CN102898469B - The two phosphine oxygen of difunctionalization replaces fluorenyl photoelectric functional material and its preparation method and application - Google Patents
The two phosphine oxygen of difunctionalization replaces fluorenyl photoelectric functional material and its preparation method and application Download PDFInfo
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Abstract
The two phosphine oxygen of difunctionalization replaces fluorenyl photoelectric functional material and its preparation method and application, it relates to organic photoelectric functional material and its preparation method and application, the present invention will solve existing Fluorenyl aromatic phosphine oxide photoelectric functional material, the major axis of aromatic phosphines oxygen groups is modified, and causes the problem that the triplet of material and blue emission cannot keep.It is as follows that the two phosphine oxygen of difunctionalization of the present invention replaces fluorenyl photoelectric functional material structure:
preparation method is: with the two phosphine oxygen phenyl fluorenes monomer of fragrance for core, modify fluorenes 2,7 with the group (carbazole etc.) with hole transport performance, has synthesized a series of two phosphine oxygen photoelectric material of ternary fluorenyl fragrance with dipole characteristic.It is applied in blue organic light-emitting devices.Present invention utilizes and indirectly connect organic phosphine oxygen groups strategy, build the two phosphine oxygen phenyl fluorenes monomer core of fragrance.Modify with cavity transmission group periphery, construct the bipolar phosphorescent light body material of ternary; And strengthen the fluorescence quantum efficiency that its luminescent properties improves material.
Description
Technical field
The present invention relates to organic photoelectric functional material and its preparation method and application, be specifically related to a class and modify fluorene derivatives its preparation method and application thereof by double carriers transport group.
Background technology
OLED luminescence refers to that hole is injected from positive electrode under the effect of electric field, and electronics injects from negative potential, transfers to luminescent layer and carries out compound, thus forms exciton, then exciton generation radiation, decays and the phenomenon of luminescence.Fluorescent material relies on singlet excitons attenuation and luminous, and the internal quantum efficiency of device can not more than 25% in theory, but its luminescent layer material is single, decreases the impact owing to adulterating on device color color purity and life time decay; And with the phosphorescent coloring that phosphorescent light body material adulterates, triplet state and singlet excitons generation attenuation can be utilized luminous, and the internal quantum efficiency of device is up to 100% in theory simultaneously.Thus, at present exploitation high efficiency blue fluorescent material and blue emitting phosphor material of main part are mainly concentrated on to the research of blue light material.
The impact of phosphine oxygen groups on excited level is less, is usually used in building high efficiency blue phosphorescent light body material, 2009 also first Application in the structure of dark blue fluorescence material.Become the important functional group building blue light material.But existing Fluorenyl aromatic phosphine oxide blue light material, aromatic phosphines oxygen groups replaces often through major axis, and P=O double bond still can cause the decline of triplet and the red shift of transmitting of material.Thus, how while introducing aromatic phosphines oxygen groups regulates material electronics to inject transmission performance, keeping the high triplet energy level of parent core and dark blue light emission, is successfully realize the problem that high efficiency blue phosphorescence and dark blue smooth fluorescent device need to solve.
Summary of the invention
The object of the invention is to solve existing Fluorenyl aromatic phosphine oxide photoelectric functional material, the major axis of aromatic phosphines oxygen groups is modified, cause the problem that the triplet of material and blue emission cannot keep, and provide the two phosphine oxygen of difunctionalization to replace fluorenyl photoelectric functional material and its preparation method and application.
It is as follows that the two phosphine oxygen of difunctionalization of the present invention replaces fluorenyl photoelectric functional material structure:
Wherein, R is
Preparation method's step that the two phosphine oxygen of difunctionalization of the present invention replaces fluorenyl photoelectric functional material is as follows:
One, by 9,9-bis--(diphenylphosphine oxygen phenyl) fluorenes is dissolved in mixed solution, add N-bromo-succinimide, methylene dichloride or ethyl acetate is adopted to extract, after extraction, collected organic layer is dry at ambient temperature, then adopts ethyl acetate to carry out column chromatography purification as leacheate, obtains 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes;
Two, step one obtained 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes is preced with-6 ethers with salt of wormwood, carbazole, cuprous iodide and 18-and is mixed, and obtains mixture; High-temperature solvent is added in mixture, then under nitrogen protection, temperature are the condition of 90 DEG C ~ 250 DEG C, 12 ~ 50h is reacted, methylene dichloride or ethyl acetate is adopted to extract in reacted mixture, collected organic layer, dry, adopt ethyl acetate to carry out column chromatography purification as leacheate, obtain the two phosphine oxygen of difunctionalization and replace fluorenyl photoelectric functional material;
Wherein, mixed solution described in step one is that the ratio being 1 ~ 3:1 by volume by Glacial acetic acid and the vitriol oil mixes, 9,9-bis--(the diphenylphosphine oxygen phenyl) amount of substance of fluorenes and the ratio of mixeding liquid volume are 1mmol:9 ~ 15mL, the mol ratio of 9,9-, bis--(diphenylphosphine oxygen phenyl) fluorenes and N-bromo-succinimide is 1:1 ~ 5;
Described in step 22, mol ratio 1:1 ~ 3 of bromo-9,9-bis-(the diphenylphosphine oxygen phenyl) fluorenes of 7-bis-and salt of wormwood, the mol ratio of salt of wormwood and carbazole is 3:1 ~ 5, salt of wormwood and cuprous iodide mol ratio be 30:0.5 ~ 2, the mol ratio that salt of wormwood and 18-are preced with-6 ethers is 150 ~ 300:2;
High-temperature solvent described in step 2 is 1,3-dimethyl-3,4,5,6-tetrahydrochysene-2-pyrimidone, and the volume ratio of bromo-9,9-bis-(diphenylphosphine oxygen phenyl) the fluorenes amount of substances of 2,7-bis-and high-temperature solvent is 1mmol:5 ~ 10mL.
Preparation method's step that the two phosphine oxygen of difunctionalization of the present invention replaces fluorenyl photoelectric functional material is as follows:
One, by 9,9-bis--(diphenylphosphine oxygen phenyl) fluorenes is dissolved in mixed solution, add N-bromo-succinimide, methylene dichloride or ethyl acetate is adopted to extract, after extraction, collected organic layer is dry at ambient temperature, then adopts ethyl acetate to carry out column chromatography purification as leacheate, obtains 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes;
Two, step one is obtained 2,7-bis-bromo-9-phenyl-9-diphenylphosphine oxygen phenyl fluorenes and tetra-triphenylphosphine palladium, Tetrabutyl amonium bromide and boric acid ester compound mix, again under argon shield, dark condition, add tetrahydrofuran (THF) to dissolve, adding concentration is again after the NaOH solution of 2mol/L, is to react 8 ~ 32h under the condition of 80 DEG C ~ 90 DEG C in temperature, obtains reaction head product; Then with saturated ammonium chloride solution, reaction head product is extracted, collected organic layer, dry, adopt ethyl acetate to carry out column chromatography purification as leacheate, obtain the single phosphine oxygen of difunctionalization and replace fluorenyl photoelectric functional material;
Wherein, mixed solution described in step one is that the ratio being 1 ~ 3:1 by volume by Glacial acetic acid and the vitriol oil mixes, 9,9-bis--(diphenylphosphine oxygen phenyl) fluorenes amount of substance and mixeding liquid volume are than being 1mmol:9 ~ 15mL, the mol ratio of 9,9-, bis--(diphenylphosphine oxygen phenyl) fluorenes and N-bromo-succinimide is 1:1 ~ 5;
Boric acid ester compound described in step 2 is
2, 7-bis-bromo-9, the mol ratio of 9-bis-(diphenylphosphine oxygen phenyl) fluorenes and tetra-triphenylphosphine palladium is 1 ~ 10:1, 2, 7-bis-bromo-9, the mol ratio of 9-bis-(diphenylphosphine oxygen phenyl) fluorenes and Tetrabutyl amonium bromide is 5 ~ 10:1, 2, 7-bis-bromo-9, 9-bis-(diphenylphosphine oxygen phenyl) fluorenes and boric acid ester mol ratio be 1:2 ~ 4, 2, 7-bis-bromo-9, 9-bis-(diphenylphosphine oxygen phenyl) fluorenes amount of substance and tetrahydrofuran (THF) volume ratio are 1mmol:10 ~ 30mL, concentration is the NaOH solution and 2 of 2mol/L, 7-bis-bromo-9, 9-bis-(diphenylphosphine oxygen phenyl) fluorenes mol ratio is 10 ~ 15:1.
The two phosphine oxygen of difunctionalization of the present invention replaces fluorenyl photoelectric functional material as the application of luminescent layer material of main part in blue organic light-emitting devices.
The present invention comprises following beneficial effect:
The present invention by indirectly connecting the design philosophy of aromatic phosphines oxygen groups, and regulates and controls its Photophysics and electric property with hole injection transmission performance functional group, realizes the structure of high efficiency blue material.
The present invention for core with the two phosphine oxygen phenyl fluorenes of the fragrance indirectly connecting structure, carries out periphery with the group with carrier transmission performance and modifies, form the Fluorenyl aromatic phosphine oxide photoelectric material that a class has bipolar carrier transmission performance.
Of the present invention pair of phosphine dibenzofuran radical derivative has the ability of stronger trapped electron, the introducing of the injection of peripheral hole and transport group, the Photophysics of material and the regulation and control of electric property can be realized, reach the object building high-performance phosphorescent light body material and high efficiency blue fluorescent material.
Accompanying drawing explanation
Fig. 1 is electroluminescent spectrum figure, wherein, curve 1 is the emission peak curve that the organic electroluminescence fluorescence device adopting the Fluorenyl aromatic phosphine oxide compound that obtains of experiment 2 to prepare records, curve 2 is the emission peak curve that organic electroluminescence fluorescence device prepared by Fluorenyl aromatic phosphine oxide compound that experiment 3 obtains records, curve 3 is the emission peak curve that organic electroluminescence fluorescence device prepared by Fluorenyl aromatic phosphine oxide compound that experiment 4 obtains records, curve 4 is the emission peak curve that organic electroluminescence fluorescence device prepared by Fluorenyl aromatic phosphine oxide compound that experiment 5 obtains records, curve 5 is the emission peak curve that organic electroluminescence fluorescence device prepared by Fluorenyl aromatic phosphine oxide compound that experiment 6 obtains records,
Fig. 2 is the current density-efficiency curve diagram of blue organic electroluminescence phosphorescent devices; Wherein, curve 1 is the curve of device A, and curve 2 is the curve of device B;
Fig. 3 is the current density-efficiency curve diagram of blue organic electroluminescence fluorescent device, and wherein, curve 1 is the curve of device C, and curve 2 is the curve of device D, and curve 3 is the curve of device E.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: difunctionalization single phosphine oxygen replacement fluorenyl photoelectric functional material structure of present embodiment is as follows:
Wherein, R is
Present embodiment by indirectly connecting the design philosophy of aromatic phosphines oxygen groups, and regulates and controls its Photophysics and electric property with hole injection transmission performance functional group, realizes the structure of high efficiency blue material.
Present embodiment for core with the two phosphine oxygen phenyl fluorenes of the fragrance indirectly connecting structure, is carried out periphery with the group with carrier transmission performance and is modified, form the Fluorenyl aromatic phosphine oxide photoelectric material that a class has bipolar carrier transmission performance.
Two phosphine dibenzofuran radical derivatives of present embodiment have the ability of stronger trapped electron, the introducing of the injection of peripheral hole and transport group, the Photophysics of material and the regulation and control of electric property can be realized, reach the object building high-performance phosphorescent light body material and high efficiency blue fluorescent material.
Specifically embodiment two: the preparation process of the preparation method of difunctionalization single phosphine oxygen replacement fluorenyl photoelectric functional material of present embodiment is as follows:
One, by 9,9-bis--(diphenylphosphine oxygen phenyl) fluorenes is dissolved in mixed solution, add N-bromo-succinimide, methylene dichloride or ethyl acetate is adopted to extract, after extraction, collected organic layer is dry at ambient temperature, then adopts ethyl acetate to carry out column chromatography purification as leacheate, obtains 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes;
Two, step one obtained 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes is preced with-6 ethers with salt of wormwood, carbazole, cuprous iodide and 18-and is mixed, and obtains mixture; High-temperature solvent is added in mixture, then under nitrogen protection, temperature are the condition of 90 DEG C ~ 250 DEG C, 12 ~ 50h is reacted, methylene dichloride or ethyl acetate is adopted to extract in reacted mixture, collected organic layer, dry, adopt ethyl acetate to carry out column chromatography purification as leacheate, obtain the two phosphine oxygen of difunctionalization and replace fluorenyl photoelectric functional material;
Wherein, mixed solution described in step one is that the ratio being 1 ~ 3:1 by volume by Glacial acetic acid and the vitriol oil mixes, 9,9-bis--(the diphenylphosphine oxygen phenyl) amount of substance of fluorenes and the ratio of mixeding liquid volume are 1mmol:9 ~ 15mL, the mol ratio of 9,9-, bis--(diphenylphosphine oxygen phenyl) fluorenes and N-bromo-succinimide is 1:1 ~ 5;
Described in step 22, mol ratio 1:1 ~ 3 of bromo-9,9-bis-(the diphenylphosphine oxygen phenyl) fluorenes of 7-bis-and salt of wormwood, the mol ratio of salt of wormwood and carbazole is 3:1 ~ 5, salt of wormwood and cuprous iodide mol ratio be 30:0.5 ~ 2, the mol ratio that salt of wormwood and 18-are preced with-6 ethers is 150 ~ 300:2;
High-temperature solvent described in step 2 is 1,3-dimethyl-3,4,5,6-tetrahydrochysene-2-pyrimidone, and the volume ratio of bromo-9,9-bis-(diphenylphosphine oxygen phenyl) the fluorenes amount of substances of 2,7-bis-and high-temperature solvent is 1mmol:5 ~ 10mL.
Present embodiment by indirectly connecting the design philosophy of aromatic phosphines oxygen groups, and regulates and controls its Photophysics and electric property with hole injection transmission performance functional group, realizes the structure of high efficiency blue material.
Present embodiment for core with the two phosphine oxygen phenyl fluorenes of the fragrance indirectly connecting structure, is carried out periphery with the group with carrier transmission performance and is modified, form the Fluorenyl aromatic phosphine oxide photoelectric material that a class has bipolar carrier transmission performance.
Two phosphine dibenzofuran radical derivatives of present embodiment have the ability of stronger trapped electron, the introducing of the injection of peripheral hole and transport group, the Photophysics of material and the regulation and control of electric property can be realized, reach the object building high-performance phosphorescent light body material and high efficiency blue fluorescent material.
Embodiment three: present embodiment and embodiment two unlike: the mol ratio of bis--(the diphenylphosphine oxygen phenyl) fluorenes of 9,9-described in step one and N-bromo-succinimide is 1:3.Other is identical with embodiment two.
Embodiment four: present embodiment and embodiment two or three unlike: the mol ratio of bromo-9,9-bis-(the diphenylphosphine oxygen phenyl) fluorenes of 2,7-described in step 2 bis-and salt of wormwood is 1:2.Other is identical with embodiment two or three.
Embodiment five: the preparation process of the preparation method of difunctionalization single phosphine oxygen replacement fluorenyl photoelectric functional material of present embodiment is as follows:
One, by 9,9-bis--(diphenylphosphine oxygen phenyl) fluorenes is dissolved in mixed solution, add N-bromo-succinimide, methylene dichloride or ethyl acetate is adopted to extract, after extraction, collected organic layer is dry at ambient temperature, then adopts ethyl acetate to carry out column chromatography purification as leacheate, obtains 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes;
Two, step one is obtained 2,7-bis-bromo-9-phenyl-9-diphenylphosphine oxygen phenyl fluorenes and tetra-triphenylphosphine palladium, Tetrabutyl amonium bromide and boric acid ester compound mix, again under argon shield, dark condition, add tetrahydrofuran (THF) to dissolve, adding concentration is again after the NaOH solution of 2mol/L, is to react 8 ~ 32h under the condition of 80 DEG C ~ 90 DEG C in temperature, obtains reaction head product; Then with saturated ammonium chloride solution, reaction head product is extracted, collected organic layer, dry, adopt ethyl acetate to carry out column chromatography purification as leacheate, obtain the single phosphine oxygen of difunctionalization and replace fluorenyl photoelectric functional material;
Wherein, mixed solution described in step one is that the ratio being 1 ~ 3:1 by volume by Glacial acetic acid and the vitriol oil mixes, 9,9-bis--(diphenylphosphine oxygen phenyl) fluorenes amount of substance and mixeding liquid volume are than being 1mmol:9 ~ 15mL, the mol ratio of 9,9-, bis--(diphenylphosphine oxygen phenyl) fluorenes and N-bromo-succinimide is 1:1 ~ 5;
Boric acid ester compound described in step 2 is
2, 7-bis-bromo-9, the mol ratio of 9-bis-(diphenylphosphine oxygen phenyl) fluorenes and tetra-triphenylphosphine palladium is 1 ~ 10:1, 2, 7-bis-bromo-9, the mol ratio of 9-bis-(diphenylphosphine oxygen phenyl) fluorenes and Tetrabutyl amonium bromide is 5 ~ 10:1, 2, 7-bis-bromo-9, 9-bis-(diphenylphosphine oxygen phenyl) fluorenes and boric acid ester mol ratio be 1:2 ~ 4, 2, 7-bis-bromo-9, 9-bis-(diphenylphosphine oxygen phenyl) fluorenes amount of substance and tetrahydrofuran (THF) volume ratio are 1mmol:10 ~ 30mL, concentration is the NaOH solution and 2 of 2mol/L, 7-bis-bromo-9, 9-bis-(diphenylphosphine oxygen phenyl) fluorenes mol ratio is 10 ~ 15:1.
Present embodiment by indirectly connecting the design philosophy of aromatic phosphines oxygen groups, and regulates and controls its Photophysics and electric property with hole injection transmission performance functional group, realizes the structure of high efficiency blue material.
Present embodiment for core with the two phosphine oxygen phenyl fluorenes of the fragrance indirectly connecting structure, is carried out periphery with the group with carrier transmission performance and is modified, form the Fluorenyl aromatic phosphine oxide photoelectric material that a class has bipolar carrier transmission performance.
Two phosphine dibenzofuran radical derivatives of present embodiment have the ability of stronger trapped electron, the introducing of the injection of peripheral hole and transport group, the Photophysics of material and the regulation and control of electric property can be realized, reach the object building high-performance phosphorescent light body material and high efficiency blue fluorescent material.
Described in present embodiment step 2
preparation method, specifically complete according to the following steps: by 15g(49.8mmol)
be dissolved in 50mL tetrahydrofuran (THF), at-78 DEG C, add 20mL(49.8mmol) n-Butyl Lithium, 12mL(49.8mmol) triisopropyl borate ester, after adding, be warming up to room temperature, reaction 12h, be cooled to 0 DEG C, add 100mL(2mmol/mL wherein) in hydrochloric acid, and at 0 DEG C, stirring reaction 12h, after reaction, use CH
2cl
2and H
2o extracts, and gets organic phase, is spin-dried for after drying, by the dissolution of solid that obtains in 50mL benzene, and adds 6g(49.8mmol wherein) tetramethyl ethylene ketone, at the temperature of backflow, reaction 12h.After reaction, use CH
2cl
2and H
2o extracts, and gets organic phase, is spin-dried for after drying, purifies, obtain using ethyl acetate as eluent column chromatography
Described in present embodiment step 2
chemSpiderId be 10024545.
Described in present embodiment step 2
chemSpiderId be 9814049.
Described in present embodiment step 2
preparation method, specifically complete according to the following steps: by 10g(26.8mmol)
be dissolved in 50mL tetrahydrofuran (THF), at-78 DEG C, add 10mL(26.8mmol) n-Butyl Lithium, 6.2mL(26.8mmol triisopropyl borate ester, after adding, be warming up to room temperature, reaction 12h, be cooled to 0 DEG C, add 80mL(2mmol/mL wherein) in hydrochloric acid, and at 0 DEG C, stirring reaction 12h, after reaction, use CH
2cl
2and H
2o extracts, and gets organic phase, is spin-dried for after drying, by the dissolution of solid that obtains in 50mL benzene, and adds 3.2g(26.8mmol wherein) tetramethyl ethylene ketone, at the temperature of backflow, reaction 12h.After reaction, use CH
2cl
2and H
2o extracts, and gets organic phase, is spin-dried for after drying, purifies, obtain using ethyl acetate as eluent column chromatography
Embodiment six: present embodiment and embodiment five unlike: the mol ratio of bis--(the diphenylphosphine oxygen phenyl) fluorenes of 9,9-described in step one and N-bromo-succinimide is 1:3.Other is identical with embodiment five.
Embodiment seven: present embodiment and embodiment six unlike: bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes of 2,7-described in step 2 bis-and boric acid ester mol ratio be 1:3.Other is identical with embodiment six.
Embodiment eight: the two phosphine oxygen of difunctionalization of present embodiment replaces the application in blue organic light-emitting devices as fluorescence radiation layer material or phosphorescent light body material of fluorenyl photoelectric functional material.
Present embodiment by indirectly connecting the design philosophy of aromatic phosphines oxygen groups, and regulates and controls its Photophysics and electric property with hole injection transmission performance functional group, realizes the structure of high efficiency blue material.
Present embodiment for core with the two phosphine oxygen phenyl fluorenes of the fragrance indirectly connecting structure, is carried out periphery with the group with carrier transmission performance and is modified, form the Fluorenyl aromatic phosphine oxide photoelectric material that a class has bipolar carrier transmission performance.
Two phosphine dibenzofuran radical derivatives of present embodiment have the ability of stronger trapped electron, the introducing of the injection of peripheral hole and transport group, the Photophysics of material and the regulation and control of electric property can be realized, reach the object building high-performance phosphorescent light body material and high efficiency blue fluorescent material.
Embodiment nine: present embodiment and embodiment eight unlike: the preparation method of blue organic light-emitting devices carries out according to following steps:
One, by vacuum evaporation technology on substrate material evaporation the first layer conductive layer as anode; Two, vacuum vapour deposition evaporation hole injection layer, hole transmission layer and hole transport/electronic barrier layer is successively adopted, and then adopt vacuum vapour deposition evaporation luminescent layer, evaporation electric transmission/exciton barrier-layer again on luminescent layer, last at electric transmission/exciton barrier-layer evaporation second layer conductive layer as negative electrode, namely complete the preparation of blue organic light-emitting devices;
Wherein, the first layer conductive layer thickness described in step one is 1 ~ 10nm, and the first layer conductive is tin indium oxide, polyaniline or PANI, and described substrate material is glass or plastics, and a kind of foam structural adhesive described in step 2 is MoO
3, hole transport layer material thickness is 10 ~ 50nm, the thickness of described hole transmission layer is 20 ~ 60nm, hole transport layer material is 4, 4 ', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine, N, N '-bis--(3-naphthyl)-N, N '-phenylbenzene-[1, 1 '-phenylbenzene]-4, 4 '-diamines or N, N '-bis--(3-aminomethyl phenyl)-N, N '-phenylbenzene-[1, 1 '-xenyl]-4, 4 '-diamines, described hole transport/electronic blocking layer thickness is 5 ~ 40nm, hole transport/electronic blocking layer material is that three (1-phenylpyrazoles) close iridium or 4, 4 ', 4 "-three (carbazole-9-base) triphenylamine, described light emitting layer thickness is 5 ~ 40nm, emitting layer material is that two phosphine oxygen replaces fluorenyl photoelectric functional material or complex of iridium and difunctionalization pair phosphine oxygen and replaces the adulterate body that fluorenyl photoelectric functional material is mixed to form, wherein, the two phosphine oxygen of difunctionalization replaces fluorenyl photoelectric functional material and accounts for 80% ~ 97% of adulterate body total mass, complex of iridium accounts for 3% ~ 20% of adulterate body total mass, the thickness of described electric transmission/exciton barrier-layer is 10 ~ 80nm, electric transmission/exciton barrier-layer material is 4, 7-phenylbenzene-1, 10-phenanthrolene or 1, 3, 5-tri-(N-phenyl-2-benzimidazolyl-2 radicals) benzene, described second layer conductive is calcium, calcium alloy, magnesium, magnesium alloy, silver, silver alloys, aluminum or aluminum alloy.Other is identical with embodiment eight.
Embodiment ten: present embodiment and embodiment eight or nine unlike: when second layer conductive is aluminium, need after electric transmission/exciton barrier-layer surface evaporation 1 ~ 5nm, material be the electron injecting layer of LiF, then in second layer conductive layer AM aluminum metallization.Other is identical with embodiment eight or nine.
By following experimental verification effect of the present invention:
Experiment 1
The synthesis step that the two phosphine oxygen of difunctionalization of this experiment replaces fluorenyl photoelectric functional material is as follows:
One, by 9 of 0.7188g, 9-diphenylphosphine oxygen phenyl fluorenes is dissolved in mixed solution, adds the N-bromo-succinimide (NBS) of 0.5337g, then adopts dichloromethane extraction, collected organic layer material after extraction, adopt anhydrous sodium sulphate at room temperature dry, then adopt ethyl acetate to carry out column chromatography as leacheate, collect product point, through concentrated, obtain 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes.
2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes that this experiment obtains is the white solid of 0.6136g, productive rate: 70%.
Adopt 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes that nuclear magnetic resonance analyser test experience obtains, detected result is as follows:
1HNMR(400MHz,CDCl
3):δ=7.69(d,J=9.6Hz,8H),7.62-7.45(m,22H),7.21(t,J=7.2Hz,4H)。
The structure of 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes that this experiment obtains is as follows:
chemical name is 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes.
Experiment 2
The synthesis step that the two phosphine oxygen of difunctionalization of this experiment replaces fluorenyl photoelectric functional material is as follows: one, by 9 of 0.7188g, 9-diphenylphosphine oxygen phenyl fluorenes is dissolved in mixed solution, add the N-bromo-succinimide (NBS) of 0.5337g, then dichloromethane extraction is adopted, collected organic layer after extraction, adopt anhydrous sodium sulphate at room temperature dry, then ethyl acetate is adopted to carry out column chromatography purification as leacheate, collect product point, through concentrated, obtain 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes; Two, 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes that step one obtains 0.8766g is got, the tetra-triphenylphosphine palladium (Pd (PPh of 0.1156g
3)
4), the Tetrabutyl amonium bromide (TBAB) of 0.0322g and the boric acid ester compound of 1.3932g mix, and then under argon shield, dark condition, the tetrahydrofuran (THF) (THF) adding 25mL mixes, and obtains mixing solutions; Be that the NaOH solution of 2mol/L mixes with mixing solutions by the concentration of 6mL, be react 24h under the condition of 80 DEG C in temperature, obtain reaction head product; Then with saturated ammonium chloride, reaction head product is extracted, collected organic layer, use anhydrous sodium sulphate drying at room temperature, adopt ethyl acetate to carry out column chromatography purification as leacheate dried material, obtain the two phosphine oxygen of difunctionalization and replace fluorenyl photoelectric functional material.
The structural formula of the boric acid ester compound in this experiment described in step 2 is
chemical name is diethyl fluorenes boric acid ester.
Described in this experimental procedure two
preparation method, specifically complete according to the following steps: by 15g(49.8mmol)
be dissolved in 50mL tetrahydrofuran (THF), at-78 DEG C, add 20mL(49.8mmol) n-Butyl Lithium, 12mL(49.8mmol) triisopropyl borate ester, after adding, be warming up to room temperature, reaction 12h, be cooled to 0 DEG C, add 100mL(2mmol/mL wherein) in hydrochloric acid, and at 0 DEG C, stirring reaction 12h, after reaction, use CH
2cl
2and H
2o extracts, and gets organic phase, is spin-dried for after drying, by the dissolution of solid that obtains in 50mL benzene, and adds 6g(49.8mmol wherein) tetramethyl ethylene ketone, at the temperature of backflow, reaction 12h.After reaction, use CH
2cl
2and H
2o extracts, and gets organic phase, is spin-dried for after drying, purifies, obtain using ethyl acetate as eluent column chromatography
It is the white solid of 0.6342g that the two phosphine oxygen of difunctionalization that this experiment obtains replaces fluorenyl photoelectric functional material, productive rate: 55%.
The two phosphine oxygen of difunctionalization adopting nuclear magnetic resonance analyser test experience to obtain replaces fluorenyl photoelectric functional material, and detected result is as follows:
1HNMR(400MHz,CDCl
3):δ=7.877(d,J=8Hz,2H),7.748-7.488（m,28H）,7.420（t,J=7.8ppm,12H）,7.339（s,6H）,2.064（m,8H）,0.363（t,J=7.2Hz,12H）。
The structure that the two phosphine oxygen of difunctionalization that this experiment obtains replaces fluorenyl photoelectric functional material is as follows:
chemical name is 2,7-bis-(diethyl fluorenes)-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes.
Experiment 3
The synthesis step that the two phosphine oxygen of difunctionalization of this experiment replaces fluorenyl photoelectric functional material is as follows:
One, by 9 of 0.7188g, 9-diphenylphosphine oxygen phenyl fluorenes is dissolved in mixed solution, adds the N-bromo-succinimide (NBS) of 0.5337g, then adopts dichloromethane extraction, collected organic layer after extraction, adopt anhydrous sodium sulphate at room temperature dry, then adopt leacheate to carry out column chromatography purification, collect product point, through concentrated, obtain 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes; Two, 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes that step one obtains 0.8766g is got, the tetra-triphenylphosphine palladium (Pd (PPh of 0.1156g
3)
4), the Tetrabutyl amonium bromide (TBAB) of 0.0322g and the boric acid ester compound of 1.4770g mix, and under argon shield, dark condition, the tetrahydrofuran (THF) (THF) adding 25mL mixes, and obtains mixing solutions; Be that the NaOH solution of 2mol/L mixes with mixing solutions by the concentration of 6mL, be react 24h under the condition of 80 DEG C in temperature, obtain reaction head product; Then with saturated ammonium chloride, reaction head product is extracted, collected organic layer, by at room temperature dry for the organic over anhydrous sodium sulfate collected, adopt leacheate to carry out column chromatography purification dried product, obtain the two phosphine oxygen of difunctionalization and replace fluorenyl photoelectric functional material.
Boric acid ester compound structural formula described in this experimental procedure two is:
chemical name is: phenyl carbazole boric acid ester.
Described in this experimental procedure two
chemSpiderId be 10024545.
It is the white solid of 0.6727g that this experiment obtains difunctionalization two phosphine oxygen replacement fluorenyl photoelectric functional material, productive rate: 56%.
The two phosphine oxygen of difunctionalization adopting nuclear magnetic resonance analyser test experience to obtain replaces fluorenyl photoelectric functional material, and detected result is as follows:
1HNMR(300MHz,CDCl
3):δ=8.164（d，J=8Hz，4H），7.945（d，J=8.4Hz，2H），7.774（t，J=7.2Hz，6H），7.702-7.572（m，18H），7.539-7.443（m，24H），7.308（t，J=7.2Hz，4H）。
The structure that the two phosphine oxygen of difunctionalization that this experiment obtains replaces fluorenyl photoelectric functional material is as follows:
chemical name is 2,7-bis-(phenyl carbazole)-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes.
Experiment 4
The synthesis step that the two phosphine oxygen of difunctionalization of this experiment replaces fluorenyl photoelectric functional material is as follows:
One, by 9 of 0.7188g, 9-diphenylphosphine oxygen phenyl fluorenes is dissolved in mixed solution, adds the N-bromo-succinimide (NBS) of 0.5337g, then adopts extraction into ethyl acetate, collected organic layer after extraction, adopt anhydrous sodium sulphate at room temperature dry, then adopt leacheate to carry out column chromatography purification, collect product point, through concentrated, obtain 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes; Two, step one is obtained 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes of 0.8766g, the tetra-triphenylphosphine palladium (Pd (PPh of 0.1156g
3)
4), the Tetrabutyl amonium bromide (TBAB) of 0.0322g and the boric acid ester compound of 1.4851g mix, and under argon shield, dark condition, the tetrahydrofuran (THF) (THF) adding 25mL mixes, and obtains mixing solutions; Be that the NaOH solution of 2mol/L mixes with mixing solutions by the concentration of 6mL, be react 24h under the condition of 80 DEG C in temperature, obtain reaction head product; Then with saturated ammonium chloride, reaction head product is extracted, collected organic layer, by the organic layer collected, at room temperature dry by anhydrous sodium sulphate, adopt leacheate to carry out column chromatography purification dried product, obtain the two phosphine oxygen of difunctionalization and replace fluorenyl photoelectric functional material.
Boric acid ester compound structural formula described in this experimental procedure two is:
chemical name is: triphenylamine boric acid ester.
Described in this experimental procedure two
chemSpiderId be 9814049.
It is the white solid of 0.6510g that this experiment obtains difunctionalization two phosphine oxygen replacement fluorenyl photoelectric functional material, productive rate 54%.
The two phosphine oxygen of difunctionalization adopting nuclear magnetic resonance analyser test experience to obtain replaces fluorenyl photoelectric functional material, and detected result is as follows:
1hNMR (400MHz, CDCl3): δ (ppm): 7.819(d, J=8,2H), (7.697-7.609 m, 10H), 7.567-7.516 (m, 10H), 7.473-7.418(m, 12H), (7.378-7.351 m, 4H), 7.309-7.284 (m, 8H), 7.159-7.119(m, 12H), 7.060(t, J=7.2,4H).
The structure that the two phosphine oxygen of difunctionalization that this experiment obtains replaces fluorenyl photoelectric functional material is as follows:
chemical name is 2,7-bis-(triphenylamine)-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes.
Experiment 5
The synthesis step that the two phosphine oxygen of difunctionalization of this experiment replaces fluorenyl photoelectric functional material is as follows:
One, by 9 of 0.7188g, 9-diphenylphosphine oxygen phenyl fluorenes is dissolved in mixed solution, adds the N-bromo-succinimide (NBS) of 0.5337g, then adopts dichloromethane extraction, collected organic layer after extraction, adopt anhydrous sodium sulphate at room temperature dry, then adopt leacheate to carry out column chromatography purification, collect product point, through concentrated, obtain 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes; Two, step one is obtained 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes of 0.8766g, the tetra-triphenylphosphine palladium (Pd (PPh of 0.1156g
3)
4), the Tetrabutyl amonium bromide (TBAB) of 0.0322g and the boric acid ester compound of 1.6854g mix, and under argon shield, dark condition, the tetrahydrofuran (THF) (THF) adding 25mL mixes, and obtains mixing solutions; Be that the NaOH solution of 2mol/L mixes with mixing solutions by the concentration of 6mL, be react 24h under the condition of 80 DEG C in temperature, obtain reaction head product; Then with saturated ammonium chloride, reaction head product is extracted, collected organic layer, by the organic layer collected, at room temperature dry by anhydrous sodium sulphate, adopt leacheate to carry out column chromatography purification dried product, obtain the two phosphine oxygen of difunctionalization and replace fluorenyl photoelectric functional material.
Boric acid ester compound structural formula described in this experimental procedure two is:
chemical name is: naphthylphenyl amine boric acid ester.
Described in this experimental procedure two
preparation method, specifically complete according to the following steps: by 10g(26.8mmol)
be dissolved in 50mL tetrahydrofuran (THF), at-78 DEG C, add 10mL(26.8mmol) n-Butyl Lithium, 6.2mL(26.8mmol triisopropyl borate ester, after adding, be warming up to room temperature, reaction 12h, be cooled to 0 DEG C, add 80mL(2mmol/mL wherein) in hydrochloric acid, and at 0 DEG C, stirring reaction 12h, after reaction, use CH
2cl
2and H
2o extracts, and gets organic phase, is spin-dried for after drying, by the dissolution of solid that obtains in 50mL benzene, and adds 3.2g(26.8mmol wherein) tetramethyl ethylene ketone, at the temperature of backflow, reaction 12h.After reaction, use CH
2cl
2and H
2o extracts, and gets organic phase, is spin-dried for after drying, purifies, obtain using ethyl acetate as eluent column chromatography
It is the white solid of 0.7031g that this experiment obtains difunctionalization two phosphine oxygen replacement fluorenyl photoelectric functional material, productive rate 54%.
The two phosphine oxygen of difunctionalization adopting nuclear magnetic resonance analyser test experience to obtain replaces fluorenyl photoelectric functional material, and detected result is as follows:
1hNMR (400MHz, CDCl
3): δ=7.922,7.883(dd, J=8Hz, 4H), 7.763(t, J=10.4Hz, 4H), 7.644-7.596(t, J=9.6Hz, 9H), 7.594-7.280(m, 37H), 7.223-7.186(m, 4H), 7.078(d, J=8,4H), 7.017(d, J=8Hz, 3H), 6.953(t, J=6.8,1H).
The structure that the two phosphine oxygen of difunctionalization that this experiment obtains replaces fluorenyl photoelectric functional material is as follows:
chemical name is 2,7-bis-(naphthylphenyl amine)-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes.
Experiment 6
The synthesis step that the two phosphine oxygen of difunctionalization of this experiment replaces fluorenyl photoelectric functional material is as follows:
One, by 9 of 0.7188g, 9-diphenylphosphine oxygen phenyl fluorenes is dissolved in mixed solution, adds the N-bromo-succinimide (NBS) of 0.5337g, then adopts extraction into ethyl acetate, collected organic layer after extraction, adopt anhydrous sodium sulphate at room temperature dry, then adopt leacheate to carry out column chromatography, collect product point, through concentrated, obtain 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes; Two, 18-step one being obtained 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes of 0.6764g, the salt of wormwood of 0.4146g, the carbazole of 0.83561g, the cuprous iodide of 0.0381g and 0.0049g is preced with-6 ethers and mixes, and obtains mixture; Three, 1 of 5mL is added in the mixture obtained to step 2; 3-dimethyl-3; 4,5,6-tetrahydrochysene-2-pyrimidone (DMPU); then to reflux under being the condition of 190 DEG C 24h in nitrogen protection, temperature; adopt ethyl acetate to extract in reacted mixture, collected organic layer, adopt anhydrous sodium sulphate at room temperature dry the organic layer collected; adopt leacheate to carry out column chromatography purification dried product, obtain the two phosphine oxygen of difunctionalization and replace fluorenyl photoelectric functional material.
It is the white solid of 0.5245g that this experiment obtains difunctionalization two phosphine oxygen replacement fluorenyl photoelectric functional material, productive rate: 50%.
The two phosphine oxygen of difunctionalization adopting nuclear magnetic resonance analyser test experience to obtain replaces fluorenyl photoelectric functional material, and detected result is as follows:
1hNMR (400MHz, CDCl3): δ (ppm): 8.129(d, J=6.4Hz, 4H), 8.054 (d, J=8,2H), 7.71 (d, J=1.6,1H), 7.689(d, J=2,1H), 7.654-7.573 (m, 15H), 7.524-7.484(m, 4H), 7.434-7.390(m, 12H), 7.316-7.255(m, 11H).
The structure that the two phosphine oxygen of difunctionalization that this experiment obtains replaces fluorenyl photoelectric functional material is as follows:
chemical name is 2,7-bis-(carbazole)-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes.
Experiment 7
The preparation method of the blue organic electroluminescence phosphorescent devices of this experiment carries out according to following steps:
One, by vacuum evaporation technology at substrate material evaporation the first layer conductive layer as anode; Two, vacuum vapour deposition evaporation hole injection layer, hole transmission layer and hole transport/electronic barrier layer is successively adopted, and then adopt vacuum vapour deposition evaporation luminescent layer, evaporation electric transmission/exciton barrier-layer on luminescent layer, evaporation electron injecting layer on electric transmission/exciton barrier-layer again, finally on electron injecting layer, evaporation second layer conductive layer, as negative electrode, namely completes the preparation of blue organic light-emitting devices;
Wherein, the first layer conductive layer thickness described in step one is 5nm, and the first layer conductive is tin indium oxide (ITO), and described substrate material is glass, and the hole injection layer material described in step 2 is MoO
3, thickness is 10 ~ 50nm, the thickness of described hole transmission layer is 50nm, hole transport layer material is NPB(N, N '-bis--(3-naphthyl)-N, N '-phenylbenzene-[1, 1 '-phenylbenzene]-4, 4 '-diamines), described hole transport/electronic blocking layer thickness is 5 ~ 40nm, hole transport/electronic blocking layer material is 4, 4 ', 4 "-three (carbazole-9-base) triphenylamine (TCTA), described light emitting layer thickness is 20nm, the emitting layer material difunctionalization two phosphine oxygen obtained with experiment 3 that are complex of iridium replace the adulterate body that fluorenyl photoelectric functional material is mixed to form, the two phosphine oxygen of difunctionalization replaces fluorenyl photoelectric functional material and accounts for 85% of adulterate body total mass, complex of iridium accounts for 15% of adulterate body total mass, the thickness of described electric transmission/exciton barrier-layer is 30nm, electric transmission/exciton barrier-layer material is 1, 3, 5-tri-(N-phenyl-2-benzimidazolyl-2 radicals) benzene (TPBI), described electron injecting layer material is LiF, electron injection layer thickness is 1nm, described second layer conductive is aluminium.
The blue organic light-emitting devices that this experiment obtains is A.
Experiment 8
This experiment and experiment 7 are unlike the preparation method of blue organic light-emitting devices: the emitting layer material described in step 2 is the adulterate body that complex of iridium difunctionalization two phosphine oxygen obtained with experiment 6 replace fluorenyl photoelectric functional material and are mixed to form, the two phosphine oxygen of difunctionalization replaces fluorenyl photoelectric functional material and accounts for 85% of adulterate body total mass, complex of iridium accounts for 15% of adulterate body total mass, other step and parameter identical with experiment 7.
The blue organic light-emitting devices that this experiment obtains is B.
Experiment 9
This experiment and experiment 7 are unlike the preparation method of blue organic light-emitting devices: the emitting layer material described in step 2 is that the two phosphine oxygen of difunctionalization of experiment 2 replaces fluorenyl photoelectric functional material, other step and parameter with experiment 7 identical.
The blue organic light-emitting devices that this experiment obtains is C.
Experiment 10
This experiment and experiment 7 are unlike the preparation method of blue organic light-emitting devices: the emitting layer material described in step 2 is that the two phosphine oxygen of difunctionalization of experiment 4 replaces fluorenyl photoelectric functional material, other step and parameter with experiment 7 identical.
The blue organic light-emitting devices that this experiment obtains is D.
Experiment 11
This experiment and experiment 7 are unlike the preparation method of blue organic light-emitting devices: the emitting layer material described in step 2 is that the two phosphine oxygen of difunctionalization of experiment 5 replaces fluorenyl photoelectric functional material, other step and parameter with experiment 7 identical.
The blue organic light-emitting devices that this experiment obtains is E.
The blue light electroluminescence device adopting Keithley2400/2000Sourcemeter and PR650 instrument obtained to experiment 8 and 9 detects, detected result as shown in Figure 1, as shown in Figure 1, during to test 2 difunctionalization obtained two phosphine oxygen replacement fluorenyl photoelectric functional material as luminescent material compositions, the blue organic light-emitting devices recorded has two emission peaks, is respectively 395 and 416nm, and during to test 3 difunctionalization obtained two phosphine oxygen replacement fluorenyl photoelectric functional material as luminescent material compositions, the emission peak of the blue organic light-emitting devices recorded is 408nm, during to test 4 difunctionalization obtained two phosphine oxygen replacement fluorenyl photoelectric functional material as luminescent material compositions, the emission peak of the blue organic light-emitting devices recorded is 445nm, during to test 5 difunctionalization obtained two phosphine oxygen replacement fluorenyl photoelectric functional material as luminescent material compositions, the emission peak of the blue organic light-emitting devices recorded is 440nm, during to test 6 difunctionalization obtained two phosphine oxygen replacement fluorenyl photoelectric functional material as luminescent material compositions, the emission peak of the blue organic light-emitting devices recorded is 377nm.
It can thus be appreciated that the two phosphine oxygen of difunctionalization replaces fluorenyl photoelectric functional material and becomes blue emission, and emission peak replaces the increase red shift of conjugate length with 2,7.
Device A and B that test experiments 7 and experiment 8 obtain, as shown in Figure 2, as shown in Figure 2, the luminous efficiency of device A, B is respectively 18cd/A and 15cd/A to detected result.
Device A and B that test experiments 9 and experiment 11 obtain, as shown in Figure 3, as shown in Figure 3, the luminous efficiency of device C, E is respectively 0.7cd/A and 1.5cd/A to detected result, and the luminous efficiency of device D is 1.4cd/A.
Claims (10)
1. the two phosphine oxygen of difunctionalization replaces fluorenyl photoelectric functional material, it is characterized in that the two phosphine oxygen of difunctionalization replaces fluorenyl photoelectric functional material structure as follows:
Wherein, R is
2. prepare the method that the two phosphine oxygen of difunctionalization as claimed in claim 1 replaces fluorenyl photoelectric functional material, it is characterized in that the preparation process that the two phosphine oxygen of difunctionalization replaces fluorenyl photoelectric functional material is as follows:
One, by 9,9-bis--(diphenylphosphine oxygen phenyl) fluorenes is dissolved in mixed solution, add N-bromo-succinimide, methylene dichloride or ethyl acetate is adopted to extract, after extraction, collected organic layer is dry at ambient temperature, then adopts ethyl acetate to carry out column chromatography purification as leacheate, obtains 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes;
Two, step one obtained 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes is preced with-6 ethers with salt of wormwood, carbazole, cuprous iodide and 18-and is mixed, and obtains mixture; High-temperature solvent is added in mixture, then under nitrogen protection, temperature are the condition of 90 DEG C ~ 250 DEG C, 12 ~ 50h is reacted, methylene dichloride or ethyl acetate is adopted to extract in reacted mixture, collected organic layer, dry, adopt ethyl acetate to carry out column chromatography purification as leacheate, obtain the two phosphine oxygen of difunctionalization and replace fluorenyl photoelectric functional material;
Wherein, mixed solution described in step one is that the ratio being 1 ~ 3:1 by volume by Glacial acetic acid and the vitriol oil mixes, 9,9-bis--(the diphenylphosphine oxygen phenyl) amount of substance of fluorenes and the ratio of mixeding liquid volume are 1mmol:9 ~ 15mL, the mol ratio of 9,9-, bis--(diphenylphosphine oxygen phenyl) fluorenes and N-bromo-succinimide is 1:1 ~ 5;
Described in step 22,7-bis-bromo-9, mol ratio 1:1 ~ 3 of 9-bis-(diphenylphosphine oxygen phenyl) fluorenes and salt of wormwood, the mol ratio of salt of wormwood and carbazole is 3:1 ~ 5, salt of wormwood and cuprous iodide mol ratio be 30:0.5 ~ 2, the mol ratio that salt of wormwood and 18-are preced with-6 ethers is 150 ~ 300:2;
High-temperature solvent described in step 2 is 1,3-dimethyl-3,4,5,6-tetrahydrochysene-2-pyrimidone, and the volume ratio of bromo-9,9-bis-(diphenylphosphine oxygen phenyl) the fluorenes amount of substances of 2,7-bis-and high-temperature solvent is 1mmol:5 ~ 10mL.
3. the two phosphine oxygen of difunctionalization according to claim 2 replaces the preparation method of fluorenyl photoelectric functional material, it is characterized in that the mol ratio of bis--(the diphenylphosphine oxygen phenyl) fluorenes of 9,9-described in step one and N-bromo-succinimide is 1:3.
4. the two phosphine oxygen of difunctionalization according to claim 2 replaces the preparation method of fluorenyl photoelectric functional material, it is characterized in that the mol ratio of bromo-9,9-bis-(the diphenylphosphine oxygen phenyl) fluorenes of 2,7-described in step 2 bis-and salt of wormwood is 1:2.
5. prepare the method that the two phosphine oxygen of difunctionalization as claimed in claim 1 replaces fluorenyl photoelectric functional material, it is characterized in that the preparation process that the two phosphine oxygen of difunctionalization replaces fluorenyl photoelectric functional material is as follows:
One, by 9,9-bis--(diphenylphosphine oxygen phenyl) fluorenes is dissolved in mixed solution, add N-bromo-succinimide, methylene dichloride or ethyl acetate is adopted to extract, after extraction, collected organic layer is dry at ambient temperature, then adopts ethyl acetate to carry out column chromatography purification as leacheate, obtains 2,7-bis-bromo-9,9-bis-(diphenylphosphine oxygen phenyl) fluorenes;
Two, step one is obtained 2,7-bis-bromo-9-phenyl-9-diphenylphosphine oxygen phenyl fluorenes and tetra-triphenylphosphine palladium, Tetrabutyl amonium bromide and boric acid ester compound mix, again under argon shield, dark condition, add tetrahydrofuran (THF) to dissolve, adding concentration is again after the NaOH solution of 2mol/L, is to react 8 ~ 32h under the condition of 80 DEG C ~ 90 DEG C in temperature, obtains reaction head product; Then with saturated ammonium chloride solution, reaction head product is extracted, collected organic layer, dry, adopt ethyl acetate to carry out column chromatography purification as leacheate, obtain the single phosphine oxygen of difunctionalization and replace fluorenyl photoelectric functional material;
Wherein, mixed solution described in step one is that the ratio being 1 ~ 3:1 by volume by Glacial acetic acid and the vitriol oil mixes, 9,9-bis--(diphenylphosphine oxygen phenyl) fluorenes amount of substance and mixeding liquid volume are than being 1mmol:9 ~ 15mL, the mol ratio of 9,9-, bis--(diphenylphosphine oxygen phenyl) fluorenes and N-bromo-succinimide is 1:1 ~ 5;
Boric acid ester compound described in step 2 is
2, 7-bis-bromo-9, the mol ratio of 9-bis-(diphenylphosphine oxygen phenyl) fluorenes and tetra-triphenylphosphine palladium is 1 ~ 10:1, 2, 7-bis-bromo-9, the mol ratio of 9-bis-(diphenylphosphine oxygen phenyl) fluorenes and Tetrabutyl amonium bromide is 5 ~ 10:1, 2, 7-bis-bromo-9, 9-bis-(diphenylphosphine oxygen phenyl) fluorenes and boric acid ester mol ratio be 1:2 ~ 4, 2, 7-bis-bromo-9, 9-bis-(diphenylphosphine oxygen phenyl) fluorenes amount of substance and tetrahydrofuran (THF) volume ratio are 1mmol:10 ~ 30mL, concentration is the NaOH solution and 2 of 2mol/L, 7-bis-bromo-9, 9-bis-(diphenylphosphine oxygen phenyl) fluorenes mol ratio is 10 ~ 15:1.
6. the two phosphine oxygen of difunctionalization according to claim 5 replaces the preparation method of fluorenyl photoelectric functional material, it is characterized in that the mol ratio of bis--(the diphenylphosphine oxygen phenyl) fluorenes of 9,9-described in step one and N-bromo-succinimide is 1:3.
7. the two phosphine oxygen of difunctionalization according to claim 5 replaces the preparation method of fluorenyl photoelectric functional material, it is characterized in that bromo-9,9-bis-(the diphenylphosphine oxygen phenyl) fluorenes of 2,7-described in step 2 bis-and boric acid ester mol ratio be 1:3.
8. the two phosphine oxygen of difunctionalization as claimed in claim 1 replaces the application of fluorenyl photoelectric functional material, it is characterized in that the two phosphine oxygen of difunctionalization replaces the application in blue organic light-emitting devices as fluorescence radiation layer material or phosphorescent light body material of fluorenyl photoelectric functional material.
9. the two phosphine oxygen of difunctionalization according to claim 8 replaces the application of fluorenyl photoelectric functional material, it is characterized in that the preparation method of described blue organic light-emitting devices carries out according to following steps:
One, by vacuum evaporation technology on substrate material evaporation the first layer conductive layer as anode; Two, vacuum vapour deposition evaporation hole injection layer, hole transmission layer and hole transport/electronic barrier layer is successively adopted, and then adopt vacuum vapour deposition evaporation luminescent layer, evaporation electric transmission/exciton barrier-layer again on luminescent layer, last at electric transmission/exciton barrier-layer evaporation second layer conductive layer as negative electrode, namely complete the preparation of blue organic light-emitting devices;
Wherein, the first layer conductive layer thickness described in step one is 1 ~ 10nm, and the first layer conductive is tin indium oxide, polyaniline or PANI, and described substrate material is glass or plastics, uses foam structural adhesive MoO in step 2
3, hole transport layer material thickness is 10 ~ 50nm, the thickness of described hole transmission layer is 20 ~ 60nm, hole transport layer material is 4, 4', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine, N, N'-pair-(3-naphthyl)-N, N'-phenylbenzene-[1, 1'-phenylbenzene]-4, 4'-diamines or N, N'-pair-(3-aminomethyl phenyl)-N, N'-phenylbenzene-[1, 1'-xenyl]-4, 4'-diamines, described hole transport/electronic blocking layer thickness is 5 ~ 40nm, hole transport/electronic blocking layer material is that three (1-phenylpyrazoles) close iridium or 4, 4', 4 "-three (carbazole-9-base) triphenylamine, described light emitting layer thickness is 5 ~ 40nm, emitting layer material is that two phosphine oxygen replaces fluorenyl photoelectric functional material or complex of iridium and difunctionalization pair phosphine oxygen and replaces the adulterate body that fluorenyl photoelectric functional material is mixed to form, wherein, the two phosphine oxygen of difunctionalization replaces fluorenyl photoelectric functional material and accounts for 80% ~ 97% of adulterate body total mass, complex of iridium accounts for 3% ~ 20% of adulterate body total mass, the thickness of described electric transmission/exciton barrier-layer is 10 ~ 80nm, electric transmission/exciton barrier-layer material is 4, 7-phenylbenzene-1, 10-phenanthrolene or 1, 3, 5-tri-(N-phenyl-2-benzimidazolyl-2 radicals) benzene, described second layer conductive is calcium, calcium alloy, magnesium, magnesium alloy, silver, silver alloys, aluminum or aluminum alloy.
10. the two phosphine oxygen of difunctionalization according to claim 9 replaces the application of fluorenyl photoelectric functional material, it is characterized in that when second layer conductive is aluminium, need after electric transmission/exciton barrier-layer surface evaporation 1 ~ 5nm, material be the electron injecting layer of LiF, then in second layer conductive layer AM aluminum metallization.
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