CN104326980A - 9,9'- connected host material based on 4,4'-difluorene structure and application thereof - Google Patents

9,9'- connected host material based on 4,4'-difluorene structure and application thereof Download PDF

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CN104326980A
CN104326980A CN201410471700.9A CN201410471700A CN104326980A CN 104326980 A CN104326980 A CN 104326980A CN 201410471700 A CN201410471700 A CN 201410471700A CN 104326980 A CN104326980 A CN 104326980A
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host material
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hydrogen
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CN104326980B (en
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杨楚罗
刘腾霄
樊聪
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Wuhan University WHU
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Abstract

A 9,9'- connected host material based on a 4,4'-difluorene structure and an application thereof. The invention discloses a host material which has high triplet state and HOMO energy level and has excellent performance. According to the host material, 4,4'- connected difluorene structure is used as a molecular skeleton, and a substituent group is connected at 9,9'- site. Diphenylamine element Dn with hole transport performance can be connected, and An element with electron-transport performance also can be connected, wherein the An element contains an oxygen-phosphorus element and a sulfur-oxygen element; and in addition to the oxygen-phosphorus element and the sulfur-oxygen element, a special spiral structure also can be formed. A synthetic method of the host material is simple and practicable, and the host material is suitable for wide application. An organic electroluminescence blue phosphorescent luminescent device made of the host material has high efficiency, high brightness, low extinction efficiency and electroluminescence performance of low starting voltage, and can widely be applied in the field of organic electroluminescence.

Description

Based on 4,4 '-Lian two fluorene structured 9, the material of main part that 9 '-position connects and application thereof
Technical field
The present invention relates to a class based on 4,4 '-Lian two fluorene structured 9, the material of main part that 9 '-position connects and application thereof,
Belong to field of light emitting materials.
Background technology
Prepared with Alq by vacuum deposition method from people's reported first such as Kodak C.W.Tang in 1987 3since bi-layer devices structure for luminescent material, organic electroluminescent just obtains the very big concern of people.Organic electroluminescent can be divided into fluorescence and phosphorescence electroluminescent, and the electroluminescent of phosphor material can utilize the energy of whole exciton, has larger superiority.
Mostly adopt Subjective and Objective structure in present electrophosphorescence device, by phosphorescent emissions material with certain doped in concentrations profiled in main substance, to avoid burying in oblivion of concentration quenching and triplet state-triplet state, improve phosphorescent emissions efficiency.
(R.J.Holmes, S.R.Forrest, the Y.-J.Tung such as Forrest and Thompson in 2003, R.C.Kwong, J.J.Brown, S.Garon, M E Thompson, Appl.Phys.Lett.2003,82,2422) by sky blue phosphor material FIrpic with the doped in concentrations profiled of 6wt% 3,5-N, in the material of main part of N '-two carbazoles-benzene (mCP), the maximum external quantum efficiency of Nan dian Yao of acquisition reaches 7.5%, and power efficiency reaches 7.9lm/W.
(S.Tokito, T.Iijima, the Y.Suzuri such as Tokito in 2003, H.Kita, T.Tsuzuki, F.Sato, Appl.Phys.Lett.2003,83,569) FIrpic is entrained in 4,4 '-two (9-carbazole)-2,2 '-dimethyl-biphenyl, obtain the maximum external quantum efficiency of device and reach 10.4%, power efficiency reaches 10.5lm/W.
In recent years, the electrophosphorescence device of green glow and ruddiness obtains and can be used in practical high-level efficiency; But the development of the sky blue photoelectricity phosphorescent device of stabilised efficiency then relatively lags behind.Wherein, one of important reason is exactly lack the material of main part simultaneously with high triplet and high HOMO value.2009 Nian Jiang Zuoquan etc. report (Jiang, Z.; Xu, X.; Zhang, Z.; Yang, C.; Liu, Z.; Tao, Y.; Qin, J.; Ma, D.J.Mater.Chem.2009,19,7661.) material of main part of the bigeminy spiral shell fluorenes connected based on part ortho position, but due to the lower (E of its triplet state t=2.55eV), so can only be used as green glow main body, Fan Cong etc. report again (Fan, C. afterwards; Chen, Y.; Gan, P.; Yang, C.; Zhong, C.; Qin, J.; Ma, D.Org.Lett.2010,12,5648.) based on 4,4 '-two bromo-9, the sky Blue-light emitting host material of 9 '-spiral shell fluorenes, but because the too low frontier orbit of luminescent layer that makes of HOMO (HOMO=-6.08eV) value does not mate with adjacent layer, cause device trigger voltage very high (4.5V), external quantum efficiency is also lower, and best external quantum efficiency also only has 11.6%.
Feed back to the triplet of material of main part in order to prevent energy from FIrpic exciton (triplet is 2.65eV), then based on the triplet of the material of main part of FIrpic blue-light device generally higher than 2.75eV, and most of material of main part also makes HOMO value become very low while maintenance is compared with high triplet, like this will be too low and cause energy transmission efficiency to decline due to HOMO energy level, thus reduce the efficiency of device.Thus there is high triplet (E simultaneously t>2.75eV), and the material of main part of HOMO value (HOMO>-5.6eV) has very great meaning in OLED, compared to (Sasabe, H. such as convention body material mCP; Toyota, N.; Nakanishi, H.; Ishizaka, T.; Pu, Y.J.; Kido, J.Adv.Mater.2012,24,3212.) its maximum external quantum efficiency only has 16.6%, and along with the raising of current density, and its external quantum efficiency declines also obvious (13.8%, 1000cd/m 2)
Based on the body making of this characteristic OLED often acquisition higher external quantum efficiency while, keep lower trigger voltage.And compared to the material reported, as SiBSTPA etc., (Fan, C.; Chen, Y.; Liu, Z.; Jiang, Z.; Zhong, C.; Ma, D.; Qin, J.; Yang, C.Journal of Materials Chemistry C2013, Isosorbide-5-Nitrae 63), its external quantum efficiency only has 10%, and at 1000cd/m 2its current efficiency lower only has 12.8cd/A, and power efficiency only has 5.2lm/W, and by contrast, the OLED made based on this patent material of main part still can keep higher efficiency (16.2%, 34.5cd/A, 22lm/W at higher current densities; 1000cd/m 2), so just make this kind of device have more actual application value standby.
Summary of the invention
The problem to be solved in the present invention is for the deficiencies in the prior art, provides a kind of blue emitting phosphor material of main part simultaneously possessing high triplet energy level and higher HOMO energy level.
The technical solution used in the present invention is:
The spiral shell fluorenes type material of main part of one organic electrofluorescent luminescence, molecule is with 4, connection two Fluorenone in 4 '-position is skeleton, its 9,9 '-position connects substituting group, and described substituting group both can be the diphenylamine cells D n with hole transport performance, can be again there is electronic transmission performance An as oxygen phosphorus unit, sulphur oxygen unit, can also form special Spirocyclic structure except both, general structure is shown below:
In described formula (I), R 1and R 2be selected from formula (1) respectively to group formula (4) Suo Shi
In described formula (II) and described formula III, Ar 1and Ar 2independently be selected from formula (5) to group formula (12) Suo Shi
The invention still further relates to a kind of organic electro-phosphorescent luminescent device, comprise glass, be attached to the Conducting Glass layer on glass, the hole injection layer closed with Conducting Glass laminating, the hole transmission layer of fitting with hole injection layer, the luminescent layer of fitting with hole transmission layer, the electron transfer layer of fitting with luminescent layer, the cathode layer of fitting with electron transfer layer, luminescent layer is made up of material of main part and dopant material, the material of main part of luminescent layer is the compound described in formula (I/II/III), dopant material is the common complex of iridium FIrpic of light (send out dark blue) with cyclic metal complexes, doping ratio: FIrpic is 10w.t.% (complex of iridium/material of main part).
Material of main part of the present invention is applied in electro phosphorescent device, can obtain efficient electroluminescent properties.The present invention take FIrpic as blue light electro phosphorescent device prepared by object, maximum luminous efficiency can reach 42 Kan Tela every ampere, maximum lumen efficiency is 41 lumen per Watt, maximum external quantum efficiency position 19.1%, simultaneously under 1000 Kan Tela every square metre, device still maintains high stability, and external quantum efficiency still remains on 16.2%.As can be seen here, the present invention has useful technique effect.
Accompanying drawing explanation
Fig. 1: the embodiment of the present invention 1 gained material of main part 10,10'-phenylbenzene-4', 4 " ' the uv-visible absorption spectra figure of-bis-spiral shell [acridine-9,9'-fluorenes] and the luminous spectrogram of low temperature 77k phosphorescence.
Fig. 2: organic electro-phosphorescent luminescent device structural representation of the present invention.
Fig. 3: the electroluminescent emmission spectrum of organic electro-phosphorescent luminescent device of the present invention.
Embodiment
Below by specific embodiment, the present invention is further illustrated, its object is to help better to understand content of the present invention, but the protection domain that these specific embodiments do not limit the present invention in any way.The present embodiment raw material used is known compound, and can commercially buy, all the other several important intermediates can synthesize by following method:
The synthesis of embodiment 110-phenyl-10 hydrogen-spiral shell [acridine-9,9'-fluorenes]-4-ylboronic acid tetramethyl ethylene ketone boric acid ester (being called for short intermediate 1)
The synthesis of intermediate (A)
Under Ar gas shielded, in 200ml Shiran gram bottle, add adjacent bromine triphenylamine (1.6g; 5mmol), anhydrous and oxygen-free tetrahydrofuran (THF) 60ml, subcooling, to-78 DEG C, instills 3ml n-Butyl Lithium (2M; 6mmol), react under low temperature after 1 hour, the bromo-9-Fluorenone of 4-(1.2 g that under instillation Ar gas shielded, anhydrous and oxygen-free tetrahydrofuran (THF) dissolves; 5mmol), stirred overnight at room temperature is taken out after continuing low-temp reaction 1h.Then with saturated ammonium chloride solution cancellation reaction, anhydrous sodium sulfate drying.After Rotary Evaporators steams solvent, remaining solid uses acetate dissolution, and 120 DEG C of backflows, add 1ml concentrated hydrochloric acid, takes out, poured into by solution in frozen water, obtain light green solid after reaction 12h.Dichloromethane extraction, Rotary Evaporators is except desolventizing, and column chromatography purification is separated.Obtain white solid 1.0g (53%)
Under Ar gas shielded, the Isosorbide-5-Nitrae of 40ml anhydrous and oxygen-free '-dioxane is by intermediate product A (1.4g; 3mmol), Glacial acetic acid potassium (0.7g; 5mmol), Pd (dppf) 2cl 2(0.057g, 0.25mmol), two borane reagent (1g; 5mmol).Then Isosorbide-5-Nitrae-dioxane the 40ml of the deoxygenation that dewaters is added, back flow reaction 24h at 110 DEG C.Rotary Evaporators solvent evaporated, thick product obtains intermediate 1 after carrying out purifying by column chromatography: white solid product 0.9g (75%).
The synthesis of the adjacent bromine triphenylphosphine oxide of synthesis of embodiment 24'-bromo-5-phenyl spiral shell [phosphine-10,9' fluorenes] 5-oxide compound (being called for short intermediate product B)
Under Ar gas shielded, in 200ml Shiran gram bottle, add o-dibromobenzene (1.2g; 5mmol) dewater with 40ml deoxygenation tetrahydrofuran (THF), is cooled to 0 DEG C in ice bath.Instillation grignard reagent 4ml (1.8M; 7.2mmol), after low-temp reaction 1h, instillation diphenyl phosphorus chloride (0.7ml; 6mmol), after continuing maintenance 0 DEG C reaction 1h, take out room temperature reaction and spend the night.Saturated ammonium chloride solution cancellation, after solvent steams by Rotary Evaporators, column chromatographic isolation and purification obtains adjacent bromine triphenylphosphine oxide 0.8g (58%) of product.
Use adjacent bromine triphenylphosphine oxide to replace adjacent bromine triphenylamine, adopt the synthesis condition consistent with intermediate A and step, finally obtain adjacent bromine triphenylphosphine oxide: faint yellow solid product 1g (55%).
Embodiment 34-(4-tetramethyl ethylene ketone boric acid fat-9 hydrogen-fluorenes-9-base)-nitrogen, the synthesis of nitrogen-phenylbenzene aniline (being called for short intermediate 2)
The synthesis of intermediate product C
Under nitrogen protection, by bromo-for 4-triphenylamine (1.6g; 5mmol) put into 200ml Shiran gram bottle, then add 40ml ether, put into low-temp reaction device and be cooled to-78 DEG C, instillation n-Butyl Lithium 3ml (2M; 6mmol), after low-temp reaction 1h, by the bromo-9-Fluorenone (1.3g of 4-be dissolved in anhydrous and oxygen-free ether; 5mmol) slowly instill in Shiran gram bottle, take out after reaction 1h.Slowly return to room temperature, in reaction flask, pass into dry ammonia (200ml), gas device is removed, adds lithium silk 200mg, after reaction 0.5h, open bottleneck and make Ammonia valatilization.Residual solvent uses saturated ammonium chloride cancellation, extraction into ethyl acetate, and Rotary Evaporators, by solvent evaporate to dryness, remains thick product column chromatography and carries out purifying and obtain intermediate product C product 1g (49%)
Use intermediate C to replace intermediate A, carry out boration reaction, step is identical with 10-phenyl-10 hydrogen-spiral shell [acridine-9,9'-fluorenes]-4-ylboronic acid tetramethyl ethylene ketone boric acid ester, obtains intermediate 2 white solid product 1.1g (53%)
The synthesis of embodiment 4 (4-(4 – tetramethyl ethylene ketone boric acid fat-9 hydrogen-fluorenes-9-base) phenyl) diphenyl phosphine oxide (being called for short intermediate 3)
The synthesis of intermediate D
Change o-dibromobenzene into paradibromobenzene, adopt the synthesis step as intermediate product B.
The bromo-triphenylphosphinc oxide of 4-will be changed into bromine triphenylamine, and adopt the synthesis step identical with intermediate C, obtain white solid E900mg (45%).
With intermediate product E for raw material, adopt the method for the boric acid of synthesis shown in embodiment 1 fat, obtain faint yellow solid intermediate 3:700mg (68%).
The synthesis of embodiment 59-(4-tosyl group phenyl)-9 hydrogen-fluorenes-4-tetramethyl ethylene ketone boric acid fat (being called for short intermediate 4)
The synthesis of intermediate product F
Under Ar gas shielded, in 150ml round-bottomed flask, add adjacent bromo-iodobenzene (1.5g; 5mmol), cuprous iodide (1g; 5mmol), DMAC40ml, 170 DEG C of back flow reaction 24h, after being cooled to room temperature, underpressure distillation is except desolventizing.Remaining solid methylene dichloride is dissolved, adds mCPBA and be oxidized.After reaction 5h, Rotary Evaporators is except desolventizing, and the thick product of column chromatography purification, obtains product Intermediate F white solid 1g (61%).
The synthesis of intermediate product G
Use F as raw material, step, with reference to synthesis C, E, obtains intermediate product G white solid 1.2g (54%)
Take G as raw material, step, with reference to embodiment 1 boric acid fat synthetic method, finally obtains product intermediate 4 white solid 1g (56%).
The synthesis of embodiment 6 substituting group (10)
1, in 150ml round-bottomed flask, p t butylbenzoic acid (1.78g is added; 10mmol), 40ml methyl alcohol, the 1ml vitriol oil, after reaction is spent the night, Rotary Evaporators removing excess of solvent, residue oily liquids uses chloroform to dissolve, and adds hydrazine hydrate 10ml, takes out after normal-temperature reaction 48h, suction filtration, obtain solid 1.6g (80%).
2, in 150ml round-bottomed flask, parabromobenzoic acid (2g is added; 10mmol), sulfur oxychloride 30ml, takes out after back flow reaction 24h, underpressure distillation removing sulfur oxychloride.
3, add in 150ml round-bottomed flask by the solid obtained in 1 and 2, use chloroform to dissolve, take out after reaction 48h, Rotary Evaporators is except desolventizing.
4, under Ar gas shielded, add aniline 2ml, phosphorus trichloride 1ml at 10ml two mouthfuls of round-bottomed flasks, after 100 DEG C of reaction 2h, add the solid obtained in 3,180 DEG C of back flow reaction 24h.Underpressure distillation removing excess of solvent, thick product obtains substituting group (10) white solid 800mg (25%) by column chromatography purification.The synthesis of embodiment 7 substituting group (11)
Under Ar gas shielded, by bromo-for 4-pyridine (1.5g; 10mmol) put into 200ml Shiran gram bottle, adding 40ml anhydrous and oxygen-free tetrahydrofuran (THF), putting into low-temp reaction device and be cooled to-78 DEG C, instillation butyllithium 5ml (2.2M; 11mmol), after reaction 1h, add 4ml first class boric acid fat, take out after low-temp reaction 1h and spend the night.Use the dilute hydrochloric acid cancellation reaction of 2mol/L, after normal hexane recrystallization, obtain product 0.8g (0.8g, productive rate 65%).
Under Ar gas shielded, using intermediate product H as raw material (620mg; 5mmol), add in 50ml two mouthfuls of flasks, add paradibromobenzene (1.2g; 5mmol), 10mgPd (PPh 3) 4, Anhydrous potassium carbonate (1.38g; 10mmol), 5ml deoxygenation distilled water, 40ml anhydrous and oxygen-free toluene, 110 DEG C of back flow reaction 48h.Saturated ammonium chloride solution cancellation is reacted, extraction into ethyl acetate.Thick product except dry, then use column chromatography purification to be separated and obtains substituting group (11) white solid 700mg (61%) by Rotary Evaporators by solvent.
(4-(9-(4-(9 hydrogen-carbazole-9-base) phenyl-4-boric acid fat-9 hydrogen-fluorenes-9-base) phenyl) diphenyl phosphine oxide is called for short the synthesis of intermediate 5 to embodiment 8
1、
Under Ar gas shielded, in 200ml Shiran gram bottle, add adjacent bromine triphenylamine (1.6g; 5mmol), anhydrous and oxygen-free tetrahydrofuran (THF) 60ml, subcooling, to-78 DEG C, instills 3ml n-Butyl Lithium (2M; 6mmol), react under low temperature after 1 hour, the bromo-9-Fluorenone (1.2g of 4-that under instillation Ar gas shielded, anhydrous and oxygen-free tetrahydrofuran (THF) dissolves; 5mmol), stirred overnight at room temperature is taken out after continuing low-temp reaction 1h.Then with saturated ammonium chloride solution cancellation reaction, anhydrous sodium sulfate drying.After Rotary Evaporators steams solvent, column chromatography is crossed post separation and is obtained product 1.1g (50%).
2、
Under Ar gas shielded, the bromo-triphenylphosphine (1.38g of 4-; 5mmol) add in 100ml round-bottomed flask, trimethylchlorosilane (6mmol), then add anhydrous and oxygen-free tetrahydrofuran (THF) 40ml, boron trifluoride (400mg; 6mmol), triphenyl (131mg; 5mmol), after back flow reaction 24h, Rotary Evaporators solvent evaporated, hydrogen peroxide oxidation after remaining solid dissolves with methylene dichloride.Separating funnel separatory, dichloromethane extraction, solvent evaporate to dryness, thick product is crossed post and is obtained faint yellow solid product 700mg (48%) mg.
3, the synthesis of intermediate compound I
Under Ar gas shielded, use solid phase prod 1g (2.5mmol), deoxygenation methylene dichloride 30ml, solid phase prod (700mg in 2 in 1; 0.25mmol), boron trifluoride (200mg; 3mmol), after reacting 2h under ice bath, except desolventizing, thick product column chromatography purification obtains product Intermediate I faint yellow solid 1g (56%).
4, by products obtained therefrom (1.5g in 3; 2mmol) boric acid preparation method as implied above, obtains product intermediate 5 white solid product 1.2g (70%).
Embodiment 9:10,10'-phenylbenzene-4', 4 " ' the preparation of-bis-spiral shell [acridine-9,9'-fluorenes] (NSF-NSF) (be abbreviated as Host1, structural formula is as follows)
Intermediate A (1g, 2mmol) and intermediate 1 (1.1g, 2.06mmol) are put into 100ml two mouthfuls of round-bottomed flasks, then add anhydrous Na successively 2cO 3(1.06g, 10mmol), Pd (PPh 3) 4(52mg, 4mmol), finds time logical argon gas repeatedly after three times, adds anhydrous and oxygen-free toluene 40ml successively, deoxygenation distilled water 6ml, 110 DEG C of back flow reaction 48 hours.The cancellation of 20ml saturated aqueous ammonium chloride, dichloromethane extraction, anhydrous sodium sulfate drying.Silica gel column chromatography is separated, and methylene dichloride/sherwood oil (v:v)=1:2, as eluent, obtains product Host1 white solid.Productive rate: 56%.Elemental Analysis theory C 38h 32n 2(%): C83.04, H5.87, N2.55. discovery value: C82.73, H6.02, N2.13.
Embodiment 10:4'-(9,9'-spiral shell two [fluorenes] pyrimidine-4-yl-10-phenyl-10 hydrogen-spiral shell [acridine-9,9'-fluorenes] (NSF-SF) is abbreviated as Host2, and structural formula is as follows:
Intermediate 9,9-spiral shell two fluorenes-4-ylboronic acid tetramethyl ethylene ketone boric acid ester (800mg, 1.96mmol) is replaced intermediate 1, carries out Suzuki reaction with intermediate A (1g, 2mmol) according to embodiment, obtain product Host2: white solid.Productive rate: 52%.Element theory analytical value: C 56h 35n (%): C93.17, H4.89, N1.94. discovery value: C93.12, H4.75, N1.81.
The preparation of embodiment 11:5-phenyl-4'-(10-phenyl-10H-spiral shell [a word used for translation-9,9'-fluorenes succinyl]-Ji) spiral shell [phosphine-10,9' fluorenes] 5-oxide compound (NSF-POSF) (be abbreviated as Host3, structural formula is as follows)
Intermediate product B (1.2g, 2mmol) and intermediate product 1 (1.1g, 2.06mmol) are carried out Suzuki reaction, obtains product Host3 white solid.Productive rate: 56%.Elemental Analysis theory C 38h 32nOP (%): C88.03, H4.77, N1.66, P3.66, O1.89. discovery value: C87.98, H4.75, N1.63, O1.80.
Embodiment 12:5,5'-phenylbenzene-4', 4 " ' the preparation of-bis-spiral shell [phosphine-10,9' fluorenes] 5,5'-dioxide (POSF-POSF) (write a Chinese character in simplified form into Host4, structural formula is as follows).
Boric acid fat (the 1.3g that intermediate product B (1.2g, 2mmol) and B is produced; 2mmol) carry out Suzuki reaction, obtain product Host4 faint yellow solid product 800mg (56%) Elemental Analysis theory C 62h 40o 2p 2(%): C84.72, H4.59, O3.64, P7.05. discovery value C84.69, H4.49, O3.62.
Two (4 – (9 hydrogen-carbazole-9-base) phenyl)-9 hydrogen of embodiment 13:9,9'-, the preparation of 9' hydrogen-4,4'-difluorene (49BFBCz) (be abbreviated as Host5, structural formula is as follows)
By intermediate C (1g; 2.1mmol) with intermediate 2 (1.1g; 2mmol) carry out Suzuki reaction, obtain product Host5 white solid product 800mg (49%).Element theory analytical value: C 50h 32n 2(%): C90.88, H4.88, N4.24. discovery value: C90.26, H4.79, N4.15.
Embodiment 14:(4-(9'-(4-(9 hydrogen-carbazole-9-base) phenyl-9 hydrogen 9' hydrogen-[4,4'-difluorene]-9-base) phenyl) preparation of diphenyl phosphine oxide (9DPOBFCz) (be abbreviated as Host6, skeleton symbol is as follows):
With intermediate 2 (1.1g; 2mmol) with intermediate E (1g; 2mmol) be raw material, carry out Suzuki reaction, obtain product Host6 white solid product 600mg (38%).Element theory analytical value: C 62h 42nOP (%): C87.82, H4.99, N1.65, O1.89, P3.65. discovery value: C87.78, H4.87, N1.62, O1.84. embodiment 15:(9 hydrogen, 9' hydrogen-[4,4-difluorene]-9,9'-bis-bases two (4,1-phenylene)) synthesis of two (diphenyl phosphine oxide) (being abbreviated as Host7)
With intermediate 3 (1.2g; 2mmol) with intermediate F (1.1g; 2mmol) be raw material, carry out Suzuki reaction, obtain product Host7 faint yellow solid 700mg (42%).Element theory analytical value C 62h 44o 2p 2(%): C84.34, H5.02, O3.62, P7.02. discovery value: C84.36, H4.88, O3.52.
Embodiment 16:4-(9'-(4-(5 (4-(tertiary butyl) phenyl)-4-phenyl-4 hydrogen-1,2,4-triazole-3-base) phenyl)-9 hydrogen-, 9' hydrogen-[4, the two fluorenes of 4'-]-9-base)-nitrogen, the synthesis of nitrogen-phenylbenzene aniline (being abbreviated as Host8).
Utilize substituting group (10), adopt the step and method synthetic intermediate G (1.2g identical with intermediate C; 2mmol), with intermediate 2 (1.1g; 2mmol) react, obtain product Host8 faint yellow solid 650mg (39%).Elemental analysis value C 68h 52n 4(%): C88.28, H5.67, N6.06. discovery value: C87.98, H5.47, N6.16.
The synthesis (being abbreviated as Host9) of embodiment 17:N ,-phenylbenzene-4-(9'-(4-tosyl group phenyl)-9 hydrogen-, 9' hydrogen-[4,4-two fluorenes]-9-base) aniline
With intermediate 2 (1.1g; 2mmol) with intermediate G (1g; 2mmol) carry out Suzuki reaction, obtain product Host9 white solid 750mg (47%).Elemental analysis value C 57h 41nO 2s (%): C85.15, H5.14, N1.74, O3.98, S3.99. discovery value: C84.75, H5.24, N1.68, O3.88, S3.93
Embodiment 18: nitrogen, the synthesis (being abbreviated as Host10) of-phenylbenzene-4-(9'-(4-(pyridin-4-yl) phenyl)-9 hydrogen-, 9' hydrogen-[4,4-two fluorenes]-9-base) aniline
With substituting group (11), adopt the method synthetic intermediate H (1g identical with intermediate C; 2.5mmol), with intermediate 2 (1.1g; 2mmol) carry out Suzuki reaction, obtain product Host10 white solid 780mg (51%).Elemental analysis value C 57h 38n 2(%): C90.88, H5.27, N3.85. discovery value: C90.58, H5.17, N 3.65.
Embodiment 19:((9,9 '-bis-(4-(9 hydrogen-carbazole-9-base) phenyl)-(9,9 '-bis-(4-(9 hydrogen-diphenylphosphine-9-base) phenyl))-9 hydrogen, 9 ' hydrogen-[4,4 '-Lian fluorenes] synthesis of (BFD9PO9Cz) (be abbreviated as Host11, structural formula is as follows):
By intermediate 5 (1.5g; 2mmol) with intermediate compound I (1.6g; 2mmol) carry out Suzuki reaction, obtain product Host11 white solid 900mg (31%).Elemental analysis value C 98h 66n 2o 2p 2(%): C86.20, H4.87, N2.05, O2.34, P4.54. discovery value: C86.10, H4.67, N2.03, O2.31, P4.48.
Embodiment 20:((9', two (4-(9 hydrogen-carbazole-9-base) phenyl)-9 hydrogen of 9'-, 9' hydrogen-[4,4'-fluorenes]-9,9-bis-base) two (4,1-phenylene)) synthesis of two (diphenyl phosphine oxide) (BFDPOCz) (be abbreviated as Host12, skeleton symbol is as follows):
According to the synthetic method of embodiment 8, synthesize ((4-bromo-9 hydrogen-fluorenes-9,9-bis-base) two (4,1-phenylene)) two (diphenyl phosphine oxide) (1.6g respectively; 2mmol) and 9,9'-(4 – boric acid fat-2-base)-9 hydrogen-fluorenes-9,9-bis-base) two (4,1-phenylene)) two (9 hydrogen-carbazole) (1.6g, 2mmol) carry out Suzuki reaction, obtain white solid 800mg (25%).Elemental analysis value: C 98h 66n 2o 2p 2(%): C86.20, H4.87, N2.05, O2.34, P4.54. discovery value: C86.14, H4.77, N2.10, O2.35, P4.46.
Embodiment 21:4,4', 4', 4 " ' the synthesis (being abbreviated as Host13) of-(9 hydrogen, 9' hydrogen-[4,4-difluorene]-9,9,9', 9'-tetra-base) four (nitrogen, nitrogen-phenylbenzene aniline)
Boric acid fat (the 1.6g of 4,4'-(4-bromo-9-fluorenes-9,9-bis-base) two (nitrogen, nitrogen-phenylbenzene aniline) (1.5g, 2mmol) and correspondence thereof; 2mmol) carry out Suzuki reaction, obtain product Host13 white solid 850mg (27%).Elemental analysis value: C 98h 70n 4(%): C90.29, H5.41, N4.30. discovery value: C89.89, H5.34, N4.19.
Embodiment 22:(9 hydrogen, 9' hydrogen-[4,4-difluorene]-9,9,9', 9'-tetra-base four (benzene-4,1-bis-base)) synthesis of four (diphenyl phosphine oxides) (is abbreviated as (Host14)
((4-bromo-9 hydrogen-fluorenes-9,9-bis-base) two (4,1-phenylene)) two (diphenyl phosphine oxide) (1.6g; 2mmol) and the boric acid fat (1.7g of correspondence; 2mmol) carry out Suzuki reaction, obtain product Host14 white solid 790mg (26%).Elemental analysis value: C 98h 70o 4p 4(%): C82.00, H4.92, O4.46, P8.63. discovery value: C81.80, H4.72, O4.38, P8.55.
The preparation of embodiment 23 electro phosphorescent device
As shown in Figure 3, bipolar carrier transmission material of the present invention, as the electro phosphorescent device of luminescent layer main body, comprises glass and conductive glass (ITO) substrate layer 1, hole injection layer 2 (molybdic oxide MoO 3), hole transmission layer 3 (1, two [(two-4-Tolylamino) phenyl]-hexanaphthene TAPC of 1-), luminescent layer 4 (material of main part prepared by Host1, Host2 and Host3 and doping phosphorescent iridium complex FIrpic), electron transfer layer 5 (1,3,5-tri-(m-pyridyl-3-) phenyl benzene Tm), cathode layer 6 (lithium fluoride/aluminium).
Electroluminescent device makes by means known in the art, makes as pressed the disclosed method of reference (Adv.Mater.2004,16,537.).Concrete grammar is: in high vacuum conditions, is passing through the MoO of evaporation 10nm successively on conductive glass (ITO) substrate cleaned 3, the luminescent layer of the TAPC of 60nm, 20nm, the Al of LiF and 120nm of the Tm of 35nm, 1nm.Obtain device as shown in Figure 3 by the method, the structure of various device is as follows:
Device architecture:
ITO/MoO 3(10nm)/TAPC(60nm)/Hosts:FIrpic(15nm)/TmPyPB(35nm)/LiF(1nm)/Al(120nm)
Current versus brightness-the voltage characteristic of device is completed by Keithley source measuring system (Keithley2400Sourcemeter, Keithley2000Currentmeter) with corrected silicon photoelectric diode, electroluminescent spectrum is by French JY company SPEX CCD3000 spectrometer measurement, and all measurements all complete in atmosphere at room temperature.The performance data of device sees the following form:
Sky blue light launched by the device 1 of preparation, electroluminescent properties is far away higher than documents (Org.Lett.2010,12,5648.), its maximum current efficiency reaches 41cd/A, and maximum power efficiency reaches 42lm/W, it should be noted that, in embodiment 1, the triplet of material of main part NSF-NSF has 2.83eV, but its HOMO energy level only has-5.31eV, still keeps high external quantum efficiency (1000cd m at higher current densities with the electroluminescent phosphor device of this body making -2, 16.2%) and trigger voltage then only has 2.5V, is one of lowest starting voltage of the sky blue light organic electroluminescence device of report at present, (Angew.Chem.Int.Ed.2012,51,10104.).Therefore, compared with other material of main parts, the present invention is to passing through 4,9,9 '-position that the two fluorenes of the connection that connects is carried out in 4 '-position is modified, prepared one roughly the same time there is the outstanding material of main part of high triplet and high HOMO energy level and device performance, obtain excellent electroluminescent properties, comprising low start voltage, the stability under high current density and higher external quantum efficiency etc., be conducive to developing efficient full-color display.

Claims (4)

1. a material of main part for organic electroluminescence device, is characterized in that: adopt 4, and connection two fluorenes in 4 '-position is skeleton, shown in structure following (I), (II) or (III) formula:
In described formula (I), R 1and R 2independently be selected from formula (1) to group formula (4) Suo Shi
In described formula (II) and described formula (III), Ar 1and Ar 2independently be selected from formula (5) to group formula (12) Suo Shi
2. an organic electro-phosphorescent luminescent device: comprise glass, be attached to the Conducting Glass layer on glass, the hole injection layer closed with Conducting Glass laminating, the hole transmission layer of fitting with hole injection layer, the luminescent layer of fitting with hole transmission layer, the electron transfer layer of fitting with luminescent layer, the cathode layer of fitting with electron transfer layer, luminescent layer is made up of material of main part and dopant material, it is characterized in that: the material of main part of luminescent layer is material of main part according to claim 1.
3. electro phosphorescent device as claimed in claim 2, is characterized in that: dopant material is the phosphorescent iridium compound F 17-hydroxy-corticosterone Irpic sending out sky blue light.
4. electro phosphorescent device as claimed in claim 3, it is characterized in that, doping ratio is 10w.t.%.
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