-tolyl; The 4-tert-butyl-phenyl; The 4-xenyl;
The 1-naphthyl; The 2-naphthyl; 9,9-dimethyl fluorene-2-base; 9,9-dibutyl fluorenes-2-base; 9,9-dihexyl fluorenes-2-base; 9,9-two (2 '-ethylhexyl) fluorenes-2-base; 9-methyl carbazole-3-base; 9-ethyl carbazole-3-base; 9-butyl carbazole-3-base; 9-hexyl carbazole-3-base; 9-(2-ethylhexyl) carbazole-3-base.
2. electroluminescent material as claimed in claim 1 is characterized in that: R is a methyl, butyl; Ar is a phenyl, 4-tert-butyl-phenyl, 4-xenyl, 1-naphthyl; The 2-naphthyl; 9,9-dibutyl fluorenes-2-base.
3. electroluminescent material as claimed in claim 1 is characterized in that: said electroluminescent material under UV-irradiation, its solution blue light-emitting, its film and solid blue light-emitting.
4. the application of electroluminescent material as claimed in claim 1 in Organic Light Emitting Diode.
Priority Applications (1)
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| WO2016190501A1 (en) * | 2015-05-22 | 2016-12-01 | 삼성에스디아이 주식회사 | Compound for organic optoelectronic diode, composition for organic optoelectronic diode, and organic optoelectronic diode and display device comprising same |
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| US9461250B2 (en) | 2009-12-28 | 2016-10-04 | Nippon Steel & Sumikin Chemical Co., Ltd. | Organic electroluminescent device |
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| KR20130121479A (en) * | 2012-04-27 | 2013-11-06 | 롬엔드하스전자재료코리아유한회사 | Novel organic electroluminescent compounds and organic electroluminescent device comprising the same |
| KR102282551B1 (en) | 2013-09-04 | 2021-07-27 | 이데미쓰 고산 가부시키가이샤 | Carbazole derivative, material for organic electroluminescent element which comprises same, and organic electroluminescent element and electronic device each manufactured using same |
| JP2015127313A (en) * | 2013-12-27 | 2015-07-09 | 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． | Carbazole compound and organic light-emitting element |
| US10396294B2 (en) * | 2013-12-27 | 2019-08-27 | Samsung Electronics Co., Ltd. | Carbazole compound and organic light-emitting device including the same |
| KR101818582B1 (en) | 2014-11-04 | 2018-01-15 | 삼성에스디아이 주식회사 | Compound for organic optoelectric device, organic optoelectric device and display device |
| CN106803542B (en) | 2017-01-16 | 2019-02-12 | 中国科学院长春应用化学研究所 | A kind of blue organic electroluminescent device and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1488707A (en) * | 2003-08-13 | 2004-04-14 | 复旦大学 | Blue organic electroluminescent material and preparing method thereof |
| CN1701111A (en) * | 2002-03-22 | 2005-11-23 | 出光兴产株式会社 | Material for organic electroluminescent device and organic electroluminescent device using the same |
-
2007
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1701111A (en) * | 2002-03-22 | 2005-11-23 | 出光兴产株式会社 | Material for organic electroluminescent device and organic electroluminescent device using the same |
| CN1488707A (en) * | 2003-08-13 | 2004-04-14 | 复旦大学 | Blue organic electroluminescent material and preparing method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016190501A1 (en) * | 2015-05-22 | 2016-12-01 | 삼성에스디아이 주식회사 | Compound for organic optoelectronic diode, composition for organic optoelectronic diode, and organic optoelectronic diode and display device comprising same |
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