CN104844661A - Donor-acceptor-donor type cyclometalated platinum complex liquid crystal luminescent material and application thereof in polymer polarized electroluminescent device - Google Patents
Donor-acceptor-donor type cyclometalated platinum complex liquid crystal luminescent material and application thereof in polymer polarized electroluminescent device Download PDFInfo
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Abstract
The invention discloses a donor-acceptor-donor type cyclometalated platinum complex liquid crystal luminescent material and application thereof in a polymer polarized electroluminescent device. According to the cyclometalated platinum complex liquid crystal luminescent material, benzophenanthrene derivative is connected to a phenylpyridine-carbazole derivative by means of conjugation or non-conjugation to form a cyclometalated ligand, and a propanedione derivative is employed to form an auxiliary ligand. The cyclometalated platinum complex is adopted as the luminescent layer doping agent, poly(9,9-dioctylfluorene) (PFO) is taken as the host material, and through rubbing alignment and heating annealing, a luminescent layer can be prepared, and the polymer polarized electrogenerated white light-emitting device with a polarization ratio of 1.32 can be obtained.
Description
Technical field
The present invention relates to a kind of donor-acceptor-donor type (D-A-D type) Cyclometalated platinum complexes liquid crystal luminescent material and the application in polymkeric substance polarization OLEDs thereof, belong to polorised electroluminescence material and Application Areas.
Background technology
Liquid-crystal display (LCD) is with its panelized, reduce power consumption, electromagnetic-radiation-free, high resolving power, high-contrast, digital interface, the advantage such as easy of integration and light, be widely used in the display such as computer monitor, televisor field, in flat-panel monitor, be in dominant position.But liquid-crystal display is a kind of passive display device, it needs to realize transmission or reflective display by backlight.Backlight is a very important integral part in liquid-crystal display, and it accounts for 20% ~ 30% of liquid crystal display device all material cost.At present, the backlight mainly cold-cathode tube light source of liquid-crystal display, and this light source is because light efficiency is low, life time is short, colour gamut performance is poor, brightness adjustment scope is little, energy consumption is large, the time of response is long, safety coefficient is low, mercurous obnoxious flavour, the defect such as not environmentally, and it is stopped using gradually.Therefore, the backlight new technology that development and Design is novel is extremely urgent.
Compared with LCD, organic/polymer electroluminescent device (OLEDs/PLEDs) has that thickness is thin, low in energy consumption, visual angle is wide, display brightness is high, fast response time, bright in luster, can the advantages such as Flexible Displays be realized, and OLEDs/PLEDs is active illuminating, does not need background light source.These advantages make OLEDs/PLEDs become a kind of very promising New flat panel display (flat panel display, FPD), probably become the leading role of New Times backlight of LCD.
Along with the development of technique of display, 3-Dimension (3D) technique of display starts the extensive concern causing scientific research personnel in recent years.Some have the OLEDs/PLEDs material of polarization property and device and the application in 3D technology thereof and are also in the news gradually
[7-9].These polarizations OLEDs/PLEDs device can initiatively polarized light-emitting, and can be applicable to replace the device such as backlight and the polarizer in LCD backlight, less power consumption and higher brightness can be obtained, reduce the number of polaroid, simplify manufacturing course and reduce costs.This polarizer combines the advantage of LCD and OLEDs/PLEDs, by the application prospect more Worth Expecting in LCD backlight lighting field.Therefore, develop efficient polarization OLEDs/PLEDs, being to promoting that the development of 3D indicating meter is significant, is one of the Main way in following display field.
As the core group part of polarization OLEDs/PLEDs, polarized luminescent material will be the research emphasis in following display field.Wherein, lyo-luminescence material is because having: the order of (1) liquid crystal material; (2) photoelectric properties of luminescent material; (3) molecule is easily self-assembled into ordered element, obtains the advantages such as high carrier mobility, becomes the polarized luminescent material of a quasi-representative.But the lyo-luminescence material that current document has been reported is few, and its principal character is: 1, material category is single, is upper liquid crystal fluorescent material substantially; 2, luminous efficiency is not high, and the liquid crystal material of major part report does not almost have luminescent properties, have ignored the design rule of luminescent material; 3, carrier transmission performance is not high.Therefore, for the lyo-luminescence material category of research is considerably less both at home and abroad at present, the bottleneck problems such as polarizer luminous efficiency is low, the High Efficiency Luminescence of development of new, the liquid crystal polarized luminescent material of high mobility and polarized light emitting device thereof are research topics had important practical significance.
In prior art, document (Wang, Y.; Liu, Y.; Luo, J.; Qi, H.; Li, X.; Ni, M.; Liu, M.; Zhu, M.; Zhu, W.; Cao, Y.Dalton Transactions, 2011,40,5046-5051.), (Shi, J.; Wang, Y.; Xiao, M.; Zhong, P.; Liu, Y.; Tan, H.; Zhu, M.; Zhu, W.Tetrahedron, 2015,71,463-469.) and (Wang, Y.; Chen, Q.; Li, Y.; Liu, Y.; Tan, H.; Yu, J.Zhu, M.; Zhu, W.; Cao, Y.Journal of Physical Chemistry C, 2012,116,5908-5914.) report 3 classes respectively based on Cyclometalated platinum complexes liquid crystal luminescent material, but the luminous efficiency of this few class material is low, and not there is polorised electroluminescence performance.
Summary of the invention
For the defect that existing polarized luminescent material exists, the object of the invention is to be to provide a class with the phenylpyridine-carbazole derivative of triphenylene conjugation or non-conjugated connection for cyclic metal complexes, the donor-acceptor-donor type being assistant ligand with propanedione derivative (D-A-D type) Cyclometalated platinum complexes liquid crystal luminescent material.
Another object of the present invention is the application being to provide D-A-D type Cyclometalated platinum complexes liquid crystal luminescent material described in a class, it can be used as luminescent layer doping agent, can prepare the polymkeric substance polarization electroluminescent white light device that polarization ratio is 1.32.
The invention provides a class D-A-D type Cyclometalated platinum complexes liquid crystal luminescent material, this lyo-luminescence material has structure shown in formula 1 or formula 2 or formula 3:
Wherein,
N is 2 ~ 8;
R be C1 ~ C12 alkyl or
r
2for the alkyl of C8 ~ C14;
R
1for the alkyl of C8 ~ C14.
In preferred D-A-D type Cyclometalated platinum complexes liquid crystal luminescent material n to be 6, R be methyl or
oC
12h
25.
R in preferred D-A-D type Cyclometalated platinum complexes liquid crystal luminescent material
1for the alkyl of C8.R
1most preferably be the straight chained alkyl of C8.
Present invention also offers the application of described D-A-D type Cyclometalated platinum complexes liquid crystal luminescent material, this application is the luminescent layer that it can be used as phosphor dopant to be applied to prepare polymkeric substance polarization electroluminescent white light device.
With poly-9 in preferred application method, 9-dioctyl fluorene is main body luminescent material, mix with described D-A-D type Cyclometalated platinum complexes liquid crystal polarized luminescent material, be there is by friction orientation and thermal anneal process preparation the luminescent layer of certain orientation, and obtain the polymkeric substance polarization electroluminescent white light device that polarization ratio is 1.32 further.
Polymkeric substance polarization electroluminescent white light device structure of the present invention is: ITO/PEDOT:PSS (30nm)/PVK (30nm)/PFO:Pt2 (80:20,70nm)/B3YMPM (50nm)/Ca (100nm)/Al (100nm).Hole transmission layer is polyvinyl carbazole (PVK) coating; Electron transfer layer is B3YMPM; Luminescent layer is the blended coating of D-A-D type Cyclometalated platinum complexes liquid crystal polarized luminescent material of the present invention and material of main part; Material of main part is poly-(9,9-dioctyl) fluorenes (PFO); Cathode layer is that calcium metal and aluminium are formed.
Hinge structure, beneficial effect of the present invention is: obtain first and a kind ofly connect with conjugation or unconjugated mode the cyclic metal complexes that phenylpyridine-carbazole derivative is formed Cyclometalated platinum complexes by triphenylene, formed the assistant ligand of Cyclometalated platinum complexes with propanedione derivative, formed donor-acceptor-donor (D-A-D) type Cyclometalated platinum complexes.This kind of D-A-D type Cyclometalated platinum complexes is compared with existing Cyclometalated platinum complexes liquid crystal luminescent material, mainly on molecular structure, introduce carbazole, introduce liquid crystal unit benzophenanthrene unit by conjugation and unconjugated mode of connection simultaneously, the introducing of carbazole facilitates the formation of compound liquid crystal and improves the luminous efficiency of compound, be conducive to obtaining polorised electroluminescence performance, the mode of connection of benzophenanthrene unit improves the liquid crystal property of material simultaneously, the Photophysics of this kind of material and liquid crystal property the are had change of matter, obtain polarization electroluminescent white light, obtained polarization electroluminescent white light device polarization ratio is 1.32.
Accompanying drawing explanation
The uv-visible absorption spectra figure of D-A-D type Cyclometalated platinum complexes liquid crystal luminescent material (Pt1 ~ Pt4) in dichloromethane solution that [Fig. 1] obtains for the embodiment of the present invention 1;
The photoluminescence spectra figure of D-A-D type Cyclometalated platinum complexes liquid crystal luminescent material (Pt1 ~ Pt4) in dichloromethane solution that [Fig. 2] obtains for the embodiment of the present invention 1;
The photoluminescence spectra figure of D-A-D type Cyclometalated platinum complexes liquid crystal luminescent material (Pt1) different concns in dichloromethane solution that [Fig. 3] obtains for the embodiment of the present invention 1;
The photoluminescence spectra figure of D-A-D type Cyclometalated platinum complexes liquid crystal luminescent material (Pt2) different concns in methylene dichloride that [Fig. 4] obtains for the embodiment of the present invention 1;
The thermal gravimetric analysis curve (TGA) of D-A-D type Cyclometalated platinum complexes liquid crystal luminescent material (Pt1 ~ Pt4) that [Fig. 5] obtains for the embodiment of the present invention 1;
Dsc (DSC) curve of D-A-D type Cyclometalated platinum complexes liquid crystal luminescent material (Pt1 ~ Pt4) that [Fig. 6] obtains for the embodiment of the present invention 1;
D-A-D type Cyclometalated platinum complexes liquid crystal luminescent material (Pt1 ~ Pt4) (R=-CH that [Fig. 7] obtains for the embodiment of the present invention 1
3) polarizing microscope figure (POM).
The polorised electroluminescence spectrogram based on D-A-D type Cyclometalated platinum complexes liquid crystal luminescent material (Pt2) that [Fig. 8] obtains for the embodiment of the present invention 1.
The current efficiency of the polorised electroluminescence device based on D-A-D type Cyclometalated platinum complexes liquid crystal luminescent material (Pt2) that [Fig. 9] obtains for the embodiment of the present invention 1 and current density plot figure.
The polorised electroluminescence spectrogram based on D-A-D type Cyclometalated platinum complexes liquid crystal luminescent material (Pt4) that [Figure 10] obtains for the embodiment of the present invention 1.
Embodiment
Following specific embodiment is intended to that the invention will be further described, but the protection domain that these specific embodiments do not limit the present invention in any way.
Embodiment 1
(1), the preparation of conjugated type Cyclometalated platinum complexes: synthetic route is as follows:
The preparation of 3,6-diacetyl-9 hydrogen-carbazole (1):
In 250mL single port bottle, add 9 hydrogen-carbazole (3.0g, 17.96mmol) successively, aluminum chloride (6.8g, 51.1mmol) and methylene dichloride (CH
2cl
2) (100mL), be cooled to 0 DEG C.Acetyl Chloride 98Min. (3.8g, 48.7mmol) is dropwise added above-mentioned mixed system, then at room temperature reacts 12h.Question response is complete, and underpressure distillation is except desolventizing, and residuum ethyl alcohol recrystallization obtains pale yellow solid 1 (2.24g, 50%).
1HNMR(CDCl
3,400MHz,TMS),δ(ppm):8.78(s,2H),8.14(d,J＝8.2HZ,2H),7.50(d,J＝8.48HZ,2H),2.7(s,6H)。
The preparation of 3,6-diethyl-9 hydrogen-carbazole (2):
In the single port bottle of 250mL, add compound 1 (3.0g, 17.96mmol) successively, aluminum chloride (6.8g, 51.1mmol) and tetrahydrofuran (THF) (THF) (130mL), be cooled to 0 DEG C.Lithium aluminum hydride (1.0g, 33.3mmol) is added in above-mentioned reaction system in batches, then at room temperature reacts 4h.Question response is complete, and underpressure distillation, except desolventizing, lefts in thing ethyl acetate (3 × 30mL) extraction; Organic layer washs with water 50mL and saturated aqueous common salt 30mL respectively; Then underpressure distillation is except desolventizing.Residuum sherwood oil/CH
2cl
2(V:V, 8/1) obtains yellow solid 2 (1.0g, 40%) for eluent column chromatography for separation.
1H NMR(CDCl
3,400MHz,TMS),δ(ppm):7.88(s,2H),7.32(d,J＝8.21HZ,2H),7.24(d,J＝8.77HZ,2H),2.85-2.79(t,J＝7.52HZ,4H),1.36-1.11(m,6H).
The preparation of 9-(4-bromophenyl)-3,6-diethyl-9 hydrogen-carbazole (3):
In 250mL single port bottle, add compound 2 (1.4g, 6.27mmol) successively, to bromo-iodobenzene (2.6g, 9.4mmol), salt of wormwood (2.5g, 18.81mmol), 1,10-phenanthroline (372mg, 1.88mmol), cuprous iodide (357mg, 1.88mmol) with o-Xylol (100mL), back flow reaction 24h under a nitrogen.Question response liquid is cooled to room temperature, and underpressure distillation is except desolventizing.Mixture CH
2cl
2(3 × 30mL) extracts, and organic layer 50mL washes, and then except desolventizing, residuum sherwood oil is that eluent column chromatography for separation obtains faint yellow solid 3 (1.68g, 70.8%).
1HNMR(DMSO,400MHz,TMS),δ(ppm):8.04(s,2H),7.99(d,J＝8.2Hz,2H),7.84(d,J＝8.4Hz,2H),7.58(d,J＝8.4Hz,2H),7.43(d,J＝8.2Hz,2H),2.78(d,J＝7.4Hz,4H),1.30-1.26(m,6H)。
3,6-diethyl-9-(4-(4,4,5,5-tetramethyl--1,3,2-dioxaborinate) phenyl)-9 hydrogen-carbazole) preparation of (4):
In 100mL there-necked flask, add compound 3 (1.09g, 2.88mmol) and THF (30mL), be cooled to-78 DEG C.Under nitrogen atmosphere, n-Butyl Lithium (5.4mL, 8.64mmol) slowly instills in above-mentioned system.After reaction 2h, after reacting 30min under reaction solution being warming up to room temperature, be again cooled to-78 DEG C.Then slowly drip 2-b propanol tetramethyl ethylene ketone boric acid ester-4,4,5,5-tetramethyl--1,3,2-to mix borine (1.07g, 5.76mmol), reaction solution at room temperature reacts and spends the night.Question response is complete, and underpressure distillation is except desolventizing, and residuum sherwood oil is that eluent column chromatography for separation obtains brown solid 4 (480mg, 38.4%).
1HNMR(CDCl
3,400MHz,TMS),δ(ppm):8.06(d,J＝7.9Hz,2H),7.96(s,2H),7.61(d,J＝7.9Hz,2H),7.40(d,J＝8.3Hz,2H),7.26(d,J＝8.4Hz,2H),2.87(q,J＝7.5Hz,4H),1.53-1.20(m,18H)。
The preparation of 9-(4-(5-bromopyridine) phenyl)-3,6-diethyl-9 hydrogen-carbazoles (5):
In 100mL single port bottle, add compound 4 (480mg successively, 1.1mmol), 2,5-dibromo pyridine (260mg, 1.65mmol), cesium carbonate (1.0g, 3.3mmol), four triphenyl phosphorus palladium (38mg, 0.032mmol) with THF (40mL), reflux under nitrogen atmosphere 24h.Question response liquid is cooled to room temperature, and underpressure distillation is except desolventizing; Residuum sherwood oil/CH
2cl
2(V:V, 8/1) obtains faint yellow solid 5 (160mg, 32%) for eluent column chromatography for separation.
1HNMR(CDCl
3,400MHz,TMS),δ(ppm):8.82(s,1H),8.21(d,J＝8.68Hz,2H),7.96(d,J＝8.78Hz,2H),7.76-7.70(m,4H),7.42(d,J＝8.2Hz,2H),7.08(d,J＝7.48Hz,1H),6.94(d,J＝8.4Hz,1H),2.90-2.85(m,4H),0.90(m,6H)。
The preparation of 10-bromo-2,3,6,7-tetra-octyloxies-benzophenanthrene-1,3,2-dioxaborinate (6):
In 100mL single port bottle, add 10-bromo-2 successively, 3,6,7-tetra-octyloxy benzophenanthrene (500mg, 0.61mmol), duplex tetramethyl ethylene ketone boric acid ester (340mg, 1.34mmol), salt of wormwood (166mg, 1.83mmol), 1 of [two (diphenylphosphine) ferrocene palladium chloride (II) of 1,1-] (22.3mg, 0.03mmol) and 35mL, 4-dioxane, under a nitrogen 80 DEG C of reaction 24h.Question response liquid is cooled to room temperature, and underpressure distillation removes desolventizing, residuum sherwood oil/CH
2cl
2(V:V, 2/1) obtains oily solid 6 (310mg, 58.7%) for eluent column chromatography for separation.
1HNMR(CDCl
3,400MHz,TMS),δ(ppm):8.56(s,1H),8.31(d,J＝8.68Hz,1H),7.93-7.81(s,4H),7.64(d,J＝8.64Hz,1H),4.24-4.22(t,J＝6.4Hz,8H),1.94(m,8H),1.40-1.31(m,52H),0.90(m,12H)。
The preparation of 9-(4-(5-(6,7,10,11-tetra-octyloxy benzophenanthrene) pyridine) phenyl)-3,6-diethyl-9 hydrogen-carbazoles (7):
In 50mL single port bottle, add compound 5 (220mg successively, 0.48mmol) He 6 (220mg, 0.48mmol), four triphenyl phosphorus palladiums (17mg, 0.014mmol), cesium carbonate (2mol/L, 6mL) and the toluene of 20mL, under a nitrogen 80 DEG C of reaction 24h.Question response liquid is cooled to room temperature, and underpressure distillation removes desolventizing, residuum sherwood oil/CH
2cl
2(V:V, 10/8) obtains yellow solid 7 (290mg, yield54%) for eluent column chromatography for separation.
1HNR(CDCl
3,400MHz,TMS),δ(ppm):9.20(s,1H),8.72(s,1H),8.61(d,J＝8.6HZ,1H),8.31(d,J＝8.34HZ,2H),8.21(d,J＝6.18HZ,3H),7.98(t,J＝7.9HZ,3H),7.87(d,J＝5.44HZ,3H),7.72(d,J＝8.34HZ,2H),7.44(d,J＝8.32HZ,2H),7.28(m,2H),4.28(t,J＝7.48HZ,8H),2.88-2.83(m,4H),1.96(t,J＝7.16HZ,8H),1.61-1.25(m,36H),0.92(m,18H)。
The preparation of intermediate 8:
In 50mL single port bottle, add compound 7 (50mg, 0.045mmol) successively, chlorine Asiaization potassium platinate (8.5mg, 0.020mmol), distilled water 2mL and 6mL THF, the lower 80 DEG C of reaction 24h of nitrogen.Question response liquid is cooled to room temperature, mixture CH
2cl
2extraction, washing organic layer, underpressure distillation are except desolventizing, and residuum vacuum-drying obtains compound 8, are directly used in next step reaction.
The preparation of D-A-D type Cyclometalated platinum complexes liquid crystal luminescent material Pt1:
In 50mL single port bottle, add compound 8 (190mg, 0.072mmol), methyl ethyl diketone (18mg, 0.288mmol), sodium carbonate (77.76mg, 0.72mmol) with 15mL ethylene glycol monoethyl ether, 100 DEG C of reaction 24h under a nitrogen.Question response liquid is cooled to room temperature, is poured into by reaction solution in 50mL distilled water.Mixture CH
2cl
2(3 × 30mL) extracts, collected organic layer, and underpressure distillation removes desolventizing, residuum sherwood oil/CH
2cl
2(V:V, 2/1) obtains yellow solid 9 (40mg, yield 12.5%) for washing and dehydrating integrated machine column chromatography for separation.
1HNR(CDCl
3,400MHz,TMS),δ(ppm):9.49(s,1H),8.69(s,1H),8.65(d,J＝8.4HZ,1H),8.26(d,J＝8.1HZ,1H),8.25(s,1H),8.11(s,1H),7.97(s,1H),7.87(t,J＝8.0HZ,4H),7.80(d,J＝8.2HZ,3H),7.70(d,J＝8.0HZ,1H),7.54(d,J＝8.2HZ,2H),7.33(d,J＝7.8HZ,2H),5.5(s,1H).4.28(t,J＝7.48HZ,8H),2.88-2.84(m,4H),1.96(t,J＝7.16HZ,8H),1.61-1.12(m,42H),0.92(m,18H)。
The preparation of D-A-D type Cyclometalated platinum complexes liquid crystal luminescent material Pt2:
In 50mL single port bottle, add compound 8 (277mg, 0.105mmol), methyl ethyl diketone derivative (160mg, 0.262mmol), sodium carbonate (111.3mg, 1.05mmol) with 13mL ethylene glycol monoethyl ether, 100 DEG C of reaction 24h under a nitrogen.Question response liquid is cooled to room temperature, is poured into by reaction solution in 50mL distilled water.Mixture CH
2cl
2(3 × 30mL) extracts, collected organic layer, and underpressure distillation removes desolventizing, residuum sherwood oil/CH
2cl
2(V:V, 10/7) obtains yellow solid 10 (90mg, yield37.6%) for eluent column chromatography for separation.
1HNR(CDCl
3,400MHz,TMS),δ(ppm):9.72(s,1H),8.74(s,1H),8.57(d,J＝8.3HZ,1H),8.06(d,J＝8.3HZ,1H),8.05(s,1H),7.88(s,1H),7.78-7.76(m,J＝8.3HZ,5H),7.73-7.72(d,J＝6.4HZ,5H),7.45(d,J＝7.52HZ,1H),7.31(m,2H),6.67(d,J＝8.4HZ,2H),6.2(d,J＝8.2HZ,2H),6.5(s,1H),4.30-4.24(t,J＝6.3HZ,8H),4.30-4.24(t,J＝6.3HZ,8H),3.79(t,J＝6.3HZ,4H)2.91-2.90(m,4H),1.98(t,J＝6.6HZ,8H),1.68-1.27(m,74H),0.93-0.85(m,18H)。
(2) preparation of non-co-yoke type Cyclometalated platinum complexes: synthetic route is as follows:
The preparation of adjacent phenol octyloxy (9):
In the single port bottle of 250mL, add o-phenol (5.0g, 45.45mmol) successively; n-octane bromide (11.40g, 59mmol), salt of wormwood (12.5g; 91.5mmol) and the ethanol of 120mL, back flow reaction 24h under nitrogen protection.Question response is complete, be cooled to room temperature, underpressure distillation is except desolventizing, DCM (3 × 30mL) extracts, 60mL washes, collected organic layer, mixture PE/DCM (V:V, 10/1) for eluent column chromatography for separation obtains pale yellow oily liquid body 9 (3.76g, 37.2%).
1HNR(CDCl
3,400MHz,TMS),δ(ppm):7.04-6.94(m,4H),5.77(s,1H),4.15(t,J＝6.16HZ,2H),1.93-1.92(m,2H),1.68-1.32(m,10H),1.01(t,J＝6.3HZ,3H).
The preparation of 3,4,3 ', 4 '-four octyloxy biphenyl (10):
In the single port bottle of 250mL, add bromo-1, the 2-bis-octyloxy benzene (2.13g of 4-successively; 5.1mmol) with 2-(3,4-bis-(octyloxy) benzene)-4,4; 5,5-tetramethyl--1,3; 2-dioxaborinate (2.37g, 5.1mmol), four triphenyl phosphorus palladium (120mg; 0.1mmol); the tetrahydrofuran (THF) of salt of wormwood (2mol/L, 15mL) and 80mL, under nitrogen protection 80 DEG C of reaction 24h.Question response is complete, be cooled to room temperature, suction filtration, then wash by ethyl acetate, collect filtrate decompression distillation except desolventizing, DCM (3 × 30mL) extracts, 60mL washes, collected organic layer, mixture PE/DCM (V:V, 8/1) for eluent column chromatography for separation obtains snow-white solid 10 (2.23g, 71%).
1HNR(CDCl
3,400MHz,TMS),δ(ppm):7.05(d,J＝7.96HZ,4H),6.91(s,2H),4.03(t,J＝6.06HZ,8H),1.82(t,J＝5.92HZ,8H),1.48-1.28(m,40H),0.87(t,J＝6.48HZ,12H).
The preparation of intermediate (11):
In the single port bottle of 100mL, add 9 (1.27g, 1.89mmol) and 10 (1.05g, 4.74mmol) successively, the DCM of FERRIC CHLORIDE ANHYDROUS (0.92g, 5.67mmol) and 25mL, at room temperature reacts 40min.Question response is complete, react with appropriate ice methyl alcohol cancellation, underpressure distillation is except desolventizing, DCM (3 × 20mL) is used to extract again, 60mL washes, collected organic layer, mixture PE/DCM (V:V, 10/8) for eluent column chromatography for separation obtains pale solid 11 (552mg, 33%).
1HNR(CDCl
3,400MHz,TMS),δ(ppm):8.0(s,1H),7.87(s,4H),7.81(s,1H),4.33(t,J＝6.35HZ,2H),4.26(t,J＝6.5HZ,8H),1.98(m,10H),1.46-1.30(m,50H),0.94(t,J＝6.5HZ,15H).
The preparation of 9-(4-(5-aldehyde radical pyridine) phenyl)-3,6-diethyl-9 hydrogen-carbazoles (12):
In the single port bottle of 100mL; add 4 (500mg successively; 1.21mmol); 2-bromo-5-aldehyde radical pyridine (271mg; 1.46mmol), four triphenyl phosphorus palladiums (419mg, 0.36mmol); unsaturated carbonate caesium (10mL) and (toluene/ethanol of 10mL/10mL), under nitrogen protection 90 DEG C of reaction 24h.Question response is complete, and underpressure distillation except desolventizing, then uses DCM (3 × 30mL) to extract, 50mL washes, collected organic layer, mixture PE/EA (V:V, 10/1) for eluent column chromatography for separation obtains yellow look solid 12 (270mg, 55%).
1HNMR(CDCl
3,400MHz,TMS),δ(ppm):8.72(s,1H),8.20(d,J＝8.63Hz,2H),7.92(d,J＝8.76Hz,2H),7.72-7.69(m,4H),7.40(d,J＝8.21Hz,2H),7.06(d,J＝7.42Hz,1H),6.92(d,J＝8.30Hz,1H),2.88-2.83(m,4H),1.30(m,6H).
The preparation of 9-(4-(5-methyl alcohol pyridine) phenyl)-3,6-diethyl-9 hydrogen-carbazoles (13):
In the single port bottle of 100mL, add 12 (270mg, 0.66mmol) successively, sodium borohydride (112mg, 1.66mmol) and (toluene/ethanol of 15mL/15mL), RT reacts 6h under nitrogen protection.Question response is complete, and underpressure distillation except desolventizing, then uses EA (3 × 30mL) to extract, and 50mL washes, collected organic layer, and underpressure distillation is except desolventizing, and vacuum-drying obtains yellow solid 13 (180mg, 67%).
1HNMR(CDCl
3,400MHz,TMS),δ(ppm):8.72(s,1H),8.20(d,J＝8.28Hz,2H),7.94(s,2H),7.85(d,J＝8.04Hz,1H),7.82(d,J＝8.08Hz,1H),7.67(d,J＝8.28Hz,2H),7.40(d,J＝8.32Hz,2H),7.24(d,J＝8.04Hz,2H),4.84(s,2H),2.87-2.81(m,4H),1.35(t,J＝7.52Hz,6H).
The preparation of 9-(4-(5-methylene radical bromopyridine) phenyl)-3,6-diethyl-9 hydrogen-carbazoles (14):
In the single port bottle of 100mL; add 13 (500mg successively; 1.23mmol); carbon tetrabromide (511mg; 1.54mmol), the THF adding 3mL makes above-mentioned raw materials just dissolve, then adds triphenylphosphine (403mg; 1.54mmol), back flow reaction 24h under nitrogen protection.Question response is complete, underpressure distillation is except desolventizing, DCM (3 × 10mL) extracts, 30mL washes, collected organic layer, and underpressure distillation is except desolventizing, collected organic layer, mixture with PE/DCM (V:V, 1/1) for eluent column chromatography for separation obtains yellow solid 14 (523mg, 97%).
1HNMR(CDCl
3,400MHz,TMS),δ(ppm):8.74(s,1H),8.21(d,J＝8.28Hz,2H),7.94(s,2H),7.86(d,J＝6.48Hz,1H),7.81(d,J＝8.08Hz,1H),7.68(d,J＝8.32Hz,2H),7.40(d,J＝8.32Hz,2H),7.25(d,J＝8.05Hz,2H),4.56(s,2H),2.87-2.81(m,4H),1.35(t,J＝7.52Hz,6H).
Part Tp-O (CH
2) preparation of-pycz (15):
In the single port bottle of 100mL; add 11 (515mg successively; 1.09mmol); 14 (1.0g, 1.09mmol), 18-are preced with-6 (10.9mg; 0.33mmol); the acetone of salt of wormwood (374mg, 2.75mmol) and 30mL, under nitrogen protection 70 DEG C of reaction 24h.Question response is complete, underpressure distillation is except desolventizing, DCM (3 × 30mL) extracts, and 60mL washes, collected organic layer, underpressure distillation is except desolventizing, collected organic layer, mixture is successively with PE/DCM (V:V, 10/8), DCM/PE (V:V, 10/6) for eluent column chromatography for separation obtains yellow solid 14 (619mg, 44.2%).
1HNR(CDCl
3,400MHz,TMS),δ(ppm):8.93(s,1H),8.24(d,J＝7.59Hz,1H),8.05(d,J＝7.92Hz,1H),7.96(s,1H),7.88-7.84(m,8H),7.77(s,1H),7.69(d,J＝7.61Hz,1H),7.41(d,J＝8.14Hz,2H),5.43(s,2H),4.24(t,J＝5.24Hz,10H),2.84(t,J＝7.1Hz,4H),1.95(t,J＝7.24Hz,10H),1.42-1.31(m,56H),0.90(m,15H).
13C NMR(100MHz,CDCl3),d(ppm):14.16,16.58,22.74,26.25,26.28,26.31,28.98,29.39,29.53,31.90,69.48,69.56,69.67,69.85,106.87,107.23,107.58,109.62,119.01,120.24,123.35,123.42,123.48,123.69,123.97,124.66,126.14,126.89,128.24,131.64,136.05,137.56,139.00,147.87,148.98,149.02,149.16,149.29,156.39.
The preparation of bridging intermediate (16):
In the single port bottle of 50mL, add compound 15 (500mg, 0.393mmol) and chlorine Asiaization potassium platinate (81mg, 0.196mmol) successively, distilled water 3mL and 9mL tetrahydrofuran (THF), in a nitrogen atmosphere 80 DEG C of reaction 24h.Question response is complete, is cooled to room temperature, and mixture DCM extraction, washing, collected organic layer, underpressure distillation is except desolventizing, and vacuum-drying obtains compound 16.
The preparation of D-A-D type Cyclometalated platinum complexes liquid crystal luminescent material Pt3:
In the single port bottle of 50mL, add compound 16 (547mg, 0.21mmol), methyl ethyl diketone (84mg, 0.84mmol), sodium carbonate (228mg, 2.1mmol) with 20mL ethylene glycol monoethyl ether, 100 DEG C of reaction 24h in a nitrogen atmosphere.Question response is complete, be cooled to room temperature, mixture DCM (3 × 40mL) extracts, 3 × 50mL washes, collected organic layer, mixture DCM/PE (V:V, 10/6) for washing and dehydrating integrated machine column chromatography for separation obtains yellow solid, use n-hexane again, obtain Pt3 (70mg, 21.2%).
1HNR(CDCl
3,400MHz,TMS),δ(ppm):9.17(s,1H),8.08(d,J＝7.64HZ,1H),7.94(d,J＝7.44HZ,1H),7.87(sHZ,1H),7.82(s,5H),7.75(s,1H),7.68(d,J＝7.72HZ,2H),7.62(d,J＝7.72HZ,2H),7.48(d,J＝8.04HZ,2H),7.22(s,2H),5.45(s,1H),5.38(s,2H),4.22(t,J＝4.76HZ,12H),2.83(t,J＝6.96HZ,4H),1.97-1.87(m,10H),1.36-1.30(m,56),0.88(m,18H).
13C NMR(100MHz,CDCl3),d(ppm):14.15,16.65,22.73,25.89,25.99,26.26,26.39,29.43,29.56,29.62,29.68,29.73,31.90,31.97,67.79,69.25,69.85,69.91,70.67,107.47,110.51,114.14,118.77,123.38,123.84,124.19,125.99,128.76,128.85,135.71,139.19,148.95,149.36,149.47,149.92,161.28,161.43.
The preparation of D-A-D type Cyclometalated platinum complexes liquid crystal luminescent material Pt4:
In the single port bottle of 100mL, add compound 16 (1.07g, 0.4mmol), 1,3-phenylbenzene derovatives (619mg, 1.01mmol), sodium carbonate (424mg, 4mmol) and 30mL ethylene glycol monoethyl ether, in a nitrogen atmosphere 100 DEG C of reaction 24h.Question response is complete, be cooled to room temperature, mixture DCM (3 × 40mL) extracts, 3 × 50mL washes, collected organic layer, mixture PE/DCM (V:V, 10/7) for washing and dehydrating integrated machine column chromatography for separation obtains yellow solid, use n-hexane again, obtain Pt4 (150mg, 18.2%).
1HNR(CDCl
3,400MHz,TMS),δ(ppm):9.96(s,1H),8.11(m,1H),8.00-7.69(m,16H),7.40(d,J＝6.84HZ,2H),6.72(s,1H),6.86(d,J＝7.64HZ,2H),5.45(s,1H),4.20(t,,8H),4.11(t,2H),3.89(t,2H),3.31(t,2H),2.86(t,J＝6.6HZ,4H),1.94-1.86(m,12H),1.36-1.30(m,86H),0.88(m,21H).
13C NMR(100MHz,CDCl3),d(ppm):14.15,16.54,22.73,26.24,26.33,27.11,28.27,28.98,29.38,29.53,31.89.69.43,69.55,69.63,69.82,69.85,102.63,106.74,106.93,107.13,107.44,110.24,118.74,121.78,123.23,123.43,123.47,123.51,124.05,124.98,125.95,128.29,131.34,135.58,138.01,138.39,139.53,140.95,142.98,147.60,148.95,149.04,149.24,149.30,149.36,167.15.
(3) preparation of non-co-yoke type Cyclometalated platinum complexes: synthetic route is as follows:
The preparation of 9-(4-(5-bromopyridine) phenyl)-3,6-diethyl 9 hydrogen-carbazoles (17):
In the single port bottle of 100mL; add 13 (250mg successively; 0.614mmol); 1,6-dibromo-hexane (179mg, 0.737mmol); potassiumiodide (3.05mg; 0.018mmol), the acetone of saturated sodium hydroxide (73mg) and 20mL, under nitrogen protection 70 DEG C of reaction 24h.Question response is complete, underpressure distillation is except desolventizing, DCM (3 × 20mL) extracts, 50mL washes, collected organic layer, and underpressure distillation is except desolventizing, collected organic layer, mixture successively with PE/EA (V:V, 10/1) for eluent column chromatography for separation obtains faint yellow oily solid 17 (70mg, 20%).8.68(s,1H),8.19(d,J＝7.16Hz,2H),7.94(s,2H),7.81(s,2H),7.67(d,J＝7.08Hz,2H),7.40(d,J＝7.72Hz,2H),7.25(s,2H),4.58(s,2H),3.54(s,2H),3.42(s,2H),3.19(s,2H),2.84(t,J＝6.88Hz,4H),1.89-1.43(m,8H)1.34(t,J＝6.4Hz,6H).
Tp-O ((CH
2) 6) preparation of-pycz (18):
In the single port bottle of 100mL; add 13 (250mg successively; 0.614mmol); 1,6-dibromo-hexane (179mg, 0.737mmol); potassiumiodide (3.05mg; 0.018mmol), the acetone of saturated sodium hydroxide (73mg) and 20mL, under nitrogen protection 70 DEG C of reaction 24h.Question response is complete, underpressure distillation is except desolventizing, DCM (3 × 20mL) extracts, 50mL washes, collected organic layer, and underpressure distillation is except desolventizing, collected organic layer, mixture successively with PE/EA (V:V, 10/1) for eluent column chromatography for separation obtains faint yellow oily solid 17 (70mg, 20%).
(4) other D-A-D type Cyclometalated platinum complexes liquid crystal luminescent material preparation, only need replace raw material and just can obtain in above-mentioned preparation method.
Embodiment 2
The production program of polymkeric substance polorised electroluminescence device and the test of luminescent properties:
Polymkeric substance polorised electroluminescence device architecture is: ITO/PEDOT:PSS (30nm)/PVK (30nm)/PFO:Pt2or Pt4 (80:20,70nm)/B3YMPM (50nm)/Ca (100nm)/Al (100nm).Hole transmission layer is polyvinyl carbazole (PVK) coating; Electron transfer layer is B3YMPM; Luminescent layer is guest materials (Pt2 or Pt4) and the blended coating of material of main part; Material of main part is poly-(9,9-dioctyl) fluorenes (PFO); Cathode layer is that calcium metal and aluminium are formed.
The production process of device: on the ito glass handled well, the poly-ethylenedioxythiophene of spin coated 30nm/poly-p styrene sulfonic acid (PEDOT-PSS) (Bayer Batron P4083) hole injection layer, the PVK hole transmission layer of 30nm and luminescent layer of 70nm, the electron transfer layer of 50nm, then evaporation 100nm calcium (Ca) layer and 100nm aluminium (Al) layer successively.The light-emitting area of device is 0.15cm
2.
The preparation procedure of ordered arrangement luminescent layer: 1, on the PVK layer that spin coating is good, repeatedly rub towards same direction with clean teflon rod, then at PVK surface spin coating Pt2 (or Pt4) material, reheat to 150 DEG C of annealing, make luminescent layer have the thin layer of certain oriented structure by induced synthesis; 2, on the PVK layer that spin coating is good, repeatedly rub towards same direction with clean teflon rod, then at PVK surface spin coating Pt2 (or Pt4) material, make luminescent layer have the thin layer of certain oriented structure by induced synthesis; 3, at the good luminescent layer of spin coating on the surface, repeatedly rub towards same direction with clean teflon rod, make luminescent layer be formed the thin layer with certain arrangement by friction orientation.
The thickness of hole injection layer, hole transmission layer and luminescent layer measures with surface profiler (Tencor, ALFA-Step500).The thickness of Ba and Al and sedimentation velocity thickness/speed instrument (the STM-100 thickness/speed instrument of Sycon company) measure, and the sedimentation velocity of Ba and Al is respectively 0.05 ~ 0.1nm/s and 1 ~ 2nm/s.All operations are all carried out in nitrogen glove box.
Electroluminescent spectrum (EL) the Instaspec4CCD grating spectrograph of Oriel company measures; The silicon photoelectric diode of luminous efficiency standard measures; Electroluminescent efficiency S80 type totalizing instrument (USLabshere company) also coordinates UDT3 digital photometer to measure; LASER Light Source is the He-Cd laser apparatus (US Dmni Chrone company) of 325nm, 442nm spectral line; Current-voltage (I-V) curve and luminous intensity-voltage (L-V) curve and external quantum efficiency Keithley source determinator measure.
Based on the polymkeric substance polorised electroluminescence device of Pt2 electroluminescent spectrum (EL) as shown in Figure 8.Current efficiency and current density plot are as shown in Figure 9.As shown in Figure 8, the device based on Pt2 demonstrates white-light spectrum, in 400nm to 750nm scope, all demonstrate strong luminescence.Its emission wavelength is respectively 439nm, 467nm, 498nm and 630nm.Wherein, the Luminescence Origin at 439nm and 467nm place derives from the luminous and state of aggregation luminescence of the unit molecule of Cyclometalated platinum complexes respectively in the luminescence of material of main part PFO, 498nm and 630nm.The high-high brightness of device is 485cd/m
2, maximum current efficiency is 2.16cd/A, and maximum external quantum efficiency is 1.75%.When adopting the preparation method of the first orderly luminescent layer, the luminous intensity of device vertical direction and the intensity ratio of horizontal direction are 1.32.As far as we know, this is the polarization electroluminescent white light device of reported first based on Cyclometalated platinum complexes.
As shown in Figure 10, the polorised electroluminescence device based on Pt4 also presents broad-band illumination, and its EL spectrum has transmitting in 400nm to 750nm scope.Wherein the transmitting of 400nm-500nm comes from material of main part PFO; Transmitting between 550nm-750nm is originating primarily from Cyclometalated platinum complexes.Further, at 420nm place, it is parallel is about 5.0 with vertical with the ratio (polarization ratio) of the EL light intensity of frictional direction with the EL light intensity of frictional direction.Compared with the polorised electroluminescence device based on Pt2, the polorised electroluminescence device based on Pt4 shows very strong polorised electroluminescence and mainly comes from PFO material of main part between 400nm-500nm.
Although combine preferred embodiment to describe the present invention, the present invention is not limited to above-described embodiment, is to be understood that claims summarise scope of the present invention.The present invention design guidance under, those skilled in the art will realize that certain change that various embodiments of the present invention scheme is carried out, all by cover by the spirit and scope of claims of the present invention.
Claims (5)
1. donor-acceptor-donor type Cyclometalated platinum complexes liquid crystal luminescent material, is characterized in that: have structure shown in formula 1 or formula 2 or formula 3:
Wherein,
N is 2 ~ 8;
R be C1 ~ C12 alkyl or
r
2for the alkyl of C8 ~ C14;
R
1for the alkyl of C8 ~ C14.
2. donor-acceptor-donor type Cyclometalated platinum complexes liquid crystal luminescent material according to claim 1, is characterized in that, n to be 6, R be methyl or
3. donor-acceptor-donor type Cyclometalated platinum complexes liquid crystal luminescent material according to claim 1, is characterized in that, R
1for the alkyl of C8.
4. the application of the donor-acceptor-donor type Cyclometalated platinum complexes liquid crystal luminescent material described in any one of claims 1 to 3, is characterized in that, it can be used as phosphor dopant to be applied to prepare the luminescent layer of polymkeric substance polarization electroluminescent white light device.
5. application according to claim 4, it is characterized in that, with poly-9,9-dioctyl fluorene is main body luminescent material, mix with described donor-acceptor-donor type Cyclometalated platinum complexes liquid crystal luminescent material, be there is by friction orientation and thermal anneal process preparation the luminescent layer of certain orientation, and obtain the polymkeric substance polarization electroluminescent white light device that polarization ratio is 1.32 further.
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