CN102924515A

CN102924515A - Uni-functional single phosphine-oxygen replaced fluorenyl compound and preparation method and application thereof

Info

Publication number: CN102924515A
Application number: CN2012104316574A
Authority: CN
Inventors: 许辉; 于东慧
Original assignee: Heilongjiang University
Current assignee: Heilongjiang University
Priority date: 2012-11-02
Filing date: 2012-11-02
Publication date: 2013-02-13

Abstract

The invention discloses to a uni-functional single phosphine-oxygen replaced fluorenyl compound and a preparation method and an application thereof and relates to a photoelectrical functional material and a preparation method and an application thereof. The uni-functional single phosphine-oxygen replaced fluorenyl compound aims at solving the problem that the existing organic electroluminescent blue-light device is high in driving voltage and low in efficiency. The method for preparing the uni-functional single phosphine-oxygen replaced fluorenyl compound includes: 1, performing bromination reaction, and then sequentially performing extracting, drying and column chromatography; and 2, firstly performing suzuki or uman reactions, and then sequentially performing extracting, drying and column chromatography. The uni-functional single phosphine-oxygen replaced fluorenyl compound serves as the main material in the electroluminescent blue-light device or the light-emitting material in the organic electroluminescent blue-light device for application. The preparation method is mainly used for preparing the uni-functional single phosphine-oxygen replaced fluorenyl compound.

Description

The single phosphine oxygen of single functionalization substituted fluorene based compound and its preparation method and application

Technical field

The present invention relates to a kind of photoelectric functional material and its preparation method and application.

Background technology

21st century, people had higher requirement for flat pannel display along with the high speed development of information industry, with the needs that satisfy life and produce.Following development tends to more that volume is little, lightweight, ultra-thin, the portable display device of imaging clearly, flexible and functional diversities, and flat panel display now can not satisfy these requirements.Electroluminescent organic material and display device because have that lightweight, thin thickness, driving voltage are low, fast response time, angular field of view is wide, display color is abundant, brightness is high, resolving power is high, easily realize the premium properties such as large-area flat-plate demonstration, has become the emphasis of studying in the world at present.

At present ruddiness and green glow have had the necessary luminous efficiency of business development and life-span, yet as the blueness of another three primary colours, realize that its high stable and high efficiency emission are still a difficult problem.Existing Organic Light Emitting Diode (OLED) blue light material efficient is generally 2% ~ 10%, and driving voltage is higher than 5V, lags far behind the development of ruddiness and green glow, has seriously hindered the industrialization paces of full color OLED and white light parts.Thereby the research and development of the efficient blue-light device of low-voltage driving are that OLED realizes business-like prerequisite.Therefore existing blue organic electroluminescence device exists driving voltage high, inefficient problem.

Summary of the invention

The objective of the invention is to solve existing blue organic electroluminescence device and exist driving voltage high, inefficient problem, and the single phosphine oxygen of a kind of single functionalization substituted fluorene based compound and its preparation method and application is provided.

The single phosphine oxygen of single functionalization substituted fluorene based compound, its chemical name is 2-R-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes, structural formula is:

Wherein said R is

Or

The preparation method of the single phosphine oxygen of single functionalization substituted fluorene based compound, chemical name is that 2-R-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is specifically finished according to the following steps: one, preparation 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes: at first 9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is dissolved in Glacial acetic acid/vitriol oil mixed solution, obtain mixing solutions after dissolving mixing fully, then add for 3 ~ 10 times N-bromo-succinimide average mark in the mixture, and N-bromo-succinimide of every adding is stirring reaction 30min～60min at room temperature, after all adding, the N-bromo-succinimide continues at room temperature stirring reaction 4h ~ 12h, namely obtain reaction solution, then reaction solution is poured in the frozen water, after all melting, the ice in the frozen water adopts methylene dichloride or ethyl acetate extraction, the organic layer that extraction obtains adopts anhydrous sodium sulphate to carry out drying, then carry out suction filtration, the filtrate that suction filtration obtains is till temperature is to be concentrated into the absence of liquid outflow under 50 ℃ ~ 70 ℃, carry out at last column chromatography take sherwood oil/methylene dichloride mixed solvent as eluent and purify, namely obtain 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes; Glacial acetic acid described in the step 1/vitriol oil mixed solution is mixed by Glacial acetic acid and the vitriol oil, and the volume ratio of wherein said Glacial acetic acid and the vitriol oil is (1 ~ 5): 1; The ratio of the 9-phenyl-9-described in the step 1 (diphenylphosphine oxygen phenyl) fluorenes amount of substance and Glacial acetic acid/vitriol oil mixeding liquid volume is 1mmol:(3mL ~ 18mL); The mol ratio 1:(0.5 of (the diphenylphosphine oxygen phenyl) fluorenes of the 9-phenyl-9-described in the step 1 and N-bromo-succinimide ~ 3); Two, suzuki reaction: at first with tetrakis triphenylphosphine palladium, Tetrabutyl amonium bromide, boric ester derivative and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes mix, then add tetrahydrofuran (THF) in argon shield with without under the optical condition, adding concentration is the NaOH aqueous solution of 1mol/L ~ 3mol/L again, and under being 80 ℃ ~ 90 ℃ and argon shield, temperature reacts 8h ~ 32h, namely obtain reacting after product, adopt saturated ammonium chloride that the reaction after product is extracted, the organic layer that extraction obtains at room temperature adopts anhydrous sodium sulphate to carry out drying, carry out at last column chromatography take sherwood oil/methylene dichloride mixed solvent as eluent and purify, namely obtain the single phosphine oxygen of single functionalization substituted fluorene based compound; The mol ratio of the tetrakis triphenylphosphine palladium described in the step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is (0.005 ~ 0.1): 1; The mol ratio of the Tetrabutyl amonium bromide described in the step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is (0.01 ~ 0.1): 1; The mol ratio of the boric ester derivative described in the step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is (0.5 ~ 2): 1; Tetrahydrofuran (THF) volume described in the step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes molar ratio are (4mL ~ 10mL): 1mmol; Concentration described in the step 2 is that the NaOH aqueous solution of 1mol/L ~ 3mol/L and the mol ratio of 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes are (0.5 ~ 7): 1.

The single phosphine oxygen of single functionalization substituted fluorene based compound, its chemical name is 2-carbazole-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes, structural formula is:

The preparation method of the single phosphine oxygen of single functionalization substituted fluorene based compound, chemical name is that 2-carbazole-9-phenyl-9-(diphenylphosphine oxygen phenyl) specifically finishes according to the following steps: one, preparation 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes: at first 9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is dissolved in Glacial acetic acid/vitriol oil mixed solution, obtain mixture after dissolving mixing fully, then add for 3 ~ 10 times N-bromo-succinimide average mark in the mixture, and N-bromo-succinimide of every adding is stirring reaction 30min～60min at room temperature, after all adding, the N-bromo-succinimide continues at room temperature stirring reaction 4h ~ 12h, namely obtain reaction solution, then reaction solution is poured in the frozen water, after all melting, the ice in the frozen water adopts methylene dichloride or ethyl acetate extraction, the organic layer that extraction obtains adopts anhydrous sodium sulphate to carry out drying, then carry out suction filtration, the filtrate that suction filtration obtains is till temperature is to be concentrated into the absence of liquid outflow under 50 ℃ ~ 70 ℃, carry out at last column chromatography take sherwood oil/methylene dichloride mixed solvent as eluent and purify, namely obtain 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes; Glacial acetic acid described in the step 1/vitriol oil mixed solution is mixed by Glacial acetic acid and the vitriol oil, and the volume ratio of wherein said Glacial acetic acid and the vitriol oil is (1 ~ 5): 1; The ratio of the 9-phenyl-9-described in the step 1 (diphenylphosphine oxygen phenyl) fluorenes amount of substance and Glacial acetic acid/vitriol oil mixeding liquid volume is 1mmol:(3mL ~ 18mL); The mol ratio 1:(0.5 of (diphenylphosphine oxygen phenyl) the fluorenes quality of the 9-phenyl-9-described in the step 1 and N-bromo-succinimide ~ 3); Two, replace: with salt of wormwood, carbazole, cuprous iodide and 18-hat-6 ethers add in 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes, then add under the nitrogen protection 1,3-dimethyl-3,4,5,6-tetrahydrochysene-2-pyrimidone, and be 90 ℃ ~ 250 ℃ lower reaction 12h ~ 50h in nitrogen protection and temperature, namely obtain reacting after product, then adopt methylene dichloride that the reaction after product is extracted, the organic layer that extraction obtains at room temperature adopts anhydrous sodium sulphate to carry out drying, carries out at last column chromatography take sherwood oil/methylene dichloride mixed solvent as eluent and purifies, and namely obtains the single phosphine oxygen of single functionalization substituted fluorene based compound; The mol ratio of the salt of wormwood described in the step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is (1 ~ 6): 1; The mol ratio of the carbazole described in the step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is (1 ~ 10): 1; The mol ratio of the cuprous iodide described in the step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is (0.05 ~ 0.5): 1; 18-hat-6 ethers described in the step 2 and the mol ratio of 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes are (0.001 ~ 0.05): 1; Described in the step 21,3-dimethyl-3,4,5,6-tetrahydrochysene-2-pyrimidone volume and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes molar ratio are (1mL ~ 10mL): 1mmol.

The application of the single phosphine oxygen of above-mentioned single functionalization substituted fluorene based compound, the single phosphine oxygen of single functionalization substituted fluorene based compound is as the application of the material of main part in the blue light electroluminescence phosphorescence device or the luminescent material in the blue organic electroluminescence device.

Advantage of the present invention: one, the single phosphine oxygen of the single functionalization substituted fluorene based compound of the present invention's preparation is take 9 single phosphorus oxygen substituted-phenyl fluorenes as nuclear, with 2 modifications of cavity transmission group, forms the fluorenyl aromatic phosphines oxygen photoelectric material that a class has dipole characteristic; By the C of 2 of fluorenes, the functional group that will have hole injection and transmission performance is incorporated into fragrant single phosphorus oxygen phenyl fluorenes nuclear, makes up the efficient blue light electroluminescence functional materials of ternary with bipolar carrier transmission performance; The building mode of indirect joint aromatic phosphines oxygen groups guarantees the triplet of fluorenes nuclear effectively, and the modification of 2 cavity transmission groups, effectively excited level is regulated and control, realized a series of fluorescence radiations in the mazarine zone, triplet is the continuously adjustable efficient organic blue light functional materials of ternary with bipolar carrier transmission performance from 2.9eV to 2.3eV; The current efficiency maximum can reach 35.5cd/A when two, the single phosphine oxygen of the single functionalization substituted fluorene based compound of the present invention's preparation was used as luminescent layer material of main part in the blue light electroluminescence device, and driving voltage is 3.1V.

Description of drawings

Fig. 1 is that test one to the single phosphine oxygen of the test single functionalization of five preparations substituted fluorene based compound is dissolved in the utilizing emitted light spectrogram in the dichloromethane solution, among the figure ■ represent to test a preparation the single phosphine oxygen of single functionalization substituted fluorene based compound---2-diethyl fluorenes-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is dissolved in the utilizing emitted light spectrogram in the dichloromethane solution, among the figure ● expression test two preparations the single phosphine oxygen of single functionalization substituted fluorene based compound---2-phenyl carbazole-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is dissolved in the utilizing emitted light spectrogram in the dichloromethane solution, among the figure ▲ expression test three preparations the single phosphine oxygen of single functionalization substituted fluorene based compound---2-triphenylamine-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is dissolved in the utilizing emitted light spectrogram in the dichloromethane solution, among the figure Expression test four preparations the single phosphine oxygen of single functionalization substituted fluorene based compound---2-naphthyl phenyl amine-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is dissolved in the utilizing emitted light spectrogram in the dichloromethane solution, among the figure ◆ expression test five preparations the single phosphine oxygen of single functionalization substituted fluorene based compound---2-carbazole-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is dissolved in the utilizing emitted light spectrogram in the dichloromethane solution; Fig. 2 is organic electrophosphorescenpolymer current density-current efficiency spectrogram, ■ among Fig. 2 represents to test the six blue light electroluminescence phosphorescence device current density for preparing-current efficiency spectrograms, among Fig. 2 ● the blue light electroluminescence phosphorescence device current density of expression test seven preparations-current efficiency spectrograms; Fig. 3 is voltage-to-current density-brightness curve figure, ■ among Fig. 3 represents to test the blue light electroluminescence fluorescent device voltage-to-current density map of eight preparations, among Fig. 3 ● the blue light electroluminescence fluorescent device voltage-to-current density spectra figure of expression test nine preparations, among Fig. 3 ▲ the blue light electroluminescence fluorescent device voltage-to-current density spectra figure of expression test ten preparations, the blue light electroluminescence fluorescent device voltage of the expression of zero among Fig. 3 test eight preparations-brightness spectrogram, among Fig. 3 represents to test the nine blue light electroluminescence fluorescent device voltage for preparing-brightness spectrograms, and the △ among Fig. 3 represents to test the ten blue light electroluminescence fluorescent device voltage for preparing-brightness spectrograms.

Embodiment

Embodiment one: present embodiment is the single phosphine oxygen of single functionalization substituted fluorene based compound, and its chemical name is 2-R-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes, and structural formula is:

Wherein said R is

Or

Embodiment two: present embodiment is the preparation method of the single phosphine oxygen of single functionalization substituted fluorene based compound, chemical name is that 2-R-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is specifically finished according to the following steps: one, preparation 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes: at first 9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is dissolved in Glacial acetic acid/vitriol oil mixed solution, obtain mixing solutions after dissolving mixing fully, then add for 3 ~ 10 times N-bromo-succinimide average mark in the mixture, and N-bromo-succinimide of every adding is stirring reaction 30min ~ 60min at room temperature, after all adding, the N-bromo-succinimide continues at room temperature stirring reaction 4h ~ 12h, namely obtain reaction solution, then reaction solution is poured in the frozen water, after all melting, the ice in the frozen water adopts methylene dichloride or ethyl acetate extraction, the organic layer that extraction obtains adopts anhydrous sodium sulphate to carry out drying, then carry out suction filtration, the filtrate that suction filtration obtains is till temperature is to be concentrated into the absence of liquid outflow under 50 ℃ ~ 70 ℃, carry out at last column chromatography take sherwood oil/methylene dichloride mixed solvent as eluent and purify, namely obtain 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes; Two; suzuki reaction: at first with tetrakis triphenylphosphine palladium; Tetrabutyl amonium bromide; boric ester derivative and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes mix; then add tetrahydrofuran (THF) in argon shield with without under the optical condition; adding concentration is the NaOH aqueous solution of 1mol/L ~ 3mol/L again; and under being 80 ℃ ~ 90 ℃ and argon shield, temperature reacts 8h ~ 32h; namely obtain reacting after product; adopt saturated ammonium chloride that the reaction after product is extracted; the organic layer that extraction obtains at room temperature adopts anhydrous sodium sulphate to carry out drying; carry out at last column chromatography take sherwood oil/methylene dichloride mixed solvent as eluent and purify, namely obtain the single phosphine oxygen of single functionalization substituted fluorene based compound.

Glacial acetic acid described in the present embodiment step 1/vitriol oil mixed solution is mixed by Glacial acetic acid and the vitriol oil, and the volume ratio of wherein said Glacial acetic acid and the vitriol oil is (1 ~ 5): 1; The ratio of the 9-phenyl-9-described in the present embodiment step 1 (diphenylphosphine oxygen phenyl) fluorenes amount of substance and Glacial acetic acid/vitriol oil mixeding liquid volume is 1mmol:(3mL ~ 18mL); The mol ratio 1:(0.5 of (the diphenylphosphine oxygen phenyl) fluorenes of the 9-phenyl-9-described in the present embodiment step 1 and N-bromo-succinimide ~ 3).

The mol ratio of the tetrakis triphenylphosphine palladium described in the present embodiment step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is (0.005 ~ 0.1): 1; The mol ratio of the Tetrabutyl amonium bromide described in the present embodiment step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is (0.01 ~ 0.1): 1; The mol ratio of the boric ester derivative described in the present embodiment step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is (0.5 ~ 2): 1; Tetrahydrofuran (THF) volume described in the present embodiment step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes molar ratio are (4mL ~ 10mL): 1mmol; Concentration described in the present embodiment step 2 is that the NaOH aqueous solution of 1mol/L ~ 3mol/L and the mol ratio of 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes are (0.5 ~ 7): 1.

H in the vitriol oil described in the present embodiment step 1 ₂SO ₄Massfraction be 95% ~ 99%.

Sherwood oil described in the present embodiment step 1/methylene dichloride mixed solvent is mixed by any ratio by sherwood oil and methylene dichloride and forms.

Saturated ammonium chloride collocation method described in the present embodiment step 2 is as follows: under room temperature and agitation condition, ammonium chloride added in the deionized water crystallization appears to the bottom and till, namely obtain saturated ammonium chloride.

Sherwood oil described in the present embodiment step 2/methylene dichloride mixed solvent is mixed by any ratio by sherwood oil and methylene dichloride and forms.

The single phosphine oxygen of the single functionalization substituted fluorene based compound of present embodiment preparation is take 9 single phosphorus oxygen substituted-phenyl fluorenes as nuclear, with 2 modifications of cavity transmission group, forms the fluorenyl aromatic phosphines oxygen photoelectric material that a class has dipole characteristic; By the C of 2 of fluorenes, the functional group that will have hole injection and transmission performance is incorporated into fragrant single phosphorus oxygen phenyl fluorenes nuclear, makes up the efficient blue light electroluminescence functional materials of ternary with bipolar carrier transmission performance; The building mode of indirect joint aromatic phosphines oxygen groups guarantees the triplet of fluorenes nuclear effectively, and the modification of 2 cavity transmission groups, effectively excited level is regulated and control, realized a series of fluorescence radiations in the mazarine zone, triplet is the continuously adjustable efficient organic blue light functional materials of ternary with bipolar carrier transmission performance from 2.9eV to 2.3eV.

The current efficiency maximum can reach 35.5cd/A when the single phosphine oxygen of the single functionalization substituted fluorene based compound of present embodiment preparation was used as luminescent layer material of main part in the blue light electroluminescence device, and driving voltage is 3.1V.

Embodiment three: the difference of present embodiment and embodiment two is: the boric ester derivative described in the step 2 is

Or

Other are identical with embodiment two.

Described in the present embodiment step 2

The preparation method, specifically finish according to the following steps: with 15g(49.8mmol)

Be dissolved in the 50ml tetrahydrofuran (THF), under-78 ℃, add 20ml(49.8mmol) n-Butyl Lithium, 12ml(49.8mmol) triisopropyl borate ester, add complete after, be warming up to room temperature, the reaction 12h, be cooled to 0 ℃, add therein 100ml(2mmol/mL) in the hydrochloric acid, and under 0 ℃, stirring reaction 12h, after the reaction, use CH ₂Cl ₂And H ₂O extracts, and gets organic phase, be spin-dried for after the drying, with the dissolution of solid that obtains in 50ml benzene, and add therein 6g(49.8mmol) tetramethyl ethylene ketone, under the temperature that refluxes, reaction 12h.After the reaction, use CH ₂Cl ₂And H ₂O extracts, and gets organic phase, is spin-dried for after the drying, purifies with column chromatography as eluent with ethyl acetate, obtains

Described in the present embodiment step 2

ChemSpider Id be 10024545.

Described in the present embodiment step 2 ChemSpider Id be 9814049.

Described in the present embodiment step 2 The preparation method, specifically finish according to the following steps: with 10g(26.8mmol)

Be dissolved in the 50ml tetrahydrofuran (THF), under-78 ℃, add 10ml(26.8mmol) n-Butyl Lithium, 6.2ml(26.8mmol triisopropyl borate ester, add complete after, be warming up to room temperature, the reaction 12h, be cooled to 0 ℃, add therein 80ml(2mmol/mL) in the hydrochloric acid, and under 0 ℃, stirring reaction 12h, after the reaction, use CH ₂Cl ₂And H ₂O extracts, and gets organic phase, be spin-dried for after the drying, with the dissolution of solid that obtains in 50ml benzene, and add therein 3.2g(26.8mmol) tetramethyl ethylene ketone, under the temperature that refluxes, reaction 12h.After the reaction, use CH ₂Cl ₂And H ₂O extracts, and gets organic phase, is spin-dried for after the drying, purifies with column chromatography as eluent with ethyl acetate, obtains

Embodiment four: present embodiment is the single phosphine oxygen of single functionalization substituted fluorene based compound, and its chemical name is 2-carbazole-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes, and structural formula is:

Embodiment five: present embodiment is the preparation method of the single phosphine oxygen of single functionalization substituted fluorene based compound, chemical name is that 2-carbazole-9-phenyl-9-(diphenylphosphine oxygen phenyl) specifically finishes according to the following steps: one, preparation 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes: at first 9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is dissolved in Glacial acetic acid/vitriol oil mixed solution, obtain mixture after dissolving mixing fully, then add for 3 ~ 10 times N-bromo-succinimide average mark in the mixture, and N-bromo-succinimide of every adding is stirring reaction 30min ~ 60min at room temperature, after all adding, the N-bromo-succinimide continues at room temperature stirring reaction 4h ~ 12h, namely obtain reaction solution, then reaction solution is poured in the frozen water, after all melting, the ice in the frozen water adopts methylene dichloride or ethyl acetate extraction, the organic layer that extraction obtains adopts anhydrous sodium sulphate to carry out drying, then carry out suction filtration, the filtrate that suction filtration obtains is till temperature is to be concentrated into the absence of liquid outflow under 50 ℃ ~ 70 ℃, carry out at last column chromatography take sherwood oil/methylene dichloride mixed solvent as eluent and purify, namely obtain 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes; Two; Umang reaction: with salt of wormwood; carbazole; cuprous iodide and 18-hat-6 ethers add in 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes; then add under the nitrogen protection 1; 3-dimethyl-3; 4; 5; 6-tetrahydrochysene-2-pyrimidone; and be 90 ℃ ~ 250 ℃ lower reaction 12h ~ 50h in nitrogen protection and temperature; namely obtain reacting after product; then adopt methylene dichloride that the reaction after product is extracted; the organic layer that extraction obtains at room temperature adopts anhydrous sodium sulphate to carry out drying, carries out at last column chromatography take sherwood oil/methylene dichloride mixed solvent as eluent and purifies, and namely obtains the single phosphine oxygen of single functionalization substituted fluorene based compound.

The mol ratio of the salt of wormwood described in the present embodiment step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is (1 ~ 6): 1; The mol ratio of the carbazole described in the present embodiment step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is (1 ~ 10): 1; The mol ratio of the cuprous iodide described in the present embodiment step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is (0.05 ~ 0.5): 1; 18-hat-6 ethers described in the present embodiment step 2 and the mol ratio of 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes are (0.001 ~ 0.05): 1; Described in the present embodiment step 21,3-dimethyl-3,4,5,6-tetrahydrochysene-2-pyrimidone volume and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes molar ratio are (1mL ~ 10mL): 1mmol.

Embodiment six: present embodiment is that the single phosphine oxygen of embodiment one and embodiment four described single functionalization substituted fluorene based compounds are as the application of the material of main part in the blue light electroluminescence phosphorescence device or the luminescent material in the blue organic electroluminescence device.

Embodiment seven: the difference of present embodiment and embodiment six is: the preparation method of described blue light electroluminescence device finishes according to the following steps:

Step 1, adopt vacuum vapour deposition the first layer conductive to be plated in to form thickness on the substrate material be the film of 1nm ~ 10nm, thickness be the film of 1nm ~ 10nm as the first layer conductive layer of anode, wherein said substrate material is glass or plastics; Step 2, adopt vacuum vapour deposition hole transport layer material to be plated in to form thickness on the first layer conductive layer be the film of 20nm ~ 60nm, thickness is that the film of 20nm ~ 60nm is hole transmission layer; Step 3, adopt vacuum vapour deposition hole transport/electronic blocking layer material to be plated in to form thickness on the hole transmission layer be the film of 1nm ~ 40nm, thickness is that the film of 1nm ~ 40nm is hole transport/electronic barrier layer; Step 4, adopt vacuum vapour deposition the luminescent layer material to be plated in to form thickness on hole transport/electronic barrier layer be the film of 5nm ~ 40nm, thickness is that the film of 5nm ~ 40nm is luminescent layer; Step 5, adopt vacuum vapour deposition electric transmission/exciton barrier-layer material to be plated in to form thickness on the luminescent layer be the film of 10nm ~ 80nm, thickness is that the film of 10nm ~ 80nm is electric transmission/exciton barrier-layer; Step 6, adopt vacuum vapour deposition second layer conductive to be plated in to form thickness on electric transmission/exciton barrier-layer be the film of 1nm ~ 120nm, thickness be the film of 1nm ~ 120nm as the second layer conductive layer of negative electrode, namely obtain the blue light electroluminescence device; The first layer conductive described in the step 1 is tin indium oxide or polyaniline; Luminescent layer material described in the step 4 is the adulterate body that the single phosphine oxygen substituted fluorene based compound of single functionalization or complex of iridium and single functionalization list phosphine oxygen substituted fluorene based compound are mixed by any ratio formation; Second layer conductive described in the step 6 is calcium, calcium alloy, magnesium, magnesium alloy, silver, silver alloys, aluminum or aluminum alloy.

When the described second layer conductive of present embodiment is aluminium, should adopt vacuum vapour deposition plating one deck lithium fluoride on the first electron transfer layer, the lithium fluoride film thickness that obtains is 0.5nm ~ 1.5nm.

Embodiment eight: the difference of present embodiment and embodiment seven is: the hole transport layer material described in the step 2 is MoO ₃, 4,4', 4 " three (N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), N, N'-is two-(3-naphthyl)-N, N'-phenylbenzene-[1; the 1'-phenylbenzene]-4; 4'-diamines (NPB) and N, N'-is two-(3-aminomethyl phenyl)-N, N'-phenylbenzene-[1; the 1'-xenyl]-4, a kind of in the 4'-diamines (TPD) or several mixture wherein.Other are identical with embodiment seven.

When the hole transport layer material described in the present embodiment step 2 is mixture, be mixed by any ratio between each component.

Embodiment nine: present embodiment and one of embodiment seven or eight difference are: the hole transport described in the step 3/electronic blocking layer material is that three (1-phenylpyrazoles) close iridium (Ir (ppz) ₃) or 4,4', 4 " three (carbazole-9-yl) triphenylamines (TCTA).Other are identical with embodiment seven or eight.

Embodiment ten: one of present embodiment and embodiment seven to nine difference is: the electric transmission described in the step 5/exciton barrier-layer material is 4,7-phenylbenzene-1,10-phenanthrolene (Bphen) or 1,3,5-three (N-phenyl-2-benzimidazolyl-2 radicals) benzene (TPBI).Other are identical with embodiment seven to nine.

Adopt following verification experimental verification effect of the present invention:

Test one: the preparation method of the single phosphine oxygen of single functionalization substituted fluorene based compound, chemical name is that 2-diethyl fluorenes-9-phenyl-9-diphenylphosphine oxygen phenyl fluorenes is specifically finished according to the following steps: one, preparation 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes: at first 9-phenyl-9-(the diphenylphosphine oxygen phenyl) fluorenes with 1mmol is dissolved in Glacial acetic acid/vitriol oil mixed solution, obtain mixture after dissolving mixing fully, then the N-bromo-succinimide average mark with 1.2mmol adds for 6 times in the mixture, and N-bromo-succinimide of every adding is stirring reaction 40min at room temperature, after all adding, the N-bromo-succinimide continues at room temperature stirring reaction 8h, namely obtain reaction solution, then reaction solution is poured in the frozen water, after all melting, the ice in the frozen water adopts dichloromethane extraction, the organic layer that extraction obtains adopts anhydrous sodium sulphate to carry out drying, then carry out suction filtration, the filtrate that suction filtration obtains is till temperature is to be concentrated into the absence of liquid outflow under 60 ℃, carry out column chromatography with sherwood oil/methylene dichloride mixed solvent at last and purify, namely obtain 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes; Two; suzuki reaction: at first with the tetrakis triphenylphosphine palladium of 0.05mmol; 0.05mmol Tetrabutyl amonium bromide; 1.5mmol boric ester derivative and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes of 1mmol mix; then in argon shield with without the tetrahydrofuran (THF) that adds 10mL under the optical condition; adding 3mL concentration is the NaOH aqueous solution of 2mol/L again; and under being 85 ℃ and argon shield, temperature reacts 24h; namely obtain reacting after product; adopt saturated ammonium chloride that the reaction after product is extracted; the organic layer that extraction obtains at room temperature adopts anhydrous sodium sulphate to carry out drying; carry out column chromatography with sherwood oil/methylene dichloride mixed solvent at last and purify, namely obtain the single phosphine oxygen of single functionalization substituted fluorene based compound.

Glacial acetic acid described in the present embodiment step 1/vitriol oil mixed solution is mixed by the Glacial acetic acid of 6mL and the vitriol oil of 2mL.

Sherwood oil described in the present embodiment step 1/methylene dichloride mixed solvent by sherwood oil and methylene dichloride by volume 1:2 mix.

H in the vitriol oil described in the present embodiment step 1 ₂SO ₄Massfraction be 98.3%.

Boric ester derivative described in the present embodiment step 2 is

Sherwood oil described in the present embodiment step 2/methylene dichloride mixed solvent by sherwood oil and methylene dichloride by volume 1:2 mix.

Adopt nuclear magnetic resonance analyser to detect 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes that this testing sequence one obtains, detected result is as follows:

¹H?NMR(400MHz,CDCl ₃):δ=7.726-7.585(m,6H),7.538-7.400(m,10H),7.352(t,J=7.4Hz,2H),7.291-7.215(m,6H),7.141-7.117(m,2H).

Because this testing sequence one is to carry out bromo take 9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes as parent, the detected result of the proton nmr spectra that the syncaryon magnetic resonance device detects as can be known: the structural formula of 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is

Adopt nuclear magnetic resonance analyser to detect the single phosphine oxygen of the single functionalization substituted fluorene based compound of this test preparation, detected result is as follows:

¹H?NMR(400MHz,CDCl ₃):δ(ppm):7.847-7.787(m,2H),7.729-7.627(m,8H),7.544-7.480(m,6H),7.445-7.209(m,17H),2.075-2.020(m,4H),0.350(t,J=7.2,6H).

This testing sequence two is in fact to adopt

Carry out suzuki reaction with 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes, the detected result of the proton nmr spectra that the syncaryon magnetic resonance device detects as can be known: the structural formula of the single phosphine oxygen of single functionalization substituted fluorene based compound is

Test two: the preparation method of the single phosphine oxygen of single functionalization substituted fluorene based compound, chemical name is that 2-phenyl carbazole-9-phenyl-9-diphenylphosphine oxygen phenyl fluorenes is specifically finished according to the following steps: one, preparation 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes: at first 9-phenyl-9-(the diphenylphosphine oxygen phenyl) fluorenes with 1mmol is dissolved in Glacial acetic acid/vitriol oil mixed solution, obtain mixture after dissolving mixing fully, then the N-bromo-succinimide average mark with 1.2mmol adds for 6 times in the mixture, and N-bromo-succinimide of every adding is stirring reaction 40min at room temperature, after all adding, the N-bromo-succinimide continues at room temperature stirring reaction 8h, namely obtain reaction solution, then reaction solution is poured in the frozen water, after all melting, the ice in the frozen water adopts dichloromethane extraction, the organic layer that extraction obtains adopts anhydrous sodium sulphate to carry out drying, then carry out suction filtration, the filtrate that suction filtration obtains is till temperature is to be concentrated into the absence of liquid outflow under 60 ℃, carry out column chromatography with sherwood oil/methylene dichloride mixed solvent at last and purify, namely obtain 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes; Two; suzuki reaction: at first with the tetrakis triphenylphosphine palladium of 0.05mmol; 0.05mmol Tetrabutyl amonium bromide; 1.5mmol boric ester derivative and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes of 1mmol mix; then in argon shield with without the tetrahydrofuran (THF) that adds 10mL under the optical condition; adding 3mL concentration is the NaOH aqueous solution of 2mol/L again; and under being 85 ℃ and argon shield, temperature reacts 24h; namely obtain reacting after product; adopt saturated ammonium chloride that the reaction after product is extracted; the organic layer that extraction obtains at room temperature adopts anhydrous sodium sulphate to carry out drying; carry out column chromatography with sherwood oil/methylene dichloride mixed solvent at last and purify, namely obtain the single phosphine oxygen of single functionalization substituted fluorene based compound.

Boric ester derivative described in the present embodiment step 2 is

¹H?NMR(400MHz,CDCl ₃):δ(ppm):8.146(d,J=7.6,2H),7.856(d,J=7.6,1H),7.811(d,J=7.2,1H),7.758(d,J=8.4,2H),7.713-7.595(m,8H),7.559-7.485(m,4H),7.460-7.365(m,12H),7.316-7.244(m,8H).

This testing sequence two is in fact to adopt

Test three: the preparation method of the single phosphine oxygen of single functionalization substituted fluorene based compound, chemical name is that 2-triphenylamine-9-phenyl-9-diphenylphosphine oxygen phenyl fluorenes is specifically finished according to the following steps: one, preparation 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes: at first 9-phenyl-9-(the diphenylphosphine oxygen phenyl) fluorenes with 1mmol is dissolved in Glacial acetic acid/vitriol oil mixed solution, obtain mixture after dissolving mixing fully, then the N-bromo-succinimide average mark with 1.2mmol adds for 6 times in the mixture, and N-bromo-succinimide of every adding is stirring reaction 40min at room temperature, after all adding, the N-bromo-succinimide continues at room temperature stirring reaction 8h, namely obtain reaction solution, then reaction solution is poured in the frozen water, after all melting, the ice in the frozen water adopts dichloromethane extraction, the organic layer that extraction obtains adopts anhydrous sodium sulphate to carry out drying, then carry out suction filtration, the filtrate that suction filtration obtains is till temperature is to be concentrated into the absence of liquid outflow under 60 ℃, carry out column chromatography with sherwood oil/methylene dichloride mixed solvent at last and purify, namely obtain 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes; Two; suzuki reaction: at first with the tetrakis triphenylphosphine palladium of 0.05mmol; 0.05mmol Tetrabutyl amonium bromide; 1.5mmol boric ester derivative and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes of 1mmol mix; then in argon shield with without the tetrahydrofuran (THF) that adds 10mL under the optical condition; adding 3mL concentration is the NaOH aqueous solution of 2mol/L again; and under being 85 ℃ and argon shield, temperature reacts 24h; namely obtain reacting after product; adopt saturated ammonium chloride that the reaction after product is extracted; the organic layer that extraction obtains at room temperature adopts anhydrous sodium sulphate to carry out drying; carry out column chromatography with sherwood oil/methylene dichloride mixed solvent at last and purify, namely obtain the single phosphine oxygen of single functionalization substituted fluorene based compound.

Boric ester derivative described in the present embodiment step 2 is

¹H?NMR(400MHz,CDCl ₃):δ(ppm):7.779(dd,J1=J2=8,2H),7.651(dd,J1=J2=7.6,4H),7.569(t,J=7.4,2H),7.552-7.316(m,14H),7.275-7.207(m,10H),7.105(t,J=7.8,6H),7.024(t，J=7.2,2H).

This testing sequence two is in fact to adopt Carry out suzuki reaction with 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes, the detected result of the proton nmr spectra that the syncaryon magnetic resonance device detects as can be known: the structural formula of the single phosphine oxygen of single functionalization substituted fluorene based compound is

Test four: the preparation method of the single phosphine oxygen of single functionalization substituted fluorene based compound, chemical name is that 2-naphthyl phenyl amine-9-phenyl-9-diphenylphosphine oxygen phenyl fluorenes is specifically finished according to the following steps: one, preparation 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes: at first 9-phenyl-9-(the diphenylphosphine oxygen phenyl) fluorenes with 1mmol is dissolved in Glacial acetic acid/vitriol oil mixed solution, obtain mixture after dissolving mixing fully, then the N-bromo-succinimide average mark with 1.2mmol adds for 6 times in the mixture, and N-bromo-succinimide of every adding is stirring reaction 40min at room temperature, after all adding, the N-bromo-succinimide continues at room temperature stirring reaction 8h, namely obtain reaction solution, then reaction solution is poured in the frozen water, after all melting, the ice in the frozen water adopts dichloromethane extraction, the organic layer that extraction obtains adopts anhydrous sodium sulphate to carry out drying, then carry out suction filtration, the filtrate that suction filtration obtains is till temperature is to be concentrated into the absence of liquid outflow under 60 ℃, carry out column chromatography with sherwood oil/methylene dichloride mixed solvent at last and purify, namely obtain 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes; Two; suzuki reaction: at first with the tetrakis triphenylphosphine palladium of 0.05mmol; 0.05mmol Tetrabutyl amonium bromide; 1.5mmol boric ester derivative and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes of 1mmol mix; then in argon shield with without the tetrahydrofuran (THF) that adds 10mL under the optical condition; adding 3mL concentration is the NaOH aqueous solution of 2mol/L again; and under being 85 ℃ and argon shield, temperature reacts 24h; namely obtain reacting after product; adopt saturated ammonium chloride that the reaction after product is extracted; the organic layer that extraction obtains at room temperature adopts anhydrous sodium sulphate to carry out drying; carry out column chromatography with sherwood oil/methylene dichloride mixed solvent at last and purify, namely obtain the single phosphine oxygen of single functionalization substituted fluorene based compound.

Boric ester derivative described in the present embodiment step 2 is

¹H?NMR(400MHz,CDCl ₃):δ(ppm):7.962(d,J=8.4,1H),7.914(d,J=8,1H),7.818-7.769(m,3H)，7.694-7.646(m,4H),7.590-7.326(m,20H),7.298-7.197(m,8H)，7.107(d，J=7.6,2H),7.053(d,J=8.4,2H),6.983(t,J=7.2,1H).

This testing sequence two is in fact to adopt

Test five: the preparation method of the single phosphine oxygen of single functionalization substituted fluorene based compound, chemical name is that 2-carbazole-9-phenyl-9-(diphenylphosphine oxygen phenyl) specifically finishes according to the following steps: one, preparation 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes: at first 9-phenyl-9-(the diphenylphosphine oxygen phenyl) fluorenes with 1mmol is dissolved in Glacial acetic acid/vitriol oil mixed solution, obtain mixture after dissolving mixing fully, then the N-bromo-succinimide average mark with 1.2mmol adds for 6 times in the mixture, and N-bromo-succinimide of every adding is stirring reaction 40min at room temperature, after all adding, the N-bromo-succinimide continues at room temperature stirring reaction 8h, namely obtain reaction solution, then reaction solution is poured in the frozen water, after all melting, the ice in the frozen water adopts dichloromethane extraction, the organic layer that extraction obtains adopts anhydrous sodium sulphate to carry out drying, then carry out suction filtration, the filtrate that suction filtration obtains is till temperature is to be concentrated into the absence of liquid outflow under 60 ℃, carry out column chromatography with sherwood oil/methylene dichloride mixed solvent at last and purify, namely obtain 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes; Two; Umang reaction: with the salt of wormwood of 1.5mmol; 2.5mmol carbazole; 0.1mmol cuprous iodide and the 18-of 0.01mmol hat-6 ethers add in 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes of 1mmol; then add 1 of 5mL under the nitrogen protection; 3-dimethyl-3; 4; 5; 6-tetrahydrochysene-2-pyrimidone; and be 190 ℃ of lower reaction 24h in nitrogen protection and temperature; namely obtain reacting after product; then adopt methylene dichloride that the reaction after product is extracted; the organic layer that extraction obtains at room temperature adopts anhydrous sodium sulphate to carry out drying; carry out column chromatography with sherwood oil/methylene dichloride mixed solvent at last and purify, namely obtain the single phosphine oxygen of single functionalization substituted fluorene based compound.

¹H?NMR(400MHz,CDCl ₃):8.125(d,J=7.6,2H),7.971(d,J=7.6,1H),7.844(d,J=7.6,1H)，7.672-7.622(m,6H),7.546-7.496(m,4H),7.430-7.412(m,6H),7.355-7.325(m,7H),7.257-7.233(m,7H).

This testing sequence two is in fact to adopt carbazole and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes to carry out the Umang reaction, the detected result of the proton nmr spectra that the syncaryon magnetic resonance device detects as can be known: the structural formula of single functionalization list phosphine oxygen substituted fluorene based compound is

Adopt SHIMADZURF-5301PC type spectrograph and PR 650 instruments to detect test one to the single phosphine oxygen of the single functionalization substituted fluorene based compound of test five preparations, detected result as described in Figure 1, Fig. 1 is that test one to the single phosphine oxygen of the test single functionalization of five preparations substituted fluorene based compound is dissolved in the utilizing emitted light spectrogram in the dichloromethane solution, among the figure ■ represent to test a preparation the single phosphine oxygen of single functionalization substituted fluorene based compound---2-diethyl fluorenes-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is dissolved in the utilizing emitted light spectrogram in the dichloromethane solution, among the figure ● expression test two preparations the single phosphine oxygen of single functionalization substituted fluorene based compound---2-phenyl carbazole-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is dissolved in the utilizing emitted light spectrogram in the dichloromethane solution, among the figure ▲ expression test three preparations the single phosphine oxygen of single functionalization substituted fluorene based compound---2-triphenylamine-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is dissolved in the utilizing emitted light spectrogram in the dichloromethane solution, among the figure

Expression test four preparations the single phosphine oxygen of single functionalization substituted fluorene based compound---2-naphthyl phenyl amine-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is dissolved in the utilizing emitted light spectrogram in the dichloromethane solution, among the figure ◆ expression test five preparations the single phosphine oxygen of single functionalization substituted fluorene based compound---2-carbazole-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is dissolved in the utilizing emitted light spectrogram in the dichloromethane solution; The single phosphine oxygen of the single functionalization substituted fluorene based compound of testing as shown in Figure 1 a preparation has two main fluorescence peaks, be respectively 369nm and 386nm, the single phosphine oxygen of the single functionalization substituted fluorene based compound of testing as can be known five preparations has two main fluorescence peaks, be respectively 355nm and 369nm, it is 396nm that the single phosphine oxygen of the single functionalization substituted fluorene based compounds of testing as can be known two preparations have an emission peak, it is 432nm that the single phosphine oxygen of the single functionalization substituted fluorene based compounds of testing as can be known three preparations have an emission peak, and it is 436nm that the single phosphine oxygen of the single functionalization substituted fluorene based compounds of testing as can be known four preparations have an emission peak; Can be used for preparing blue light so test the single phosphine oxygen of a single functionalization substituted fluorene based compound to test five preparations, even dark blue optical device.

Test six: the preparation method of blue light electroluminescence phosphorescence device, specifically finish according to the following steps:

Step 1, adopt vacuum vapour deposition tin indium oxide to be plated in to form thickness on the substrate material be the film of 5nm, thickness be the film of 5nm as the first layer conductive layer of anode, wherein said substrate material is glass or plastics; Step 2, employing vacuum vapour deposition are successively with MoO ₃And N, N'-pair-(3-naphthyl)-N, N'-phenylbenzene-[1,1'-phenylbenzene]-4, the 4'-diamines is plated on the first layer conductive layer, and it is 5nm that MoOx forms film thickness, N, N'-pair-(3-naphthyl)-N, N'-phenylbenzene-[1, the 1'-phenylbenzene]-4, it is 50nm that the 4'-diamines forms film thickness, the hole transmission layer total thickness that obtains is 55nm; Step 3, adopt vacuum vapour deposition with 4,4', 4 " three (carbazole-9-yl) triphenylamine is plated in that formation thickness is the film of 5nm on the hole transmission layer, and thickness is that the film of 5nm is hole transport/electronic barrier layer; Step 4, adopt vacuum vapour deposition the luminescent layer material to be plated in to form thickness on hole transport/electronic barrier layer be the film of 20nm, thickness is that the film of 20nm is luminescent layer; Step 5, adopt vacuum vapour deposition 1,3,5-three (N-phenyl-2-benzimidazolyl-2 radicals) benzene to be plated in to form thickness on the luminescent layer be the film of 30nm, thickness is that the film of 30nm is electric transmission/exciton barrier-layer; Step 6, employing vacuum vapour deposition are plated in lithium fluoride and aluminium on the electron transfer layer successively, and it is 1nm that lithium fluoride forms film thickness, it is 100nm that aluminium forms film thickness, and the second layer conductive layer thick film total thickness that obtains as negative electrode is 101nm, namely obtains the blue light electroluminescence device.

This is tested described luminescent layer material and is two (4,6-difluorophenyl pyridine-N, C2) the pyridine formyl closes iridium mixes formation with the single phosphine oxygen of the single functionalization substituted fluorene based compound of test two preparations adulterate body, and in the described luminescent layer material two (4,6-difluorophenyl pyridine-N, C2) to close the massfraction of iridium (FIrpic) be 15% to the pyridine formyl.

Test seven: the preparation method of blue light electroluminescence phosphorescence device, specifically finish according to the following steps:

This is tested described luminescent layer material and is two (4,6-difluorophenyl pyridine-N, C2) the pyridine formyl closes iridium mixes formation with the single phosphine oxygen of the single functionalization substituted fluorene based compound of test five preparations adulterate body, and in the described luminescent layer material two (4,6-difluorophenyl pyridine-N, C2) to close the massfraction of iridium (FIrpic) be 15% to the pyridine formyl.

Adopt Keithley 2400/2000Sourcemeter instrument to detect the blue light electroluminescence phosphorescence device of test six and test seven preparations, detected result as shown in Figure 2, Fig. 2 is organic electrophosphorescenpolymer current density-current efficiency spectrogram, ■ among Fig. 2 represents to test the six blue light electroluminescence phosphorescence device current density for preparing-current efficiency spectrograms, among Fig. 2 ● the blue light electroluminescence phosphorescence device current density of expression test seven preparations-current efficiency spectrograms; The current efficiency of testing as shown in Figure 2 the blue light electroluminescence phosphorescence device of six preparations is 28.8cd/A, the current efficiency of testing as can be known the blue light electroluminescence phosphorescence device of seven preparations is 35.5cd/A, and therefore the single phosphine oxygen of the single functionalization substituted fluorene based compound of proof test two and test five preparations has high efficiency as the blue emitting phosphor material of main part.

Test eight: the preparation method of blue light electroluminescence fluorescent device, specifically finish according to the following steps:

This is tested described luminescent layer material and is the single phosphine oxygen of the single functionalization substituted fluorene based compound of test one preparation.

Test nine: the preparation method of blue light electroluminescence fluorescent device, specifically finish according to the following steps:

This is tested described luminescent layer material and is the single phosphine oxygen of the single functionalization substituted fluorene based compound of test three preparations.

Test ten: the preparation method of blue light electroluminescence fluorescent device, specifically finish according to the following steps:

This is tested described luminescent layer material and is the single phosphine oxygen of the single functionalization substituted fluorene based compound of test four preparations.

Adopt Keithley 2400/2000 Sourcemeter and PR 650 instruments to detect the blue light electroluminescence fluorescent device of test eight and test ten preparations, detected result as shown in Figure 3, Fig. 3 is voltage-to-current density-brightness curve figure, ■ among Fig. 3 represents to test the blue light electroluminescence fluorescent device voltage-to-current density map of eight preparations, among Fig. 3 ● the blue light electroluminescence fluorescent device voltage-to-current density spectra figure of expression test nine preparations, among Fig. 3 ▲ the blue light electroluminescence fluorescent device voltage-to-current density spectra figure of expression test ten preparations, the blue light electroluminescence fluorescent device voltage of the expression of zero among Fig. 3 test eight preparations-brightness spectrogram, among Fig. 3 represents to test the nine blue light electroluminescence fluorescent device voltage for preparing-brightness spectrograms, and the △ among Fig. 3 represents to test the ten blue light electroluminescence fluorescent device voltage for preparing-brightness spectrograms; The trigger voltage of testing as shown in Figure 3 the blue light electroluminescence fluorescent device of eight preparations is 4.1V, the trigger voltage of testing as shown in Figure 3 the blue light electroluminescence fluorescent device of nine preparations is 3.1V, the trigger voltage of testing as shown in Figure 3 the ten blue light electroluminescence fluorescent device that prepare is 3.3V, and therefore proving test one, test three and testing the four single phosphine oxygen of the single functionalization substituted fluorene based compounds that prepare is low-voltage high-efficiency blue light functional materialss.

Claims

1. the single phosphine oxygen of single functionalization substituted fluorene based compound is characterized in that the single phosphine oxygen of single functionalization substituted fluorene based compound chemical name is 2-R-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes, and structural formula is:

Wherein said R is

Or

2. the preparation method of the single phosphine oxygen of single functionalization as claimed in claim 1 substituted fluorene based compound, it is characterized in that what the single phosphine oxygen of single functionalization substituted fluorene based compound was specifically finished according to the following steps: one, preparation 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes: at first 9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is dissolved in Glacial acetic acid/vitriol oil mixed solution, obtain mixing solutions after dissolving mixing fully, then add for 3 ~ 10 times N-bromo-succinimide average mark in the mixture, and N-bromo-succinimide of every adding is stirring reaction 30min ~ 60min at room temperature, after all adding, the N-bromo-succinimide continues at room temperature stirring reaction 4h ~ 12h, namely obtain reaction solution, then reaction solution is poured in the frozen water, after all melting, the ice in the frozen water adopts methylene dichloride or ethyl acetate extraction, the organic layer that extraction obtains adopts anhydrous sodium sulphate to carry out drying, then carry out suction filtration, the filtrate that suction filtration obtains is till temperature is to be concentrated into the absence of liquid outflow under 50 ℃ ~ 70 ℃, carry out at last column chromatography take sherwood oil/methylene dichloride mixed solvent as eluent and purify, namely obtain 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes; Glacial acetic acid described in the step 1/vitriol oil mixed solution is mixed by Glacial acetic acid and the vitriol oil, and the volume ratio of wherein said Glacial acetic acid and the vitriol oil is (1 ~ 5): 1; The ratio of the 9-phenyl-9-described in the step 1 (diphenylphosphine oxygen phenyl) fluorenes amount of substance and Glacial acetic acid/vitriol oil mixeding liquid volume is 1mmol:(3mL ~ 18mL); The mol ratio 1:(0.5 of (the diphenylphosphine oxygen phenyl) fluorenes of the 9-phenyl-9-described in the step 1 and N-bromo-succinimide ~ 3); Two, suzuki reaction: at first with tetrakis triphenylphosphine palladium, Tetrabutyl amonium bromide, boric ester derivative and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes mix, then add tetrahydrofuran (THF) in argon shield with without under the optical condition, adding concentration is the NaOH aqueous solution of 1mol/L ~ 3mol/L again, and under being 80 ℃ ~ 90 ℃ and argon shield, temperature reacts 8h ~ 32h, namely obtain reacting after product, adopt saturated ammonium chloride that the reaction after product is extracted, the organic layer that extraction obtains at room temperature adopts anhydrous sodium sulphate to carry out drying, carry out at last column chromatography take sherwood oil/methylene dichloride mixed solvent as eluent and purify, namely obtain the single phosphine oxygen of single functionalization substituted fluorene based compound; The mol ratio of the tetrakis triphenylphosphine palladium described in the step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is (0.005 ~ 0.1): 1; The mol ratio of the Tetrabutyl amonium bromide described in the step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is (0.01 ~ 0.1): 1; The mol ratio of the boric ester derivative described in the step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is (0.5 ~ 2): 1; Tetrahydrofuran (THF) volume described in the step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes molar ratio are (4mL ~ 10mL): 1mmol; Concentration described in the step 2 is that the NaOH aqueous solution of 1mol/L ~ 3mol/L and the mol ratio of 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes are (0.5 ~ 7): 1.

3. the preparation method of the single phosphine oxygen of single functionalization according to claim 2 substituted fluorene based compound is characterized in that the boric ester derivative described in the step 2 is

Or

4. the single phosphine oxygen of single functionalization substituted fluorene based compound is characterized in that the single phosphine oxygen of single functionalization substituted fluorene based compound chemical name is 2-carbazole-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes, and structural formula is:

5. the preparation method of the single phosphine oxygen of single functionalization as claimed in claim 4 substituted fluorene based compound, it is characterized in that what the single phosphine oxygen of single functionalization substituted fluorene based compound was specifically finished according to the following steps: one, preparation 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes: at first 9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is dissolved in Glacial acetic acid/vitriol oil mixed solution, obtain mixture after dissolving mixing fully, then add for 3 ~ 10 times N-bromo-succinimide average mark in the mixture, and N-bromo-succinimide of every adding is stirring reaction 30min ~ 60min at room temperature, after all adding, the N-bromo-succinimide continues at room temperature stirring reaction 4h ~ 12h, namely obtain reaction solution, then reaction solution is poured in the frozen water, after all melting, the ice in the frozen water adopts methylene dichloride or ethyl acetate extraction, the organic layer that extraction obtains adopts anhydrous sodium sulphate to carry out drying, then carry out suction filtration, the filtrate that suction filtration obtains is till temperature is to be concentrated into the absence of liquid outflow under 50 ℃ ~ 70 ℃, carry out at last column chromatography take sherwood oil/methylene dichloride mixed solvent as eluent and purify, namely obtain 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes; Glacial acetic acid described in the step 1/vitriol oil mixed solution is mixed by Glacial acetic acid and the vitriol oil, and the volume ratio of wherein said Glacial acetic acid and the vitriol oil is (1 ~ 5): 1; The ratio of the 9-phenyl-9-described in the step 1 (diphenylphosphine oxygen phenyl) fluorenes amount of substance and Glacial acetic acid/vitriol oil mixeding liquid volume is 1mmol:(3mL ~ 18mL); The mol ratio 1:(0.5 of (the diphenylphosphine oxygen phenyl) fluorenes of the 9-phenyl-9-described in the step 1 and N-bromo-succinimide ~ 3); Two, Umang reaction: with salt of wormwood, carbazole, cuprous iodide and 18-hat-6 ethers add in 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes, then add under the nitrogen protection 1,3-dimethyl-3,4,5,6-tetrahydrochysene-2-pyrimidone, and be 90 ℃ ~ 250 ℃ lower reaction 12h ~ 50h in nitrogen protection and temperature, namely obtain reacting after product, then adopt methylene dichloride that the reaction after product is extracted, the organic layer that extraction obtains at room temperature adopts anhydrous sodium sulphate to carry out drying, carries out at last column chromatography take sherwood oil/methylene dichloride mixed solvent as eluent and purifies, and namely obtains the single phosphine oxygen of single functionalization substituted fluorene based compound; The mol ratio of the salt of wormwood described in the step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is (1 ~ 6): 1; The mol ratio of the carbazole described in the step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is (1 ~ 10): 1; The mol ratio of the cuprous iodide described in the step 2 and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes is (0.05 ~ 0.5): 1; 18-hat-6 ethers described in the step 2 and the mol ratio of 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes are (0.001 ~ 0.05): 1; Described in the step 21,3-dimethyl-3,4,5,6-tetrahydrochysene-2-pyrimidone volume and 2-bromo-9-phenyl-9-(diphenylphosphine oxygen phenyl) fluorenes molar ratio are (1mL ~ 10mL): 1mmol.

6. such as the application of claim 1 or the single phosphine oxygen of 4 described single functionalization substituted fluorene based compound, it is characterized in that the single phosphine oxygen of single functionalization substituted fluorene based compound is as the application of the material of main part in the blue light electroluminescence phosphorescence device or the luminescent material in the blue organic electroluminescence device.

7. the application of the single phosphine oxygen of single functionalization according to claim 6 substituted fluorene based compound is characterized in that the preparation method of described blue light electroluminescence device finishes according to the following steps:

1), adopt vacuum vapour deposition the first layer conductive to be plated in to form thickness on the substrate material be the film of 1nm ~ 10nm, thickness be the film of 1nm ~ 10nm as the first layer conductive layer of anode, wherein said substrate material is glass or plastics; 2), adopt vacuum vapour deposition hole transport layer material to be plated in to form thickness on the first layer conductive layer be the film of 20nm ~ 60nm, thickness is that the film of 20nm ~ 60nm is hole transmission layer; 3), adopt vacuum vapour deposition hole transport/electronic blocking layer material to be plated in to form thickness on the hole transmission layer be the film of 1nm ~ 40nm, thickness is that the film of 1nm ~ 40nm is hole transport/electronic barrier layer; 4), adopt vacuum vapour deposition the luminescent layer material to be plated in to form thickness on hole transport/electronic barrier layer be the film of 5nm ~ 40nm, thickness is that the film of 5nm ~ 40nm is luminescent layer; 5), adopt vacuum vapour deposition electric transmission/exciton barrier-layer material to be plated in to form thickness on the luminescent layer be the film of 10nm ~ 80nm, thickness is that the film of 10nm ~ 80nm is electric transmission/exciton barrier-layer; 6), adopt vacuum vapour deposition second layer conductive to be plated in to form thickness on electric transmission/exciton barrier-layer be the film of 1nm ~ 120nm, thickness be the film of 1nm ~ 120nm as the second layer conductive layer of negative electrode, namely obtain the blue light electroluminescence device; The first layer conductive described in the step 1 is tin indium oxide or polyaniline; Luminescent layer material described in the step 4 is that the single phosphine oxygen substituted fluorene based compound of single functionalization or complex of iridium mix the adulterate body that forms with the single phosphine oxygen of single functionalization substituted fluorene based compound; Second layer conductive described in the step 6 is calcium, calcium alloy, magnesium, magnesium alloy, silver, silver alloys, aluminum or aluminum alloy.

8. the preparation method of blue light electroluminescence device according to claim 7 is characterized in that the hole transport layer material described in the step 2 is MoO ₃, 4,4', 4 " three (N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N'-is two-(3-naphthyl)-N, N'-phenylbenzene-[1; the 1'-phenylbenzene]-4; 4'-diamines and N, N'-is two-(3-aminomethyl phenyl)-N, N'-phenylbenzene-[1; the 1'-xenyl]-4, a kind of in the 4'-diamines or several mixture wherein.

9. the preparation method of blue light electroluminescence device according to claim 8 is characterized in that the hole transport described in the step 3/electronic blocking layer material " three (carbazole-9-yl) triphenylamine that is that three (1-phenylpyrazoles) close iridium or 4,4', 4.

10. according to claim 7, the preparation method of 8 or 9 described blue light electroluminescence devices, it is characterized in that the electric transmission described in the step 5/exciton barrier-layer material is 4,7-phenylbenzene-1,10-phenanthrolene or 1,3,5-three (N-phenyl-2-benzimidazolyl-2 radicals) benzene.