CN103509043B - Two carborane analog derivatives, preparation method and application and electroluminescent device - Google Patents
Two carborane analog derivatives, preparation method and application and electroluminescent device Download PDFInfo
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Abstract
The present invention discloses two carborane analog derivatives, preparation method and application and electroluminescent device, and described two carborane analog derivatives are connected with carbazole group by two carborane monomers, and connects electron donating group gained on carborane monomer; When between carborane monomer is during carborane, the molecular structure of described two carborane analog derivatives is; Wherein, R1 group is alkanes group or arene group; When carborane monomer is to carborane, the molecular structure of described two carborane analog derivatives; Wherein, R2 group is alkanes group or arene group. The present invention is keeping under the prerequisite that host compound triplet energy level is relatively high, bipolar transmission performance and the HOMO/LUMO energy level of host compound is regulated by the ratio and link position adjusting push-and-pull electron group, improve luminescent layer current carrier utilization ratio, improve the luminous efficiency of device further.
Description
Technical field
The present invention relates to luminous organic material field, particularly relate to a kind of two carborane analog derivatives, preparation method and application and electroluminescent device.
Background technology
In recent years, the blue emitting phosphor host compound with bipolar transmission performance is paid close attention to widely, but makes the triplet energy level of host compound can not meet the needs of dark blue smooth object well due to the strong push-and-pull electronic action between bipolar transmission group. Therefore, the bipolar transmission phosphorescent light body material developing high triplet energy level becomes the important component part promoting Organic Light Emitting Diode development. Lot of documents is reported, improve bipolar phosphorescent light body material triplet energy level and mainly contain following two kinds of methods: 1. by the change of link position, strengthen the space steric hindrance between push-and-pull electron group, thus play the effect reducing compound conjugated degree, improve host compound triplet energy level further; 2. by connecting atom or the group of particularly conjugated structure between push-and-pull electronics, interrupt the conjugation between push-and-pull electron group, improve the triplet energy level of host compound further. For the mode of the conjugated degree utilizing special construction atom or group minimizing compound, document (J.Am.Chem.Soc, DOI:10.1021/ja3066623; Adv.Mater.2010,22,4775-4778.) report by introducing carborane and the diamantane group of particularly conjugated structure in the middle of compound, have adjusted the triplet energy level of carborane class phosphorescence host compound well, it is possible to be advantageously applied to dark blue host compound. Although the triplet state of existing carborane class phosphorescence host compound can meet the requirement of dark Blue-light emitting host material well, but its special conjugated structure can not adjust the bipolar transmission performance of whole host compound well, simultaneously, also there is its HOMO/LUMO and the not good shortcoming of adjacent active layer level-density parameter in carborane human subject compound, so that when host compound is applied to luminescent device, its efficiency is relatively low.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of two carborane analog derivatives, preparation method and application and electroluminescent device, described two carborane analog derivatives are that a class has high triplet energy level, the bipolar blue emitting phosphor material of main part of high electron mobility and high thermal stability, can using described two carborane analog derivatives as blue emitting phosphor main body luminescent material for the preparation of efficient electro-phosphorescent luminescent device, the vitrifying conversion temp being intended to make up existing carborane class phosphorescence main body is not high, its bipolar transmission performance can not meet the requirement of blue emitting phosphor luminescent device well simultaneously, and carborane its HOMO/LUMO of human subject compound and the not good shortcoming of adjacent active layer level-density parameter.
The technical scheme of the present invention is as follows:
A kind of two carborane analog derivatives, wherein, described two carborane analog derivatives are connected with carbazole group by two carborane monomers, and connects electron donating group gained on carborane monomer;
When between carborane monomer is during carborane, the molecular structure of described two carborane analog derivatives is
; Wherein, R1 group is alkanes group or arene group;
When carborane monomer is to carborane, the molecular structure of described two carborane analog derivatives; Wherein, R2 group is alkanes group or arene group.
Two described carborane analog derivatives, wherein, the molecular structure of described two carborane analog derivatives is, R1 group is��Or��
Two described carborane analog derivatives, wherein, the molecular structure of described two carborane analog derivatives is, R2 group is��Or��
A preparation method for two carborane analog derivatives as above, wherein, comprises the following steps:
A, carborane monomer is dissolved in dry diethyl ether solution, N2Under protective condition, at the temperature of 0 ~-80 DEG C, dropwise add the n-BuLi solution of 2.5M, under keeping cold condition, continue stirring 30 ~ 90min; The disposable CuCl adding drying, at room temperature stirs 0.5 ~ 4.0h; Adding 1,4-dibromobenzene and pyridine, reflux 12 ~ 24h at 60 ~ 120 DEG C of temperature; Question response liquid is cooled to room temperature, is steamed by solvent wherein dry, gained solid water dissolution, with dichloromethane extraction, merge organic phase, simultaneously with anhydrous magnesium sulfate drying, filtering, solvent evaporated, the crude product of gained obtains white solid powder by the mode purifying of column chromatography;
B, the white solid powder dissolution that steps A is obtained in the diethyl ether solution of drying, N2Under protective condition, at the temperature of 0 ~-80 DEG C, dropwise add the n-BuLi solution of 2.5M, under keeping cold condition, continue stirring 30 ~ 90min; The disposable CuCl adding drying, at room temperature stirs 0.5 ~ 4.0h; Adding 9-(bromophenyl) carbazole and pyridine, reflux 12 ~ 24h at 60 ~ 120 DEG C of temperature; Question response liquid is cooled to room temperature, is steamed by solvent wherein dry, gained solid water dissolution, with dichloromethane extraction, merge organic phase, simultaneously with anhydrous magnesium sulfate drying, filtering, solvent evaporated, the crude product of gained obtains white solid powder by the mode purifying of column chromatography; The white solid powder of gained in high vacuum conditions at 300 ~ 400 DEG C distillation obtain final product two carborane analog derivative.
The preparation method of two described carborane analog derivatives, wherein, in steps A, carborane monomer, n-BuLi, CuCl, 1,4-dibromobenzene, pyridine molar mass are than being 1:(0.9 ~ 1.05): (1 ~ 4): (0.2 ~ 0.55): (1 ~ 10);
In step B, white solid powder that steps A obtains, n-BuLi, CuCl, 9-(bromophenyl) carbazole, pyridine molar mass are than being 1:(2.0 ~ 4.0): (2.0 ~ 8.0): (2.0 ~ 5.0): (1.0 ~ 15.0).
The preparation method of two described carborane analog derivatives, wherein, described carborane monomer be between carborane or to carborane;
Described 9-(bromophenyl) carbazole is 9-(4-bromophenyl) carbazole, 9-(3-bromophenyl) carbazole or 9-(2-bromophenyl) carbazole.
An application for two carborane analog derivatives as above, wherein, using described two carborane analog derivatives as blue emitting phosphor main body luminescent material for the preparation of electroluminescent device.
A kind of electroluminescent device, wherein, described electroluminescent device comprises ito glass, and described ito glass is outwards attached with hole injection layer, hole transmission layer, exciton barrier, luminescent layer, electron transfer layer, electron injecting layer, aluminium electrode successively from inner; Described luminescent layer is made up of two carborane analog derivatives as claimed in claim 1 and dopant material, and described dopant material is iridium metal complexes.
Described electroluminescent device, wherein, described dopant material is FIr6, and doping content is 4% ~ 12%.
Described electroluminescent device, wherein, described electroluminescent device is with 3,3 ', 3, and "-three (3-pyridyl)-1,3,5-triphenylbenzene is as electron transfer layer.
Useful effect: two carborane analog derivatives provided by the present invention is that the host compound being connected with 9-phenyl carbazole by two carborane unit is connected by phenyl and obtains; While the two carborane analog derivatives so obtained keep higher triplet energy level, there is relatively high vitrifying conversion temp, and HOMO/LUMO energy level and the adjacent active layer level-density parameter of host compound is adjusted further by changing the conjugated structure of host compound, be conducive to the stable of device and make it obtain excellent electroluminescent properties, be conducive to developing efficient full-color display, it is possible to be widely used in the OLED large screen display that brightness requirement is higher and OLED white-light illuminating.
Accompanying drawing explanation
Fig. 1 is the structural representation of the electroluminescent device in the present invention.
Fig. 2 is the power efficiency graphic representation of device 1 and device 2 in the embodiment of the present invention 7.
Fig. 3 is the electroluminescent light spectrogram of device 1 and device 2 in the embodiment of the present invention 7.
Embodiment
The present invention provides a kind of two carborane analog derivatives, preparation method and application and electroluminescent device, and for making the object of the present invention, technical scheme and effect clearly, clearly, the present invention is described in more detail below. It is to be understood that specific embodiment described herein is only in order to explain the present invention, it is not intended to limit the present invention.
The present invention is keeping under the prerequisite that host compound triplet energy level is relatively high, bipolar transmission performance and the HOMO/LUMO energy level of host compound is regulated by the ratio and link position adjusting push-and-pull electron group, improve luminescent layer current carrier utilization ratio, improve the luminous efficiency of device further. Specifically, two carborane analog derivatives provided by the present invention are connected by a phenyl ring by two carborane monomers, simultaneously at the electron donating group (such as carbazole, triphenylamine etc.) that the peripheral connection of carborane is different, to reach the object of the bipolar transmission performance of adjustment host compound; In addition due to the structure of its twist relative, it is possible to adjust the vitrifying conversion temp of host compound well, it is to increase the life-span of device.
Specifically, described two carborane analog derivatives, are be connected with carbazole group by two carborane monomers, and connect electron donating group gained on carborane monomer; Its general structure is such as formula shown in (1) or formula (2):
Formula (1);
Formula (2).
When between carborane monomer is during carborane, the molecular structure of described two carborane analog derivatives is as the formula (1); When carborane monomer is to carborane, the molecular structure of described two carborane analog derivatives is as the formula (2). Described electron donating group can be trianilino group or other alkanes group or arene group.
Wherein, in formula (1), R1=is worked asTime, compound is 1,4-bis-(1-(9-(N-phenyl carbazole base))-4-(a carborane base)) benzene (being abbreviated as DpCPmCB), molecular structure as the formula (3):
Formula (3);
Work as R1=Time, compound is: 1,4-bis-(1-(9-(N-phenyl carbazole base))-3-(a carborane base)) benzene (being abbreviated as DmCPmCB), molecular structure as the formula (4):
Formula (4);
Work as R1=Time, compound is 1,4-bis-(1-(9-(N-phenyl carbazole base))-2-(a carborane base)) benzene (being abbreviated as DoCPmCB), molecular structure as the formula (5):
Formula (5);
Work as R2=Time, compound is 1,4-bis-(1-(9-(N-phenyl carbazole base))-4-(to carborane base)) benzene (being abbreviated as DpCPpCB), molecular structure as the formula (6):
Formula (6);
Work as R2=Time, compound is 1,4-bis-(1-(9-(N-phenyl carbazole base))-3-(to carborane base)) benzene (being abbreviated as DmCPpCB), molecular structure as the formula (7):
Formula (7);
Work as R2=Time, compound is 1,4-bis-(1-(9-(N-phenyl carbazole base))-2-(to carborane base)) benzene (being abbreviated as DoCPpCB), molecular structure as the formula (8):
Formula (8).
All two carborane analog derivatives are all containing identical 1,4-bis-carborane base phenyl group, change carborane group and 9-phenyl carbazole or trianilino group link position, the triplet energy level of whole host compound is kept to be in higher level, adjust the bipolar transmission performance of host compound well, the HOMO/LUMO energy level of adjustment host compound simultaneously. Owing to the structural distortion degree of gained compound strengthens further, improve the second-order transition temperature of host compound further, efficiency and the stability of phosphorescence luminescent device can be improved. All two carborane analog derivatives all can be used as dark blue emitting phosphor main body luminescent material.
In two carborane analog derivatives, it is connected the triplet energy level of the host compound obtained with carbazole group all more than 3.0eV by two carboranes; The blue emitting phosphor object FIr6 that adulterated forms luminescent layer, and the maximum external quantum efficiency of its device reaches 14.7%. And, owing to the structural distortion degree of two carborane analog derivatives is relatively large, its vitrifying conversion temp is all more than 150 DEG C, it is possible to improve the stability of phosphorescence luminescent device well, it is to increase the life-span of phosphorescence luminescent device. And after two carboranes and carbazole group link together, due to the change of its conjugated structure, the highest electronics of host compound can be adjusted further occupy track (HOMO) and minimum do not occupy track (LUMO), it is made to mate well with adjacent active layer energy level, adjust the ratio of push-and-pull electron group simultaneously, increase the recombination probability of hole and electronics, improve the efficiency of phosphorescence luminescent device further, reduce device efficiency roll-off under high illumination.
Also providing the preparation method of described two carborane analog derivatives in the present invention, raw material wherein used is known compound, can commercially buy or the synthesis of available methods known in the art.
The preparation method of described two carborane analog derivatives, its synthetic route as the formula (9), specifically comprises the following steps:
Formula (9)
A, carborane monomer is dissolved in dry diethyl ether solution, N2Under protective condition, at the temperature of 0 ~-80 DEG C, dropwise add the n-BuLi normal hexane solution of 2.5M, under keeping cold condition, continue stirring 30 ~ 90min; The disposable CuCl adding drying, the mixed solution of gained at room temperature stirs 0.5 ~ 4.0h; 1,4-dibromobenzene and pyridine being added rapidly wherein, the mixed solution obtained refluxes 12 ~ 24h at 60 ~ 120 DEG C of temperature; Question response liquid is cooled to room temperature, is steamed by solvent wherein dry, gained solid water dissolution, with dichloromethane extraction, merge organic phase, simultaneously with anhydrous magnesium sulfate drying, filtering, solvent evaporated, the crude product of gained obtains white solid powder by the mode purifying of column chromatography; Wherein, carborane monomer, n-BuLi, CuCl, 1,4-dibromobenzene, pyridine molar mass ratio are: 1:(0.9 ~ 1.05): (1 ~ 4): (0.2 ~ 0.55): (1 ~ 10);
B, the white solid powder dissolution that steps A is obtained in the diethyl ether solution of drying, N2Under protective condition, at the temperature of 0 ~-80 DEG C, dropwise add the n-BuLi normal hexane solution of 2.5M, under keeping cold condition, continue stirring 30 ~ 90min; The disposable CuCl adding drying, the mixed solution of gained at room temperature stirs 0.5 ~ 4.0h; 9-(bromophenyl) carbazole and pyridine being added rapidly wherein, the mixed solution obtained refluxes 12 ~ 24h at 60 ~ 120 DEG C of temperature; Question response liquid is cooled to room temperature, is steamed by solvent wherein dry, gained solid water dissolution, with dichloromethane extraction, merge organic phase, simultaneously with anhydrous magnesium sulfate drying, filtering, solvent evaporated, the crude product of gained obtains white solid powder by the mode purifying of column chromatography; The product of gained continues in high vacuum (< 10-3Pa) under condition, at 300 ~ 400 DEG C, distillation obtains final product two carborane analog derivative. Wherein, steps A obtains white solid powder, n-BuLi, CuCl, 9-(bromophenyl) carbazole, pyridine molar mass are than being 1:(2.0 ~ 4.0): (2.0 ~ 8.0): (2.0 ~ 5.0): (1.0 ~ 15.0).
Wherein, in steps A, when between carborane monomer is during carborane, in steps A, gained white solid powder is 1,4-bis-carborane benzene; When carborane monomer is to carborane, in steps A, gained white solid powder is that 1,4-bis-is to carborane benzene.
In step B, 9-(bromophenyl) carbazole can be 9-(4-bromophenyl) carbazole, 9-(3-bromophenyl) carbazole or 9-(2-bromophenyl) carbazole.
Carborane between carborane monomer is, when 9-(bromophenyl) carbazole is 9-(4-bromophenyl) carbazole, product is DpCPmCB; Carborane between carborane monomer is, when 9-(bromophenyl) carbazole is 9-(3-bromophenyl) carbazole, product is DmCPmCB; Carborane between carborane monomer is, when 9-(bromophenyl) carbazole is 9-(2-bromophenyl) carbazole, product is DoCPmCB;
When carborane monomer is to carborane, when 9-(bromophenyl) carbazole is 9-(4-bromophenyl) carbazole, product is DpCPpCB; When carborane monomer is to carborane, when 9-(bromophenyl) carbazole is 9-(3-bromophenyl) carbazole, product is DmCPpCB; When carborane monomer is to carborane, when 9-(bromophenyl) carbazole is 9-(2-bromophenyl) carbazole, product is DoCPpCB.
The present invention also provides the application of described two carborane analog derivatives, using described two carborane analog derivatives as blue emitting phosphor main body luminescent material for the preparation of electroluminescent device.
The present invention also provides a kind of electroluminescent device, it it is a kind of electro-phosphorescent luminescent device, comprising ito glass, described ito glass is attached with Conducting Glass layer, and described ito glass is outwards attached with hole injection layer successively from inner, hole transmission layer, exciton barrier, luminescent layer, electron transfer layer, electron injecting layer, aluminium electrode. Specifically, described electro-phosphorescent luminescent device, as shown in Figure 1, ITO is ito glass (anode), MoO3For hole injection layer, NPB is hole transmission layer, and mCP is exciton barrier, and EML is luminescent layer, and TmPyPB is electron transfer layer, and LiF is electron injecting layer, and Al is aluminium electrode (negative electrode). Wherein, luminescent layer is made up of described two carborane analog derivatives and dopant material, and described dopant material is mainly the iridium metal complexes of conventional commercialization, and such as blue light object FIr6, the doping content of usual doping agent FIr6 is 4% ~ 12%, is preferably 8%.
The present invention will have the 1 of particularly conjugated structure and better electronic transmission performance, the hole-transporting type 9-phenyl carbazole group that 4-bis-carborane base phenyl is strong with electron repulsive ability is connected, and forms high the triplet energy level (> 3.0eV of hole and electronics bipolar transmission) phosphorescent light body material. Due to the conjugated structure that two carborane unit are special, the structural distortion degree of compound becomes big, it is possible to improves host compound vitrifying conversion temp well, increases the stability of phosphorescence luminescent device. Simultaneously owing to the conjugated structure of phosphorescent light body material changes, impel the HOMO/LUMO level-density parameter of the HOMO/LUMO energy level of host compound and adjacent active layer better, improve triplet exciton recombination probability, it is to increase device light emitting efficiency, reduce phosphorescence device efficiency roll-off under high illumination. Using them as luminescent layer in the present invention, with 3,3 ', 3 " the phosphorescence luminescent device high-high brightness that-three (3-pyridyl)-1,3,5-triphenylbenzene (TmPyPB) are prepared as electron transfer layer reaches 18540cd/m2Maximum power efficiency reaches 20.0lm/W, efficiency roll-off is less under high illumination, the intrinsic of luminescent spectrum display object FIr6 is luminous, it it is one of current dark blue emitting phosphor luminescent device power efficiency maximum, device performance is far above the dark blue emitting phosphor luminescent device taking the most frequently used material 1,3-bis-carbazyl benzene (mCP) as main body luminescent material.
With example, the present invention being described further below, described example should not be construed as limiting the invention.
Embodiment 1
The preparation of 1,4-bis-(1-(9-(N-phenyl carbazole base))-4-(a carborane base)) benzene:
Between inciting somebody to action, carborane (2.0mmol) is dissolved in dry diethyl ether solution (100ml), N2Under protective condition, at the temperature of-5 DEG C, dropwise add n-BuLi normal hexane (2.0mmol) solution of 2.5M, continue to stir 30min under keeping cold condition; The disposable CuCl (3.0mmol) adding drying, the mixed solution of gained at room temperature stirs 1.0h; Finally 1,4-dibromobenzene (1.0mmol) and pyridine (5.0ml) being added rapidly wherein, the mixed solution obtained refluxes 18h at 80 DEG C of temperature; Question response liquid is cooled to room temperature, is steamed by solvent wherein dry, gained solid water dissolution, with dichloromethane extraction, merge organic phase, simultaneously with anhydrous magnesium sulfate drying, filtering, solvent evaporated, the crude product of gained obtains white solid powder by the mode purifying of column chromatography;
White solid powder 1,4-obtained in the previous step bis-carborane benzene (1.0mmol) are dissolved in dry ether (80ml) solution, N2Under protective condition, at the temperature of-5 DEG C, dropwise add n-BuLi normal hexane (2.4mmol) solution of 2.5M, continue to stir 45min under keeping cold condition; The disposable CuCl (3.0mmol) adding drying, the mixed solution of gained at room temperature stirs 1.5h; Finally 9-(4-bromophenyl) carbazole (2.4mmol) and pyridine (4.0ml) being added rapidly wherein, reflux at the mixing obtained 80 DEG C of temperature 18h; Question response liquid is cooled to room temperature, solvent wherein is steamed dry, gained solid water dissolution, with dichloromethane extraction, merge organic phase, simultaneously with anhydrous magnesium sulfate drying, filter, solvent evaporated, the crude product of gained obtains white solid powder by the mode purifying of column chromatography, and the product of gained continues in high vacuum (< 10-3Pa) at lower 380 DEG C of condition, distillation obtains final product is two carborane analog derivatives, i.e. 1,4-bis-(1-(9-(N-phenyl carbazole base))-4-(a carborane base)) benzene (DpCPmCB) (0.5mmol). Product rate: 50.0%. MS (APCI): calcdforC46H28B20N2:824.9,found,826.4(M+1)+��
Embodiment 2
The preparation of 1,4-bis-(1-(9-(N-phenyl carbazole base))-3-(a carborane base)) benzene:
Adopting the method similar with Compound D pCPmCB, difference is in rear single step reaction using 9-(3-bromophenyl) carbazole replacement 9-(4-bromophenyl) carbazole as starting raw material. 1,4-bis-(1-(9-(N-phenyl carbazole base))-3-(a carborane base)) benzene (DmCPmCB) white solid powder can be obtained, product rate: 54%. MS (APCI): calcdforC46H28B20N2:824.9,found,826.2(M+1)+��
Embodiment 3
The preparation of 1,4-bis-(1-(9-(N-phenyl carbazole base))-2-(a carborane base)) benzene:
Adopting the method similar with Compound D pCPmCB, difference is in rear single step reaction using 9-(2-bromophenyl) carbazole replacement 9-(4-bromophenyl) carbazole as starting raw material. 1,4-bis-(1-(9-(N-phenyl carbazole base))-2-(a carborane base)) benzene (DoCPmCB) white solid powder can be obtained, product rate: 45%. MS (APCI): calcdforC46H28B20N2:824.9,found,826.4(M+1)+��
Embodiment 4
The preparation of 1,4-bis-(1-(9-(N-phenyl carbazole base))-4-(to carborane base)) benzene:
Adopting and the similar method of Compound D pCPmCB, difference is the first step in reacting using carborane between being replaced by carborane as starting raw material. 1,4-bis-(1-(9-(N-phenyl carbazole base))-4-(to carborane base)) benzene (DpCPpCB) white solid powder can be obtained, product rate: 58%. MS (APCI): calcdforC46H28B20N2:824.9,found,826.2(M+1)+��
Embodiment 5
The preparation of 1,4-bis-(1-(9-(N-phenyl carbazole base))-3-(to carborane base)) benzene:
Adopting and the similar method of Compound D mCPmCB, difference is the first step in reacting using carborane between being replaced by carborane as starting raw material. 1,4-bis-(1-(9-(N-phenyl carbazole base))-3-(to carborane base)) benzene (DmCPpCB) white solid powder can be obtained, product rate: 54%. MS (APCI): calcdforC46H28B20N2:824.9,found,825.8(M+1)+��
Embodiment 6
The preparation of 1,4-bis-(1-(9-(N-phenyl carbazole base))-2-(to carborane base)) benzene:
Adopting and the similar method of Compound D oCPmCB, difference is the first step in reacting using carborane between being replaced by carborane as starting raw material. 1,4-bis-(1-(9-(N-phenyl carbazole base))-2-(to carborane base)) benzene (DoCPpCB) white solid powder can be obtained, product rate: 44%. MS (APCI): calcdforC46H28B20N2:824.9,found,825.9(M+1)+��
Embodiment 7
The preparation of electro-phosphorescent luminescent device: owing to two carborane analog derivatives preparation-obtained in embodiment 1 ~ 6 can be divided into two big classes, therefore for electro-phosphorescent luminescent device preparation mainly with DpCPmCB and DpCPpCB two host compounds representatively, other each compound has similar device performance.
Using DpCPmCB as dark blue emitting phosphor, luminous material of main part prepares phosphorescence luminescent device 1:
Ito glass in succession in clean-out system and deionized water with ultrasonic cleaning 30 minutes. Then vacuum-drying 2 hours (105 DEG C), then ito glass is put into the CFx plasma treatment that plasma reactor carries out 1 minute, it is sent in vacuum chamber and prepares organic membrane and metal electrode. By the method for vacuum evaporation, DpCPmCB is prepared into device as the luminous material of main part of blue emitting phosphor. Specifically, as shown in table 1, this experiment apparatus 1 structure is:
ITO/MoO3(10nm)/NPB(40nm)/mCP(5nm)/DpCPmCB:FIr6(20nm)/TmPyPB(40nm)/LiF(1nm)/Al��
Using DpCPpCB as blue emitting phosphor luminescent material fabricate devices 2:
Ito glass in succession in clean-out system and deionized water with ultrasonic cleaning 30 minutes. Then vacuum-drying 2 hours (105 DEG C), then ito glass is put into the CFx plasma treatment that plasma reactor carries out 1 minute, it is sent in vacuum chamber and prepares organic membrane and metal electrode. By the method for vacuum evaporation, DpCPpCB is prepared into device as blue emitting phosphor main body luminescent material. Specifically, as shown in table 1, this experiment apparatus 1 structure is:
ITO/MoO3(10nm)/NPB(40nm)/mCP(5nm)/DpCPpCB:FIr6(20nm)/TmPyPB(40nm)/LiF(1nm)/Al��
Table 1 prepares the device architecture of Organic Light Emitting Diode with the compounds of this invention
| Device number | Device architecture |
| Device 1 | ITO/MoO3( 10 nm)/NPB(40 nm)/mCP (5 nm)/ DpCPmCB: FIr6 (20 nm)/ TmPyPB (40 nm)/ LiF(1 nm)/Al |
| Device 2 | ITO/MoO3(10 nm)/NPB(40 nm)/mCP (5 nm)/ DpCPpCB: FIr6 (20 nm)/ TmPyPB (40 nm)/ LiF(1 nm)/Al |
Keithley source measuring system (Keithley2400) that the current-voltage-brightness curve of device 1 and 2 and electroluminescent spectrum are the silicon photoelectric diodes by band overcorrection records, its electroluminescent spectrum has been tested by PR655 simultaneously, and all measurements all complete in atmosphere at room temperature. As shown in Figure 2, electroluminescent spectrum is as shown in Figure 3 for the power efficiency graphic representation of described device 1 and device 2.
Made device 1 and 2 and document (Appl.Phys.Lett.2003,82,2422.) device efficiency of the most frequently used blue emitting phosphor material of main part mCP in is compared, device efficiency increases substantially, and its electroluminescent spectrum color be the intrinsic luminescent spectrum of object FIr6 is (0.15,0.25), Fig. 3 is seen. Based on DpCPpCB, FIr6 is the luminescent layer that object forms phosphorescence luminescent device, and its device maximum current efficiency reaches 25.5lm/W, sees Fig. 2, and high-high brightness reaches 18540cd/m simultaneously2��
The host compound that two carborane unit are connected with 9-phenyl carbazole is connected by the present invention by phenyl, while being obtained the triplet energy level that two carborane analog derivatives keep higher, there is relatively high vitrifying conversion temp, and HOMO/LUMO energy level and the adjacent active layer level-density parameter of host compound is adjusted further by changing the conjugated structure of host compound, be conducive to the stable of device and make it obtain excellent electroluminescent properties, be conducive to developing efficient full-color display, the OLED large screen display that brightness requirement is higher and OLED white-light illuminating can be widely used in.
Should be understood that, the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, it is possible to is improved according to the above description or converts, and all these improve and convert the protection domain that all should belong to claims of the present invention.
Claims (7)
1. a carborane analog derivative, it is characterised in that, described two carborane analog derivatives are connected with phenyl ring group by two carborane monomers, and connects electron donating group gained on carborane monomer;
When between carborane monomer is during carborane, the molecular structure of described two carborane analog derivatives is
; Wherein, R1Group is��Or;
When carborane monomer is to carborane, the molecular structure of described two carborane analog derivatives; Wherein, R2Group is��Or��
2. the preparation method of two carborane analog derivatives as claimed in claim 1, it is characterised in that, comprise the following steps:
A, carborane monomer is dissolved in dry diethyl ether solution, N2Under protective condition, at the temperature of 0 ~-80 DEG C, dropwise add the n-BuLi solution of 2.5M, under keeping cold condition, continue stirring 30 ~ 90min; The disposable CuCl adding drying, at room temperature stirs 0.5 ~ 4.0h; Adding 1,4-dibromobenzene and pyridine, reflux 12 ~ 24h at 60 ~ 120 DEG C of temperature; Question response liquid is cooled to room temperature, is steamed by solvent wherein dry, gained solid water dissolution, with dichloromethane extraction, merge organic phase, simultaneously with anhydrous magnesium sulfate drying, filtering, solvent evaporated, the crude product of gained obtains white solid powder by the mode purifying of column chromatography;
B, the white solid powder dissolution that steps A is obtained in the diethyl ether solution of drying, N2Under protective condition, at the temperature of 0 ~-80 DEG C, dropwise add the n-BuLi solution of 2.5M, under keeping cold condition, continue stirring 30 ~ 90min; The disposable CuCl adding drying, at room temperature stirs 0.5 ~ 4.0h; Adding 9-(bromophenyl) carbazole and pyridine, reflux 12 ~ 24h at 60 ~ 120 DEG C of temperature; Question response liquid is cooled to room temperature, is steamed by solvent wherein dry, gained solid water dissolution, with dichloromethane extraction, merge organic phase, simultaneously with anhydrous magnesium sulfate drying, filtering, solvent evaporated, the crude product of gained obtains white solid powder by the mode purifying of column chromatography; The white solid powder of gained in high vacuum conditions at 300 ~ 400 DEG C distillation obtain final product two carborane analog derivative.
3. the preparation method of two carborane analog derivatives according to claim 2, it is characterized in that, in steps A, carborane monomer, n-BuLi, CuCl, 1,4-dibromobenzene, pyridine molar mass are than being 1:(0.9 ~ 1.05): (1 ~ 4): (0.2 ~ 0.55): (1 ~ 10);
In step B, white solid powder that steps A obtains, n-BuLi, CuCl, 9-(bromophenyl) carbazole, pyridine molar mass are than being 1:(2.0 ~ 4.0): (2.0 ~ 8.0): (2.0 ~ 5.0): (1.0 ~ 15.0).
4. the application of two carborane analog derivatives as claimed in claim 1, it is characterised in that, using described two carborane analog derivatives as blue emitting phosphor main body luminescent material for the preparation of electroluminescent device.
5. an electroluminescent device, it is characterised in that, described electroluminescent device comprises ito glass, and described ito glass is outwards attached with hole injection layer, hole transmission layer, exciton barrier, luminescent layer, electron transfer layer, electron injecting layer, aluminium electrode successively from inner; Described luminescent layer is made up of two carborane analog derivatives as claimed in claim 1 and dopant material, and described dopant material is iridium metal complexes.
6. electroluminescent device according to claim 5, it is characterised in that, described dopant material is FIr6, and doping content is 4% ~ 12%.
7. electroluminescent device according to claim 5, it is characterised in that, described electroluminescent device is with 3,3 ', 3, and "-three (3-pyridyl)-1,3,5-triphenylbenzene is as electron transfer layer.
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| JP6307332B2 (en) * | 2014-04-21 | 2018-04-04 | 新日鉄住金化学株式会社 | Organic electroluminescence device |
| TWI684595B (en) * | 2015-03-30 | 2020-02-11 | 日商日鐵化學材料股份有限公司 | Material for organic electric field light emitting element and organic electric field light emitting element using the same |
| CN106866716B (en) * | 2017-04-28 | 2019-01-08 | 南京大学 | A kind of carborane derivative as well as preparation method and application thereof |
| CN107353302A (en) * | 2017-07-03 | 2017-11-17 | 南京邮电大学 | A kind of carborane derivative material based on carbazole and preparation method and application |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6492570B1 (en) * | 1996-08-11 | 2002-12-10 | British Nuclear Fuels Plc | Metallacarboranes |
| JP2005162709A (en) * | 2003-12-05 | 2005-06-23 | Canon Inc | Carborane compound |
| JP2005166574A (en) * | 2003-12-05 | 2005-06-23 | Canon Inc | Organic luminescent element |
-
2012
- 2012-12-04 CN CN201210511082.7A patent/CN103509043B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6492570B1 (en) * | 1996-08-11 | 2002-12-10 | British Nuclear Fuels Plc | Metallacarboranes |
| JP2005162709A (en) * | 2003-12-05 | 2005-06-23 | Canon Inc | Carborane compound |
| JP2005166574A (en) * | 2003-12-05 | 2005-06-23 | Canon Inc | Organic luminescent element |
Non-Patent Citations (2)
| Title |
|---|
| 《Carborane Photochemistry Triggered by Aryl Substitution: Carborane-Based Dyads with Phenyl Carbazoles》;Kyung-Ryang Wee等;《Angew. Chem. Int. Ed.》;20120201;第51卷;2677-2680 * |
| A.S.Batsanov等.《Synthesis and solid state structure of α,α’-bis(2-phenyl-1,2-carboran-1-yl)lutidine》.《Journal of Organometallic Chemistry》.2001,第643卷(第1期), * |
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