CN102898473A - Multifunctional modified dibenzofuran-based di-phosphineoxy compound and preparation method and application thereof - Google Patents

Multifunctional modified dibenzofuran-based di-phosphineoxy compound and preparation method and application thereof Download PDF

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CN102898473A
CN102898473A CN201210431656XA CN201210431656A CN102898473A CN 102898473 A CN102898473 A CN 102898473A CN 201210431656X A CN201210431656X A CN 201210431656XA CN 201210431656 A CN201210431656 A CN 201210431656A CN 102898473 A CN102898473 A CN 102898473A
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dibenzothiophene
bromo
oxygen base
diphenylphosphine oxygen
base
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许辉
韩春苗
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Heilongjiang University
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Heilongjiang University
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Abstract

The invention discloses a multifunctional modified dibenzofuran-based di-phosphineoxy compound and a preparation method and an application thereof, which relate to a luminescent layer main body material in an electron phosphorescent device and a preparation method and an application thereof, and are used for solving the problem of high starting voltage during application of an electron phosphorescent device main body material prepared by using the conventional method since a high triple state energy level and high current carrier injection transport capability cannot be realized simultaneously. The preparation method of the multifunctional modified dibenzofuran-based di-phosphineoxy compound comprises the following steps of: I, performing a bromination reaction, and performing extraction, drying, spinning drying and column chromatography in sequence; and II, performing a substitution reaction, and performing extraction, drying, spinning drying and column chromatography in sequence. The multifunctional modified dibenzofuran-based di-phosphineoxy compound is applied as a luminescent layer main body material in an electron phosphorous device. The method is mainly used for preparing a multifunctional modified dibenzofuran-based di-phosphineoxy compound.

Description

Multifunction is modified two phosphine oxide compounds of dibenzothiophene base and its preparation method and application
Technical field
The present invention relates to luminescent layer material of main part and its preparation method and application in a kind of electro phosphorescent device.
Background technology
Organic Light Emitting Diode has the characteristics such as luminous, high brightness, high-level efficiency, frivolous, wide visual angle and easy processing, be called " inferior epoch flat-panel monitor ", " fantasy indicating meter " by the insider, have broad application prospects in fields such as information demonstration and solid state lightings.In electroluminescent, the organic molecule that is excited by the compound of electronics and hole, the restriction of the choosing rule that do not spinned is calculated as can be known in theory according to statistical distribution, and the ratio that is produced excited triplet state and excited singlet state by the organic molecule that is stimulated is 3:1; In other words, in electroluminescent, if do not consider the power loss that other are possible, the fluorescence electroluminescent has only utilized approximately 25% of input energy; All the other input energy that are in excited triplet state are not effectively utilized, but have lost with the form of nonradiative transition, and this point Forrest etc. are confirmed in their experiment, and they have measured Alq 3The singlet state mark be 22% ± 3%.But for phosphor material, it can pass through by between being, realization has mixed the phosphorescent emissions of triplet exciton and singlet state exciton, in theory, utilize the maximum internal quantum efficiency of the OLED that phosphor material makes can reach 100%, its luminous efficiency has improved three times than fluorescent material.Therefore, the EL efficient of the OLED device that phosphor material is made is all very high, and the theoretical value of EL power efficiency is 120lm/W.So in order to obtain high performance electroluminescent device, developing high efficiency phosphor material is a very important approach.But, because most electromechanical phosphorescent material is easier to that all concentration quenching occurs and triplet state is buried in oblivion, thereby greatly reduce luminous efficiency and the brightness of device.Therefore, how to solve these cancellation and bury in oblivion effect and become the key that improves device efficiency.At present, a kind of very effective way is exactly to select a kind of suitable material as matrix, guest materials is evenly dispersed in this matrix, thus the distance between the increase guest molecule, reduce Molecular interaction, reach the effect that inhibition concentration cancellation and triplet state are buried in oblivion.So far existing many seminars are studied this field, and result of study is selected the various aspects of performance that suitable material of main part really can decades of times ground raising device.And people study triplet excitation attitude energy level and the carrier injection/transmittability of finding material of main part and can directly have influence on the device synthesis performance.For effective transmission ofenergy between the assurance Subjective and Objective requires material of main part to have higher triplet usually, and wide energy gap is unfavorable for injection and the transmission of current carrier, finally causes the driving voltage of electro phosphorescent device higher.There is the problem that can not have simultaneously the high carrier injection transmittability of becoming reconciled of triplet concurrently in therefore existing electro phosphorescent device material of main part.
Summary of the invention
The electro phosphorescent device material of main part that the objective of the invention is to solve existing method preparation can not have the problem of the high carrier injection transmittability of becoming reconciled of triplet simultaneously concurrently, there is the high problem of trigger voltage when causing the electro phosphorescent device material of main part of its conduct to be used, and provides multifunction to modify two phosphine oxide compounds of dibenzothiophene base and its preparation method and application.
Multifunction is modified the two phosphine oxide compounds of dibenzothiophene base, and its chemical name is 4,6-two (diphenylphosphine oxygen base) dibenzothiophene derivatives, and structure is as follows:
Figure BDA00002349009500011
Wherein said X, Y is as follows: (1) as X is
Figure BDA00002349009500012
Y is-H or
Figure BDA00002349009500021
(2) as X be Y is-H or (3) as X be Y is-H or
Figure BDA00002349009500025
(4) as X be
Figure BDA00002349009500026
Y is-H or
Figure BDA00002349009500027
Multifunction is modified the preparation method of the two phosphine oxide compounds of dibenzothiophene base, chemical name is 4,6-two (diphenylphosphine oxygen base) dibenzothiophene derivatives is specifically finished according to the following steps: one, bromo: at first with 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is dissolved in the vitriol oil, then press N-bromo-succinimide and 4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (1 ~ 1.2): 1 adds the N-bromo-succinimide, and at stirring reaction 2h ~ 4h, obtain the bromo-reaction product and adopt CH 2Cl 2And H 2O extracts, and the bromo organic layer that obtains adopts first siccative to carry out drying, adopts the rotary evaporation method to be spin-dried for again, and carries out at last column chromatography take ethyl acetate as eluent and purifies, and namely obtains 2-bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene; Described in the step 14, the ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene amount of substance and vitriol oil volume are 1mmol:(2mL ~ 4mL); Siccative described in the step 1 is anhydrous sodium sulphate or anhydrous magnesium sulfate; Two, replace: at first pinacol borate compound, Tetrabutyl amonium bromide and tetra-triphenylphosphine palladium are added 2-bromo-4, in 6-two (the diphenylphosphine oxygen base) dibenzothiophene, adding successively, tetrahydrofuran (THF) and concentration are the NaOH aqueous solution of 1mmol/mL ~ 3mmol/mL again, then be warming up to 80 ℃ ~ 100 ℃ from room temperature, and be stirring reaction 12h ~ 24h under 80 ℃ ~ 100 ℃ the condition in temperature, obtain the substitution reaction product and adopt CH 2Cl 2With saturated NH 4The Cl aqueous solution extracts, the replacement organic layer that obtains adopts first siccative to carry out drying, adopt again the rotary evaporation method to be spin-dried for, carry out at last column chromatography take ethyl acetate as eluent and purify, namely obtain multifunction and modify the two phosphine oxide compounds of dibenzothiophene base; Pinacol borate compound described in the step 2 is
Figure BDA00002349009500028
Figure BDA00002349009500029
Or
Figure BDA000023490095000210
The pinacol borate compound that adds described in the step 2 and 2-bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (1 ~ 1.2): 1; The Tetrabutyl amonium bromide that adds described in the step 2 and 2-bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.08 ~ 0.12): 1; The tetra-triphenylphosphine palladium that adds described in the step 2 and 2-bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.08 ~ 0.12): 1; The tetrahydrofuran (THF) volume that adds described in the step 2 and 2-bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene molar ratio are (5mL ~ 10mL): 1mmol; Adding concentration described in the step 2 is the NaOH aqueous solution and the 2-bromo-4 of 1mmol/mL ~ 3mmol/mL, and 6-two (diphenylphosphine oxygen base) dibenzothiophene mass ratio is (2.5 ~ 3.5): 1; Siccative described in the step 2 is anhydrous sodium sulphate or anhydrous magnesium sulfate.
Multifunction is modified the preparation method of the two phosphine oxide compounds of dibenzothiophene base, chemical name is 4,6-two (diphenylphosphine oxygen base) dibenzothiophene derivatives is specifically finished according to the following steps: one, bromo: at first with 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is dissolved in the vitriol oil, then press N-bromo-succinimide and 4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (2 ~ 2.5): 1 adds the N-bromo-succinimide, and at stirring reaction 2h ~ 4h, obtain the bromo-reaction product and adopt CH 2Cl 2And H 2O extracts, and the bromo organic layer that obtains adopts first siccative to carry out drying, adopts the rotary evaporation method to be spin-dried for again, carry out at last column chromatography purifies take ethyl acetate as eluent, namely obtain 2,8-, two bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene; Described in the step 14, the ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene amount of substance and vitriol oil volume are 1mmol:(2mL ~ 4mL); Siccative described in the step 1 is anhydrous sodium sulphate or anhydrous magnesium sulfate; Two, replace: at first pinacol borate compound, Tetrabutyl amonium bromide and tetra-triphenylphosphine palladium are added 2,8-two bromo-4, in 6-two (the diphenylphosphine oxygen base) dibenzothiophene, adding successively, tetrahydrofuran (THF) and concentration are the NaOH aqueous solution of 1mmol/mL ~ 3mmol/mL again, then be warming up to 80 ℃ ~ 100 ℃ from room temperature, and be stirring reaction 12h ~ 24h under 80 ℃ ~ 100 ℃ the condition in temperature, obtain the substitution reaction product and adopt CH 2Cl 2With saturated NH 4The Cl aqueous solution extracts, the replacement organic layer that obtains adopts first siccative to carry out drying, adopt again the rotary evaporation method to be spin-dried for, carry out at last column chromatography take ethyl acetate as eluent and purify, namely obtain multifunction and modify the two phosphine oxide compounds of dibenzothiophene base; Pinacol borate compound described in the step 2 is
Figure BDA00002349009500031
Figure BDA00002349009500032
Or The pinacol borate compound that adds described in the step 2 and 2,8-, two bromo-4, the mol ratio (2 ~ 2.1) of 6-two (diphenylphosphine oxygen base) dibenzothiophene: 1; The Tetrabutyl amonium bromide that adds described in the step 2 and 2,8-, two bromo-4, the mol ratio (0.19 ~ 0.21) of 6-two (diphenylphosphine oxygen base) dibenzothiophene: 1; The tetra-triphenylphosphine palladium that adds described in the step 2 and 2,8-, two bromo-4, the mol ratio (0.19 ~ 0.21) of 6-two (diphenylphosphine oxygen base) dibenzothiophene: 1; The tetrahydrofuran (THF) volume that adds described in the step 2 and 2,8-, two bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene molar ratio are (5mL ~ 10mL): 1mmol; Adding concentration described in the step 2 is the NaOH aqueous solution and 2,8-, two bromo-4 of 1mmol/mL ~ 3mmol/mL, and 6-two (diphenylphosphine oxygen base) dibenzothiophene mass ratio is (5.5 ~ 6.5): 1; Siccative described in the step 2 is anhydrous sodium sulphate or anhydrous magnesium sulfate.
Multifunction is modified the two phosphine oxide compounds of dibenzothiophene base, and its chemical name is 4,6-two (diphenylphosphine oxygen base) dibenzothiophene derivatives, and structure is as follows:
Figure BDA00002349009500034
Wherein said X is
Figure BDA00002349009500035
Wherein said Y is-H or
Figure BDA00002349009500036
Multifunction is modified the preparation method of the two phosphine oxide compounds of dibenzothiophene base, chemical name is 2-carbazyl-4,6-two (diphenylphosphine oxygen base) dibenzothiophene is finished according to the following steps: one, bromo: at first with 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is dissolved in the vitriol oil, then press N-bromo-succinimide and 4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (1 ~ 1.2): 1 adds the N-bromo-succinimide, and stirring reaction 2h ~ 4h, obtain the bromo-reaction product and adopt CH 2Cl 2And H 2O extracts, and the bromo organic layer that obtains adopts first siccative to carry out drying, adopts the rotary evaporation method to be spin-dried for again, and carries out at last column chromatography take ethyl acetate as eluent and purifies, and namely obtains 2-bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene; Described in the step 14, the ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene amount of substance and vitriol oil volume are 1mmol:(2mL ~ 4mL); Siccative described in the step 1 is anhydrous sodium sulphate or anhydrous magnesium sulfate; Two, replace: at first carbazole, salt of wormwood, cuprous iodide, 18-are preced with-6 ethers and 1,3-dimethyl-2-imidazolidone adds 2-bromo-4, in 6-two (the diphenylphosphine oxygen base) dibenzothiophene, then be stirring reaction 24h ~ 48h under 160 ℃ ~ 200 ℃ conditions in temperature, obtain the substitution reaction product and adopt CH 2Cl 2With saturated NH 4The Cl aqueous solution extracts, the replacement organic layer that obtains adopts first siccative to carry out drying, adopt again the rotary evaporation method to be spin-dried for, carry out at last column chromatography take ethyl acetate as eluent and purify, namely obtain multifunction and modify the two phosphine oxide compounds of dibenzothiophene base; The carbazole that adds described in the step 2 and 2-bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (1 ~ 1.2): 1; The salt of wormwood that adds described in the step 2 and 2-bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.8 ~ 1.2): 1; The cuprous iodide that adds described in the step 2 and 2-bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.08 ~ 0.12): 1; 18-hat-6 ethers and the 2-bromo-4 that add described in the step 2, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.08 ~ 0.12): 1; Add described in the step 21,3-dimethyl-2-imidazolidone volume and 2-bromo-4, the ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene amount of substance are (8mL ~ 12mL): 1mmol; Siccative described in the step 2 is anhydrous sodium sulphate or anhydrous magnesium sulfate.
Multifunction is modified the preparation method of the two phosphine oxide compounds of dibenzothiophene base, chemical name is 2,8-two (carbazyl)-4,6-two (diphenylphosphine oxygen base) dibenzothiophene is finished according to the following steps: one, bromo: at first with 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is dissolved in the vitriol oil, then press N-bromo-succinimide and 4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (2 ~ 2.5): 1 adds the N-bromo-succinimide, and stirring reaction 2h ~ 4h, obtain the bromo-reaction product and adopt CH 2Cl 2And H 2O extracts, and the bromo organic layer that obtains adopts first siccative to carry out drying, adopts the rotary evaporation method to be spin-dried for again, carry out at last column chromatography purifies take ethyl acetate as eluent, namely obtain 2,8-, two bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene; Described in the step 14, the ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene amount of substance and vitriol oil volume are 1mmol:(2mL ~ 4mL); Siccative described in the step 1 is anhydrous sodium sulphate or anhydrous magnesium sulfate; Two, replace: at first carbazole, salt of wormwood, cuprous iodide, 18-are preced with-6 ethers and 1,3-dimethyl-2-imidazolidone adds 2,8-two bromo-4, in 6-two (the diphenylphosphine oxygen base) dibenzothiophene, then be stirring reaction 24h ~ 48h under 160 ℃ ~ 200 ℃ conditions in temperature, obtain the substitution reaction product and adopt CH 2Cl 2With saturated NH 4The Cl aqueous solution extracts, the replacement organic layer that obtains adopts first siccative to carry out drying, adopt again the rotary evaporation method to be spin-dried for, carry out at last column chromatography take ethyl acetate as eluent and purify, namely obtain multifunction and modify the two phosphine oxide compounds of dibenzothiophene base; The carbazole that adds described in the step 2 and 2,8-, two bromo-4, the mol ratio (2 ~ 2.1) of 6-two (diphenylphosphine oxygen base) dibenzothiophene: 1; The salt of wormwood that adds described in the step 2 and 2,8-, two bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (1.9 ~ 2.1): 1; The cuprous iodide that adds described in the step 2 and 2,8-, two bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.19 ~ 0.21): 1; 18-hat-6 ethers and 2,8-, two bromo-4 that add described in the step 2, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.19 ~ 0.21): 1; Add described in the step 21,3-dimethyl-2-imidazolidone volume and 2,8-, two bromo-4, the ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene amount of substance are (8mL ~ 12mL): 1mmol; Siccative described in the step 2 is anhydrous sodium sulphate or anhydrous magnesium sulfate.
Above-mentioned multifunction is modified the application of the two phosphine oxide compounds of dibenzothiophene base, and multifunction is modified the two phosphine oxide compounds of dibenzothiophene base as the application of luminescent layer material of main part in the electro phosphorescent device.
Advantage of the present invention: one, the multifunction of the present invention's preparation is modified the two phosphine oxide compounds of dibenzothiophene base with 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is as parent fraction, 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is the dibenzothiophene that the diphenylphosphine oxygen groups has been modified at the ortho position, still have higher triplet (~ 3.0eV), and the introducing of phosphine oxygen groups makes it have certain electronic injection and transmittability, and the present invention selects the modification of functional group is carried out in the contraposition of parent, introduce the carbazole group that some have the hole transport performance, 9,9-diethyl fluorene group, naphthyl diphenylamine group or trianilino group, strengthen the hole transport performance of molecule when guaranteeing not affect the high triplet of parent, position by the regulatory function group and number are with energy state and the carrier transmission performance of careful adjustment molecule, so compare with existing electro phosphorescent device material of main part, the multifunction of the present invention's preparation is modified the two phosphine oxide compounds of dibenzothiophene base and has been kept higher triplet, guarantee the effective communication of energy from the main body to the object, and the carrier injection transmittability is good, reduce trigger voltage when using as the electro phosphorescent device material of main part, improved efficient and the stability thereof of electro phosphorescent device; Two, the multifunction of the present invention's preparation is modified the thermogravimetric good stability of the two phosphine oxide compounds of dibenzothiophene base, and general cracking temperature is between 420 ℃ ~ 550 ℃.
Description of drawings
Fig. 1 is that test one prepares the Ultraluminescence spectrum spectrogram that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base, among Fig. 1 represents the two phosphine oxide compounds of multifunction modification dibenzothiophene base/dichloromethane solution UV spectrum spectrogram, among Fig. 1 zero expression multifunction is modified the two phosphine oxide compound film ultraviolet spectrum of dibenzothiophene base spectrogram, ■ among Fig. 1 represents the two phosphine oxide compounds of multifunction modification dibenzothiophene base/dichloromethane solution fluorescence spectrum spectrogram, among Fig. 1 ● the expression multifunction is modified the two phosphine oxide compound film fluorescence spectrum spectrograms of dibenzothiophene base, among Fig. 1 ▲ the expression multifunction modifies the phosphorescence spectrum spectrogram of the two phosphine oxide compounds of dibenzothiophene base; Fig. 2 is that test one prepares the thermogravimetric analysis spectrogram that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base; Fig. 3 is that test two prepares the Ultraluminescence spectrum spectrogram that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base, ■ among Fig. 3 represents the two phosphine oxide compounds of multifunction modification dibenzothiophene base/dichloromethane solution UV spectrum spectrogram, among Fig. 3 ● the expression multifunction is modified the two phosphine oxide compound film ultraviolet spectrum of dibenzothiophene base spectrogram, among Fig. 3 represents the two phosphine oxide compounds of multifunction modification dibenzothiophene base/dichloromethane solution fluorescence spectrum spectrogram, among Fig. 3 zero expression multifunction is modified the two phosphine oxide compound film fluorescence spectrum spectrograms of dibenzothiophene base, and the △ among Fig. 3 represents the phosphorescence spectrum spectrogram of the two phosphine oxide compounds of multifunction modification dibenzothiophene base; Fig. 4 is that test two prepares the thermogravimetric analysis spectrogram that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base; Fig. 5 is that test three prepares the Ultraluminescence spectrum spectrogram that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base, among Fig. 5 represents the two phosphine oxide compounds of multifunction modification dibenzothiophene base/dichloromethane solution UV spectrum spectrogram, among Fig. 5 zero expression multifunction is modified the two phosphine oxide compound film ultraviolet spectrum of dibenzothiophene base spectrogram, ■ among Fig. 5 represents the two phosphine oxide compounds of multifunction modification dibenzothiophene base/dichloromethane solution fluorescence spectrum spectrogram, among Fig. 5 ▲ the expression multifunction modifies the two phosphine oxide compound film fluorescence spectrum spectrograms of dibenzothiophene base, among Fig. 5 ▲ the expression multifunction modifies the phosphorescence spectrum spectrogram of the two phosphine oxide compounds of dibenzothiophene base; Fig. 6 is that test three prepares the thermogravimetric analysis spectrogram that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base; Fig. 7 is the voltage-to-current density relationship curve of the blue light electroluminescence device of test four preparations; Fig. 8 is the voltage-brightness relationship curve of the blue light electroluminescence devices of test four preparations; Fig. 9 is the brightness-current efficiency relation curve of the blue light electroluminescence devices of test four preparations; Figure 10 is the brightness-power efficiency relation curve of the blue light electroluminescence devices of test four preparations; Figure 11 is the brightness-external quantum efficiency relation curve of the blue light electroluminescence devices of test four preparations; Figure 12 is the electroluminescent spectrum of the blue light electroluminescence device of test four preparations; Figure 13 is the voltage-to-current density relationship curve of the electro-green light device of test five preparations; Figure 14 is the voltage-brightness relationship curve of the electro-green light devices of test five preparations; Figure 15 is the brightness-current efficiency relation curve of the electro-green light devices of test five preparations; Figure 16 is the brightness-power efficiency relation curve of the electro-green light devices of test five preparations; Figure 17 is the brightness-external quantum efficiency relation curve of the electro-green light devices of test five preparations; Figure 18 is the electroluminescent spectrum of the electro-green light device of test five preparations; Figure 19 is the voltage-to-current density relationship curve that the electricity of test six preparations causes the gold-tinted device; Figure 20 is that the electricity of test six preparations cause the voltage of gold-tinted device-brightness relationship curve; Figure 21 is that the electricity of test six preparations cause the brightness of gold-tinted device-current efficiency relation curve; Figure 22 is that the electricity of test six preparations cause the brightness of gold-tinted device-power efficiency relation curve; Figure 23 is that the electricity of test six preparations cause the brightness of gold-tinted device-external quantum efficiency relation curve; Figure 24 is the electroluminescent spectrum that the electricity of test six preparations causes the gold-tinted device; Figure 25 is the voltage-to-current density relationship curve of the red electroluminescent device of test seven preparations; Figure 26 is the voltage-brightness relationship curve of the red electroluminescent devices of test seven preparations; Figure 27 is the brightness-current efficiency relation curve of the red electroluminescent devices of test seven preparations; Figure 28 is the brightness-power efficiency relation curve of the red electroluminescent devices of test seven preparations; Figure 29 is the brightness-external quantum efficiency relation curve of the red electroluminescent devices of test seven preparations; Figure 30 is the electroluminescent spectrum of the red electroluminescent device of test seven preparations.
Embodiment
Embodiment one: present embodiment is that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base, and its chemical name is 4,6-two (diphenylphosphine oxygen base) dibenzothiophene derivatives, and structure is as follows:
Figure BDA00002349009500061
Wherein said X, Y is as follows: (1) as X is Y is-H or (2) as X be
Figure BDA00002349009500064
Y is-H or
Figure BDA00002349009500065
(3) as X be
Figure BDA00002349009500066
Y is-H or
Figure BDA00002349009500067
(4) as X be
Figure BDA00002349009500068
Y is-H or
Figure BDA00002349009500069
Embodiment two: present embodiment is the preparation method that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base, chemical name is 4,6-two (diphenylphosphine oxygen base) dibenzothiophene derivatives is specifically finished according to the following steps: one, bromo: at first with 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is dissolved in the vitriol oil, then press N-bromo-succinimide and 4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (1 ~ 1.2): 1 adds the N-bromo-succinimide, and at stirring reaction 2h ~ 4h, obtain the bromo-reaction product and adopt CH 2Cl 2And H 2O extracts, and the bromo organic layer that obtains adopts first siccative to carry out drying, adopts the rotary evaporation method to be spin-dried for again, and carries out at last column chromatography take ethyl acetate as eluent and purifies, and namely obtains 2-bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene; Two, replace: at first pinacol borate compound, Tetrabutyl amonium bromide and tetra-triphenylphosphine palladium are added 2-bromo-4, in 6-two (the diphenylphosphine oxygen base) dibenzothiophene, adding successively, tetrahydrofuran (THF) and concentration are the NaOH aqueous solution of 1mmol/mL ~ 3mmol/mL again, then be warming up to 80 ℃ ~ 100 ℃ from room temperature, and be stirring reaction 12h ~ 24h under 80 ℃ ~ 100 ℃ the condition in temperature, obtain the substitution reaction product and adopt CH 2Cl 2With saturated NH 4The Cl aqueous solution extracts, the replacement organic layer that obtains adopts first siccative to carry out drying, adopt again the rotary evaporation method to be spin-dried for, carry out at last column chromatography take ethyl acetate as eluent and purify, namely obtain multifunction and modify the two phosphine oxide compounds of dibenzothiophene base.
Described in the present embodiment step 14, the ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene amount of substance and vitriol oil volume are 1mmol:(2mL ~ 4mL); Siccative described in the present embodiment step 1 is anhydrous sodium sulphate or anhydrous magnesium sulfate.
Pinacol borate compound described in the present embodiment step 2 is
Figure BDA00002349009500071
Figure BDA00002349009500072
Or
Figure BDA00002349009500073
The pinacol borate compound that adds described in the present embodiment step 2 and 2-bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (1 ~ 1.2): 1; The Tetrabutyl amonium bromide that adds described in the present embodiment step 2 and 2-bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.08 ~ 0.12): 1; The tetra-triphenylphosphine palladium that adds described in the present embodiment step 2 and 2-bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.08 ~ 0.12): 1; The tetrahydrofuran (THF) volume that adds described in the present embodiment step 2 and 2-bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene molar ratio are (5mL ~ 10mL): 1mmol; Adding concentration described in the present embodiment step 2 is the NaOH aqueous solution and the 2-bromo-4 of 1mmol/mL ~ 3mmol/mL, and 6-two (diphenylphosphine oxygen base) dibenzothiophene mass ratio is (2.5 ~ 3.5): 1; Siccative described in the present embodiment step 2 is anhydrous sodium sulphate or anhydrous magnesium sulfate.
Described in the present embodiment step 2
Figure BDA00002349009500074
The preparation method, specifically finish according to the following steps: with 15g(49.8mmol)
Figure BDA00002349009500075
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
Figure BDA00002349009500076
Described in the present embodiment step 2
Figure BDA00002349009500077
ChemSpider Id be 10024545.
Described in the present embodiment step 2
Figure BDA00002349009500081
ChemSpider Id be 9814049.
Described in the present embodiment step 2
Figure BDA00002349009500082
The preparation method, specifically finish according to the following steps: with 10g(26.8mmol)
Figure BDA00002349009500083
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 Phosphine oxygen (P=O) group couples together aromatic group by the C-P saturated bond, can effectively block conjugation, can guarantee that molecule has higher triplet; The P=O group has the effect of polar molecule simultaneously, can put forward high molecular electronic injection transmittability.Phosphine oxide compound has a plurality of aryl usually in addition, is fit to very much carry out the design ﹠ formulation of complicated molecule.Therefore the multifunction of present embodiment preparation is modified the two phosphine oxide compounds of dibenzothiophene base with 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is as parent fraction, 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is the dibenzothiophene that the diphenylphosphine oxygen groups has been modified at the ortho position, still have higher triplet (~ 3.0eV), and the introducing of phosphine oxygen groups makes it have certain electronic injection and transmittability, and present embodiment is selected the modification of functional group is carried out in the contraposition of parent, introduce some and have 9 of hole transport performance, 9-diethyl fluorene group, naphthyl diphenylamine group or trianilino group, strengthen the hole transport performance of molecule when guaranteeing not affect the high triplet of parent, position by the regulatory function group and number are with energy state and the carrier transmission performance of careful adjustment molecule, so compare with existing electro phosphorescent device material of main part, the multifunction of present embodiment preparation is modified the two phosphine oxide compounds of dibenzothiophene base and has been kept higher triplet, guarantee the effective communication of energy from the main body to the object, and the carrier injection transmittability is good, reduce trigger voltage when using as the electro phosphorescent device material of main part, improved efficient and the stability thereof of electro phosphorescent device.
The multifunction of present embodiment preparation is modified the thermogravimetric good stability of the two phosphine oxide compounds of dibenzothiophene base, and general cracking temperature is between 420 ℃ ~ 550 ℃.
Embodiment three: present embodiment is the preparation method that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base, chemical name is 4,6-two (diphenylphosphine oxygen base) dibenzothiophene derivatives is specifically finished according to the following steps: one, bromo: at first with 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is dissolved in the vitriol oil, then press N-bromo-succinimide and 4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (2 ~ 2.5): 1 adds the N-bromo-succinimide, and at stirring reaction 2h ~ 4h, obtain the bromo-reaction product and adopt CH 2Cl 2And H 2O extracts, and the bromo organic layer that obtains adopts first siccative to carry out drying, adopts the rotary evaporation method to be spin-dried for again, carry out at last column chromatography purifies take ethyl acetate as eluent, namely obtain 2,8-, two bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene; Described in the step 14, the ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene amount of substance and vitriol oil volume are 1mmol:(2mL ~ 4mL); Siccative described in the step 1 is anhydrous sodium sulphate or anhydrous magnesium sulfate; Two, replace: at first pinacol borate compound, Tetrabutyl amonium bromide and tetra-triphenylphosphine palladium are added 2,8-two bromo-4, in 6-two (the diphenylphosphine oxygen base) dibenzothiophene, adding successively, tetrahydrofuran (THF) and concentration are the NaOH aqueous solution of 1mmol/mL ~ 3mmol/mL again, then be warming up to 80 ℃ ~ 100 ℃ from room temperature, and be stirring reaction 12h ~ 24h under 80 ℃ ~ 100 ℃ the condition in temperature, obtain the substitution reaction product and adopt CH 2Cl 2With saturated NH 4The Cl aqueous solution extracts, the replacement organic layer that obtains adopts first siccative to carry out drying, adopt again the rotary evaporation method to be spin-dried for, carry out at last column chromatography take ethyl acetate as eluent and purify, namely obtain multifunction and modify the two phosphine oxide compounds of dibenzothiophene base.
Described in the present embodiment step 14, the ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene amount of substance and vitriol oil volume are 1mmol:(2mL ~ 4mL); Siccative described in the present embodiment step 1 is anhydrous sodium sulphate or anhydrous magnesium sulfate.
Pinacol borate compound described in the present embodiment step 2 is
Figure BDA00002349009500091
Figure BDA00002349009500092
Or
Figure BDA00002349009500093
The pinacol borate compound that adds described in the present embodiment step 2 and 2,8-, two bromo-4, the mol ratio (2 ~ 2.1) of 6-two (diphenylphosphine oxygen base) dibenzothiophene: 1; The Tetrabutyl amonium bromide that adds described in the present embodiment step 2 and 2,8-, two bromo-4, the mol ratio (0.19 ~ 0.21) of 6-two (diphenylphosphine oxygen base) dibenzothiophene: 1; The tetra-triphenylphosphine palladium that adds described in the present embodiment step 2 and 2,8-, two bromo-4, the mol ratio (0.19 ~ 0.21) of 6-two (diphenylphosphine oxygen base) dibenzothiophene: 1; The tetrahydrofuran (THF) volume that adds described in the present embodiment step 2 and 2,8-, two bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene molar ratio are (5mL ~ 10mL): 1mmol; Adding concentration described in the present embodiment step 2 is the NaOH aqueous solution and 2,8-, two bromo-4 of 1mmol/mL ~ 3mmol/mL, and 6-two (diphenylphosphine oxygen base) dibenzothiophene mass ratio is (5.5 ~ 6.5): 1; Siccative described in the present embodiment step 2 is anhydrous sodium sulphate or anhydrous magnesium sulfate.
Phosphine oxygen (P=O) group couples together aromatic group by the C-P saturated bond, can effectively block conjugation, can guarantee that molecule has higher triplet; The P=O group has the effect of polar molecule simultaneously, can put forward high molecular electronic injection transmittability.Phosphine oxide compound has a plurality of aryl usually in addition, is fit to very much carry out the design ﹠ formulation of complicated molecule.Therefore the multifunction of present embodiment preparation is modified the two phosphine oxide compounds of dibenzothiophene base with 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is as parent fraction, 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is the dibenzothiophene that the diphenylphosphine oxygen groups has been modified at the ortho position, still have higher triplet (~ 3.0eV), and the introducing of phosphine oxygen groups makes it have certain electronic injection and transmittability, and present embodiment is selected the modification of functional group is carried out in the contraposition of parent, introduce some and have 9 of hole transport performance, 9-diethyl fluorene group, naphthyl diphenylamine group or trianilino group, strengthen the hole transport performance of molecule when guaranteeing not affect the high triplet of parent, position by the regulatory function group and number are with energy state and the carrier transmission performance of careful adjustment molecule, so compare with existing electro phosphorescent device material of main part, the multifunction of present embodiment preparation is modified the two phosphine oxide compounds of dibenzothiophene base and has been kept higher triplet, guarantee the effective communication of energy from the main body to the object, and the carrier injection transmittability is good, reduce trigger voltage when using as the electro phosphorescent device material of main part, improved efficient and the stability thereof of electro phosphorescent device.
The multifunction of present embodiment preparation is modified the thermogravimetric good stability of the two phosphine oxide compounds of dibenzothiophene base, and general cracking temperature is between 420 ℃ ~ 550 ℃.
Embodiment four: present embodiment is that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base, and its chemical name is 4,6-two (diphenylphosphine oxygen base) dibenzothiophene derivatives, and structure is as follows:
Figure BDA00002349009500101
Wherein said X is Wherein said Y is-H or
Figure BDA00002349009500103
Embodiment five: present embodiment is the preparation method that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base, chemical name is 2-carbazyl-4,6-two (diphenylphosphine oxygen base) dibenzothiophene is finished according to the following steps: one, bromo: at first with 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is dissolved in the vitriol oil, then press N-bromo-succinimide and 4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (1 ~ 1.2): 1 adds the N-bromo-succinimide, and stirring reaction 2h ~ 4h, obtain the bromo-reaction product and adopt CH 2Cl 2And H 2O extracts, and the bromo organic layer that obtains adopts first siccative to carry out drying, adopts the rotary evaporation method to be spin-dried for again, and carries out at last column chromatography take ethyl acetate as eluent and purifies, and namely obtains 2-bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene; Two, replace: at first carbazole, salt of wormwood, cuprous iodide, 18-are preced with-6 ethers and 1,3-dimethyl-2-imidazolidone adds 2-bromo-4, in 6-two (the diphenylphosphine oxygen base) dibenzothiophene, then be stirring reaction 24h ~ 48h under 160 ℃ ~ 200 ℃ conditions in temperature, obtain the substitution reaction product and adopt CH 2Cl 2With saturated NH 4The Cl aqueous solution extracts, the replacement organic layer that obtains adopts first siccative to carry out drying, adopt again the rotary evaporation method to be spin-dried for, carry out at last column chromatography take ethyl acetate as eluent and purify, namely obtain multifunction and modify the two phosphine oxide compounds of dibenzothiophene base.
Described in the present embodiment step 14, the ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene amount of substance and vitriol oil volume are 1mmol:(2mL ~ 4mL); Siccative described in the present embodiment step 1 is anhydrous sodium sulphate or anhydrous magnesium sulfate.
The carbazole that adds described in the present embodiment step 2 and 2-bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (1 ~ 1.2): 1; The salt of wormwood that adds described in the present embodiment step 2 and 2-bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.8 ~ 1.2): 1; The cuprous iodide that adds described in the present embodiment step 2 and 2-bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.08 ~ 0.12): 1; 18-hat-6 ethers and the 2-bromo-4 that add described in the present embodiment step 2, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.08 ~ 0.12): 1; Add described in the present embodiment step 21,3-dimethyl-2-imidazolidone volume and 2-bromo-4, the ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene amount of substance are (8mL ~ 12mL): 1mmol; Siccative described in the present embodiment step 2 is anhydrous sodium sulphate or anhydrous magnesium sulfate.
Phosphine oxygen (P=O) group couples together aromatic group by the C-P saturated bond, can effectively block conjugation, can guarantee that molecule has higher triplet; The P=O group has the effect of polar molecule simultaneously, can put forward high molecular electronic injection transmittability.Phosphine oxide compound has a plurality of aryl usually in addition, is fit to very much carry out the design ﹠ formulation of complicated molecule.Therefore the multifunction of present embodiment preparation is modified the two phosphine oxide compounds of dibenzothiophene base with 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is as parent fraction, 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is the dibenzothiophene that the diphenylphosphine oxygen groups has been modified at the ortho position, still have higher triplet (~ 3.0eV), and the introducing of phosphine oxygen groups makes it have certain electronic injection and transmittability, and present embodiment is selected the modification of functional group is carried out in the contraposition of parent, introduce some and have 9 of hole transport performance, 9-diethyl fluorene group, naphthyl diphenylamine group or trianilino group, strengthen the hole transport performance of molecule when guaranteeing not affect the high triplet of parent, position by the regulatory function group and number are with energy state and the carrier transmission performance of careful adjustment molecule, so compare with existing electro phosphorescent device material of main part, the multifunction of present embodiment preparation is modified the two phosphine oxide compounds of dibenzothiophene base and has been kept higher triplet, guarantee the effective communication of energy from the main body to the object, and the carrier injection transmittability is good, reduce trigger voltage when using as the electro phosphorescent device material of main part, improved efficient and the stability thereof of electro phosphorescent device.
The multifunction of present embodiment preparation is modified the thermogravimetric good stability of the two phosphine oxide compounds of dibenzothiophene base, and general cracking temperature is between 420 ℃ ~ 550 ℃
Embodiment six: present embodiment is the preparation method that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base, chemical name is 2,8-two (carbazyl)-4,6-two (diphenylphosphine oxygen base) dibenzothiophene is finished according to the following steps: one, bromo: at first with 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is dissolved in the vitriol oil, then press N-bromo-succinimide and 4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (2 ~ 2.5): 1 adds the N-bromo-succinimide, and stirring reaction 2h ~ 4h, obtain the bromo-reaction product and adopt CH 2Cl 2And H 2O extracts, and the bromo organic layer that obtains adopts first siccative to carry out drying, adopts the rotary evaporation method to be spin-dried for again, carry out at last column chromatography purifies take ethyl acetate as eluent, namely obtain 2,8-, two bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene; Described in the step 14, the ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene amount of substance and vitriol oil volume are 1mmol:(2mL ~ 4mL); Siccative described in the step 1 is anhydrous sodium sulphate or anhydrous magnesium sulfate; Two, replace: at first carbazole, salt of wormwood, cuprous iodide, 18-are preced with-6 ethers and 1,3-dimethyl-2-imidazolidone adds 2,8-two bromo-4, in 6-two (the diphenylphosphine oxygen base) dibenzothiophene, then be stirring reaction 24h ~ 48h under 160 ℃ ~ 200 ℃ conditions in temperature, obtain the substitution reaction product and adopt CH 2Cl 2With saturated NH 4The Cl aqueous solution extracts, the replacement organic layer that obtains adopts first siccative to carry out drying, adopt again the rotary evaporation method to be spin-dried for, carry out at last column chromatography take ethyl acetate as eluent and purify, namely obtain multifunction and modify the two phosphine oxide compounds of dibenzothiophene base; The carbazole that adds described in the step 2 and 2,8-, two bromo-4, the mol ratio (2 ~ 2.1) of 6-two (diphenylphosphine oxygen base) dibenzothiophene: 1; The salt of wormwood that adds described in the step 2 and 2,8-, two bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (1.9 ~ 2.1): 1; The cuprous iodide that adds described in the step 2 and 2,8-, two bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.19 ~ 0.21): 1; 18-hat-6 ethers and 2,8-, two bromo-4 that add described in the step 2, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.19 ~ 0.21): 1; Add described in the step 21,3-dimethyl-2-imidazolidone volume and 2,8-, two bromo-4, the ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene amount of substance are (8mL ~ 12mL): 1mmol; Siccative described in the step 2 is anhydrous sodium sulphate or anhydrous magnesium sulfate.
Phosphine oxygen (P=O) group couples together aromatic group by the C-P saturated bond, can effectively block conjugation, can guarantee that molecule has higher triplet; The P=O group has the effect of polar molecule simultaneously, can put forward high molecular electronic injection transmittability.Phosphine oxide compound has a plurality of aryl usually in addition, is fit to very much carry out the design ﹠ formulation of complicated molecule.Therefore the multifunction of present embodiment preparation is modified the two phosphine oxide compounds of dibenzothiophene base with 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is as parent fraction, 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is the dibenzothiophene that the diphenylphosphine oxygen groups has been modified at the ortho position, still have higher triplet (~ 3.0eV), and the introducing of phosphine oxygen groups makes it have certain electronic injection and transmittability, and present embodiment is selected the modification of functional group is carried out in the contraposition of parent, introduce some and have 9 of hole transport performance, 9-diethyl fluorene group, naphthyl diphenylamine group or trianilino group, strengthen the hole transport performance of molecule when guaranteeing not affect the high triplet of parent, position by the regulatory function group and number are with energy state and the carrier transmission performance of careful adjustment molecule, so compare with existing electro phosphorescent device material of main part, the multifunction of present embodiment preparation is modified the two phosphine oxide compounds of dibenzothiophene base and has been kept higher triplet, guarantee the effective communication of energy from the main body to the object, and the carrier injection transmittability is good, reduce trigger voltage when using as the electro phosphorescent device material of main part, improved efficient and the stability thereof of electro phosphorescent device.
The multifunction of present embodiment preparation is modified the thermogravimetric good stability of the two phosphine oxide compounds of dibenzothiophene base, and general cracking temperature is between 420 ℃ ~ 550 ℃.
Embodiment seven: present embodiment is that embodiment one and embodiment four described multifunctions are modified the two phosphine oxide compounds of dibenzothiophene base as the application of luminescent layer material of main part in the electro phosphorescent device.
Embodiment eight: the difference of present embodiment and embodiment seven is: the preparation method of described electro phosphorescent device finishes according to the following steps:
1, adopt vacuum vapour deposition tin indium oxide to be plated in to form thickness on the substrate material be the film of 1nm ~ 20nm, thickness be the film of 1nm ~ 20nm 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 2nm ~ 60nm, thickness is that the film of 2nm ~ 60nm is hole transmission layer, and wherein said hole transport layer material is a kind of in hole-injecting material, hole mobile material and hole transport/electronic blocking material or several mixture wherein; 3, adopt vacuum vapour deposition the luminescent layer material to be plated in to form thickness on the hole transmission layer be the film of 5nm ~ 60nm, thickness is that the film of 5nm ~ 60nm is luminescent layer, and wherein said luminescent layer material is that complex of iridium and multifunction are modified adulterate body or the two phosphine oxide compounds of multifunction modification dibenzothiophene base that the two phosphine oxide compounds of dibenzothiophene base are mixed by any ratio formation; 4, adopt vacuum vapour deposition the electric transmission 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 electron transfer layer, and wherein said electric transmission layer material is the mixture of one or both any ratios in electron transport material and the electric transmission/hole barrier materials; 5, adopt vacuum vapour deposition second layer conductive to be plated in to form thickness on the electron transfer layer be the film of 0.5nm ~ 120nm, thickness is that the film of 0.5nm ~ 120nm is as the second layer conductive layer of negative electrode, namely obtain electro phosphorescent device, wherein said second layer conductive 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.
When the hole transport layer material described in the present embodiment step 2 is mixture, be mixed by any ratio between each component.
The described electro phosphorescent device of present embodiment is that blue light electroluminescence device, electro-green light device, electricity cause gold-tinted device or red electroluminescent device.
Adopt following verification experimental verification effect of the present invention:
Test one: multifunction is modified the preparation method of the two phosphine oxide compounds of dibenzothiophene base, specifically finish according to the following steps: one, bromo: at first with 4 of 1mmol, 6-two (diphenylphosphine oxygen base) dibenzothiophene is dissolved in the vitriol oil of 4mL, then press N-bromo-succinimide and 4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is that 1:1 adds the N-bromo-succinimide, and stirring reaction 4h, obtain the bromo-reaction product and adopt CH 2Cl 2And H 2O extracts, the bromo organic layer that obtains adopts first anhydrous sodium sulphate to carry out drying, adopts the rotary evaporation method to be spin-dried for again, and carries out at last column chromatography take ethyl acetate as eluent and purifies, namely obtain 2-bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene; Two, replace: the 2-bromo-4 that at first tetrakis triphenylphosphine palladium of the Tetrabutyl amonium bromide of the pinacol borate compound of 1mmol, 0.1mmol and 0.1mmol is added 1mmol, in 6-two (the diphenylphosphine oxygen base) dibenzothiophene, add again the tetrahydrofuran (THF) of 10mL and the NaOH aqueous solution that 1.5mL concentration is 2mmol/mL, then be warming up to 90 ℃ from room temperature, and be stirring reaction 24h under 90 ℃ the condition in temperature, obtain the substitution reaction product and adopt CH 2Cl 2With saturated NH 4The Cl aqueous solution extracts, the replacement organic layer that obtains adopts first anhydrous sodium sulphate to carry out drying, adopt again the rotary evaporation method to be spin-dried for, carry out at last column chromatography take ethyl acetate as eluent and purify, namely obtain multifunction and modify the two phosphine oxide compounds of dibenzothiophene base.
Rotary evaporation method specific operation process described in this testing sequence one is as follows: will adopt the anhydrous sodium sulfate drying after product to change in the Rotary Evaporators, then be that 60 ℃ ~ 80 ℃ and rotating speed are to carry out 20min～40min under the condition of 20r/min ~ 40r/min in temperature, namely obtain being spin-dried for after product.
Pinacol borate compound described in this testing sequence two is
Figure BDA00002349009500131
Adopt nuclear magnetic resonance analyser to detect the 2-bromo-4 that this testing sequence one obtains, 6-two (diphenylphosphine oxygen base) dibenzothiophene, detected result is as follows:
1H?NMR(TMS,CDCl 3,400MHz)：ppm?δ=8.439(s,1H);8.271(d,J=8.0Hz,1H);7.912(d,J=12.4Hz,1H);7.696(q,J=7.4Hz,13Hz,1H);7.688-7.584(m,8H);7.583-7.505(m,5H);7.481-7.367(m,8H).
Because this testing sequence one is with 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is that parent carries out bromo, the detected result of the proton nmr spectra that the syncaryon magnetic resonance device detects is as can be known: 2-bromo-4, the structural formula of 6-two (diphenylphosphine oxygen base) dibenzothiophene is
Figure BDA00002349009500132
The multifunction that adopts nuclear magnetic resonance analyser to detect this test preparation is modified the two phosphine oxide compounds of dibenzothiophene base, and detected result is as follows:
1H?NMR(TMS,CDCl 3,400MHz)：ppmδ=8.511(s,1H);8.398(d,J=8.0Hz,1H);8.095(q,J=1.6Hz,13.6Hz,1H);7.773(q,J=3.0Hz,13.0Hz,1H);7.752-7.625(m,8H);7.622-7.498(m,7H);7.491-7.389(m,8H);7.301(t,J=8.0Hz,4H);7.198-7.128(m,6H);7.075(t,J=7.2Hz,2H).
This testing sequence two is in fact to adopt
Figure BDA00002349009500133
With 2-bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene carries out substitution reaction, the detected result of the proton nmr spectra that the syncaryon magnetic resonance device detects as can be known: the structural formula that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base is
Figure BDA00002349009500134
At first the multifunction for preparing of this test is modified the two phosphine oxide compounds of dibenzothiophene base at 100 ℃ of lower dry 12h, then adds methylene dichloride and is configured to 1 * 10 -6The multifunction of mol/L is modified the two phosphine oxide compound/dichloromethane solutions of dibenzothiophene base, with 1 * 10 -6The multifunction of mol/L is modified the two phosphine oxide compound/dichloromethane solutions of dibenzothiophene base and is dripped on quartz plate, the dried solvent that volatilizees namely obtains multifunction and modifies the two phosphine oxide compound films of dibenzothiophene base, then adopt Ultravioblet spectrophotometer and fluorescence spectrophotometer to detect, detected result as shown in Figure 1, Fig. 1 is that this test prepares the Ultraluminescence spectrum spectrogram that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base, among Fig. 1 represents the two phosphine oxide compounds of multifunction modification dibenzothiophene base/dichloromethane solution UV spectrum spectrogram, among Fig. 1 zero expression multifunction is modified the two phosphine oxide compound film ultraviolet spectrum of dibenzothiophene base spectrogram, ■ among Fig. 1 represents the two phosphine oxide compounds of multifunction modification dibenzothiophene base/dichloromethane solution fluorescence spectrum spectrogram, among Fig. 1 ● the expression multifunction is modified the two phosphine oxide compound film fluorescence spectrum spectrograms of dibenzothiophene base, among Fig. 1 ▲ the expression multifunction modifies the phosphorescence spectrum spectrogram of the two phosphine oxide compounds of dibenzothiophene base; Multifunction is modified the ultraviolet absorption peak of the two phosphine oxide compound/dichloromethane solutions of dibenzothiophene base respectively at 227nm, 253nm, 294nm and 341nm as shown in Figure 1; And multifunction is modified the ultraviolet absorption peak of the two phosphine oxide compound films of dibenzothiophene base at 260nm, 299nm and 351nm; Multifunction is modified the fluorescence emission peak of the two phosphine oxide compound/dichloromethane solutions of dibenzothiophene base at 461nm as shown in Figure 1; The fluorescence emission peak of film is at 441nm.Multifunction is modified the phosphorescent emissions peak of the two phosphine oxide compound films of dibenzothiophene base at 492nm.
Adopt thermogravimetric analyzer to detect the two phosphine oxide compounds of multifunction modification dibenzothiophene base that this test prepares, detected result as shown in Figure 2, Fig. 2 is that this test prepares the thermogravimetric analysis spectrogram that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base, the two phosphine oxide compound cracking temperatures of multifunction modification dibenzothiophene base that prepare by this test of Fig. 2 are 500 ℃, so the multifunction that this test prepares is modified the two phosphine oxide compound thermogravimetric good stabilities of dibenzothiophene base.
Test two: multifunction is modified the preparation method of the two phosphine oxide compounds of dibenzothiophene base, specifically finish according to the following steps: one, bromo: at first with 4 of 1mmol, 6-two (diphenylphosphine oxygen base) dibenzothiophene is dissolved in the vitriol oil of 4mL, then press N-bromo-succinimide and 4,6-two (diphenylphosphine oxygen base) dibenzothiophene mol ratio is that 2:1 adds the N-bromo-succinimide, and stirring reaction 4h, obtain the bromo-reaction product and adopt CH 2Cl 2And H 2O extracts, and the bromo organic layer that obtains adopts first anhydrous sodium sulphate to carry out drying, adopts the rotary evaporation method to be spin-dried for again, carry out at last column chromatography purifies take ethyl acetate as eluent, namely obtain 2,8-, two bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene; Two, replace: at first the pinacol borate compound of 2mmol, the Tetrabutyl amonium bromide of 0.2mmol and the tetrakis triphenylphosphine palladium of 0.2mmol are added 2 of 1mmol, 8-two bromo-4, in 6-two (the diphenylphosphine oxygen base) dibenzothiophene, add again the tetrahydrofuran (THF) of 20mL and the NaOH aqueous solution that 3mL concentration is 2mmol/mL, then be warming up to 90 ℃ from room temperature, and be stirring reaction 24h under 90 ℃ the condition in temperature, obtain the substitution reaction product and adopt CH 2Cl 2With saturated NH 4The Cl aqueous solution extracts, the replacement organic layer that obtains adopts first anhydrous sodium sulphate to carry out drying, adopt again the rotary evaporation method to be spin-dried for, carry out at last column chromatography take ethyl acetate as eluent and purify, namely obtain multifunction and modify the two phosphine oxide compounds of dibenzothiophene base.
Rotary evaporation method specific operation process described in this testing sequence one is as follows: will adopt the anhydrous sodium sulfate drying after product to change in the Rotary Evaporators, then be that 60 ℃ ~ 80 ℃ and rotating speed are to carry out 20min ~ 40min under the condition of 20r/min ~ 40r/min in temperature, namely obtain being spin-dried for after product.
Pinacol borate compound described in this testing sequence two is
Figure BDA00002349009500141
Adopt that nuclear magnetic resonance analyser detects that this testing sequence one obtains 2,8-two bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene, detected result is as follows:
1H?NMR(TMS,CDCl 3,400M?Hz):ppmδ=8.422(s,2H);7.858(q,J=2.0Hz,12.8Hz,2H);7.627(q,J=7.2Hz,12.4Hz,8H);7.563(dt,J=1.2Hz,7.4Hz,4H);7.434(q,J=2.8Hz,7.6Hz,8H).
Because this testing sequence one is with 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is that parent carries out bromo, the detected result of the proton nmr spectra that the syncaryon magnetic resonance device detects is as can be known: 2,8-, two bromo-4, the structural formula of 6-two (diphenylphosphine oxygen base) dibenzothiophene is
The multifunction that adopts nuclear magnetic resonance analyser to detect this test preparation is modified the two phosphine oxide compounds of dibenzothiophene base, and detected result is as follows:
1H?NMR(TMS,CDCl 3,400MHz)：ppm?δ=8.553(s,2H);8.072(q,J=1.6Hz,13.6Hz,2H);7.657(q,J=7.2Hz,12.4Hz,8H);7.541(dt,J=1.2Hz,7.4Hz,4H);7.515(d,J=8.8Hz,4H);7.418(dt,J=2.8Hz,7.6Hz,8H);7.340-7.262(m,8H);7.198-7.123(m,12H);7.072(t,J=7.2Hz,4H).
This testing sequence two is in fact to adopt
Figure BDA00002349009500152
With 2,8-, two bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene carries out substitution reaction, the detected result of the proton nmr spectra that the syncaryon magnetic resonance device detects as can be known: the structural formula that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base is
Figure BDA00002349009500153
At first the multifunction for preparing of this test is modified the two phosphine oxide compounds of dibenzothiophene base at 100 ℃ of lower dry 12h, then adds methylene dichloride and is configured to 1 * 10 -6The multifunction of mol/L is modified the two phosphine oxide compound/dichloromethane solutions of dibenzothiophene base, with 1 * 10 -6The multifunction of mol/L is modified the two phosphine oxide compound/dichloromethane solutions of dibenzothiophene base and is dripped on quartz plate, the dried solvent that volatilizees namely obtains multifunction and modifies the two phosphine oxide compound films of dibenzothiophene base, then adopt Ultravioblet spectrophotometer and fluorescence spectrophotometer to detect, detected result as shown in Figure 3, Fig. 3 is that this test prepares the Ultraluminescence spectrum spectrogram that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base, ■ among Fig. 3 represents the two phosphine oxide compounds of multifunction modification dibenzothiophene base/dichloromethane solution UV spectrum spectrogram, among Fig. 3 ● the expression multifunction is modified the two phosphine oxide compound film ultraviolet spectrum of dibenzothiophene base spectrogram, among Fig. 3 represents the two phosphine oxide compounds of multifunction modification dibenzothiophene base/dichloromethane solution fluorescence spectrum spectrogram, among Fig. 3 zero expression multifunction is modified the two phosphine oxide compound film fluorescence spectrum spectrograms of dibenzothiophene base, and the △ among Fig. 3 represents the phosphorescence spectrum spectrogram of the two phosphine oxide compounds of multifunction modification dibenzothiophene base; Multifunction is modified the ultraviolet absorption peak of the two phosphine oxide compound/dichloromethane solutions of dibenzothiophene base respectively at 227nm, 258nm, 296nm and 341nm as shown in Figure 3; And multifunction is modified the ultraviolet absorption peak of the two phosphine oxide compound films of dibenzothiophene base at 264nm, 302nm and 353nm; Multifunction is modified the fluorescence emission peak of the two phosphine oxide compound/dichloromethane solutions of dibenzothiophene base at 458nm, multifunction is modified the fluorescence emission peak of the two phosphine oxide compound films of dibenzothiophene base at 450nm, and the multifunction that this test prepares is modified the two phosphine oxide compound phosphorescent emissions peaks of dibenzothiophene base at 514nm.
Adopt thermogravimetric analyzer to detect the two phosphine oxide compounds of multifunction modification dibenzothiophene base that this test prepares, detected result as shown in Figure 4, Fig. 4 is that this test prepares the thermogravimetric analysis spectrogram that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base, the two phosphine oxide compound cracking temperatures of multifunction modification dibenzothiophene base that prepare by this test of Fig. 4 are 516 ℃, so the multifunction that this test prepares is modified the two phosphine oxide compound thermogravimetric good stabilities of dibenzothiophene base.
Test three: multifunction is modified the preparation method of the two phosphine oxide compounds of dibenzothiophene base, specifically finish according to the following steps: one, bromo: at first with 4 of 1mmol, 6-two (diphenylphosphine oxygen base) dibenzothiophene is dissolved in the vitriol oil of 4mL, then press N-bromo-succinimide and 4,6-two (diphenylphosphine oxygen base) dibenzothiophene mol ratio is that 1:1 adds the N-bromo-succinimide, and stirring reaction 4h, obtain the bromo-reaction product and adopt CH 2Cl 2And H 2O extracts, the bromo organic layer that obtains adopts first anhydrous sodium sulphate to carry out drying, adopts the rotary evaporation method to be spin-dried for again, and carries out at last column chromatography take ethyl acetate as eluent and purifies, namely obtain 2-bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene; Two, replace: at first the carbazole of 1mmol, the salt of wormwood of 1mmol, the cuprous iodide of 0.1mmol, the 18-of 0.1mmol are preced with 1 of-6 ethers and 10mL, 3-dimethyl-2-imidazolidone adds the 2-bromo-4 of 1mmol, in 6-two (the diphenylphosphine oxygen base) dibenzothiophene, then be stirring reaction 24h under 180 ℃ of conditions in temperature, obtain the substitution reaction product and adopt CH 2Cl 2With saturated NH 4The Cl aqueous solution extracts, the replacement organic layer that obtains adopts first anhydrous sodium sulphate to carry out drying, adopt again the rotary evaporation method to be spin-dried for, carry out at last column chromatography take ethyl acetate as eluent and purify, namely obtain multifunction and modify the two phosphine oxide compounds of dibenzothiophene base.
Rotary evaporation method specific operation process described in this testing sequence one is as follows: will adopt the anhydrous sodium sulfate drying after product to change in the Rotary Evaporators, then be that 60 ℃ ~ 80 ℃ and rotating speed are to carry out 20min ~ 40min under the condition of 20r/min ~ 40r/min in temperature, namely obtain being spin-dried for after product.
The multifunction that adopts nuclear magnetic resonance analyser to detect this test preparation is modified the two phosphine oxide compounds of dibenzothiophene base, and detected result is as follows:
1H?NMR(TMS,CDCl 3,400MHz)：ppm?δ=8.504(t,J=1.4Hz,1H);8.290(d,J=8.0Hz,1H);8.162-8.113(m,2H);7.900-7.783(m,2H);7.774-7.654(m,8H);7.608-7.503(m,5H);7.496-7.345(m,10H);7.331-7.269(m,4H).
This testing sequence two is in fact to adopt carbazole and 2-bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene carries out substitution reaction, the detected result of the proton nmr spectra that the syncaryon magnetic resonance device detects as can be known: the structural formula that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base is
Figure BDA00002349009500161
At first the multifunction for preparing of this test is modified the two phosphine oxide compounds of dibenzothiophene base at 100 ℃ of lower dry 12h, then adds methylene dichloride and is configured to 1 * 10 -6The multifunction of mol/L is modified the two phosphine oxide compound/dichloromethane solutions of dibenzothiophene base, with 1 * 10 -6The multifunction of mol/L is modified the two phosphine oxide compound/dichloromethane solutions of dibenzothiophene base and is dripped on quartz plate, the dried solvent that volatilizees namely obtains multifunction and modifies the two phosphine oxide compound films of dibenzothiophene base, then adopt Ultravioblet spectrophotometer and fluorescence spectrophotometer to detect, detected result as shown in Figure 5, Fig. 5 is that this test prepares the Ultraluminescence spectrum spectrogram that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base, among Fig. 5 represents the two phosphine oxide compounds of multifunction modification dibenzothiophene base/dichloromethane solution UV spectrum spectrogram, among Fig. 5 zero expression multifunction is modified the two phosphine oxide compound film ultraviolet spectrum of dibenzothiophene base spectrogram, ■ among Fig. 5 represents the two phosphine oxide compounds of multifunction modification dibenzothiophene base/dichloromethane solution fluorescence spectrum spectrogram, among Fig. 5 ▲ the expression multifunction modifies the two phosphine oxide compound film fluorescence spectrum spectrograms of dibenzothiophene base, among Fig. 5 ▲ the expression multifunction modifies the phosphorescence spectrum spectrogram of the two phosphine oxide compounds of dibenzothiophene base; Multifunction is modified the ultraviolet absorption peak of the two phosphine oxide compound/dichloromethane solutions of dibenzothiophene base respectively at 226nm and 291nm as shown in Figure 5; And multifunction is modified the ultraviolet absorption peak of the two phosphine oxide compound films of dibenzothiophene base at 232nm and 295nm.Multifunction is modified the fluorescence emission peak of the two phosphine oxide compound/dichloromethane solutions of dibenzothiophene base at 414nm, multifunction is modified the fluorescence emission peak of the two phosphine oxide compound films of dibenzothiophene base at 414nm, and the multifunction that this test prepares is modified the phosphorescent emissions peak of the two phosphine oxide compounds of dibenzothiophene base at 442nm.
Adopt thermogravimetric analyzer to detect the two phosphine oxide compounds of multifunction modification dibenzothiophene base that this test prepares, detected result as shown in Figure 6, Fig. 6 is that this test prepares the thermogravimetric analysis spectrogram that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base, the two phosphine oxide compound cracking temperatures of multifunction modification dibenzothiophene base that prepare by this test of Fig. 6 are 484 ℃, so the multifunction that this test prepares is modified the two phosphine oxide compound thermogravimetric good stabilities of dibenzothiophene base.
Test four: the preparation method of blue light electroluminescence device, specifically finish according to the following steps:
1, adopt vacuum vapour deposition tin indium oxide to be plated in to form thickness on the substrate material be the film of 10nm, thickness be the film of 10nm as the first layer conductive layer of anode, wherein said substrate material is glass; 2, adopt vacuum vapour deposition successively with MoOx, 4,4', 4 " mixture, 4 of three (N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine/MoOx(m-MTDATA/MoOx); 4', 4 " three (N-3-aminomethyl phenyls-N-phenyl amino) (m-MTDATA) and three (1-phenylpyrazoles) close iridium (Ir (ppz) 3) be plated on the first layer conductive layer, and it is 2nm that MoOx forms film thickness, 4,4', 4 " three (N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine/MoOx(m-MTDATA/MoOx) mixture forming film thickness is 30nm, 4,4'; 4 " it is 10nm that-three (N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine forms film thickness, and three (1-phenylpyrazoles) close iridium (Ir (ppz) 3) the formation film thickness is 10nm, the hole transmission layer total thickness that obtains is 52nm; 3, adopt vacuum vapour deposition that complex of iridium and multifunction are modified adulterate body that the two phosphine oxide compounds of dibenzothiophene base mix formation and be plated in that formation thickness is the film of 10nm on the hole transmission layer, thickness is that the film of 10nm is luminescent layer; 4, adopt vacuum vapour deposition successively with 4,7-phenylbenzene-1,10-phenanthrolene (Bphen) and Cs 2CO 3Be plated on the luminescent layer, and 4,7-phenylbenzene-1, it is 40nm that 10-phenanthrolene (Bphen) forms film thickness, Cs 2CO 3The formation film thickness is 1nm, and the electron transfer layer total thickness that obtains is 41nm; 5, adopt vacuum vapour deposition aluminium to be plated in to form thickness on the electron transfer layer be the film of 100nm, thickness be the film of 100nm as the second layer conductive layer of negative electrode, namely obtain the blue light electroluminescence device.
" massfraction of MoOx is 15% in the mixture of three (N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine/MoOx(m-MTDATA/MoOx) for described in this testing sequence 24,4', 4.
Complex of iridium described in this testing sequence 3 and multifunction are modified the two phosphine oxide compounds of dibenzothiophene base and are mixed in the adulterate body that forms complex of iridium and be pairs (4,6-difluorophenyl pyridine-N, C2) the pyridine formyl closes iridium (FIrpic), multifunction is modified the two phosphine oxide compounds of dibenzothiophene base and is modified the two phosphine oxide compounds (DBTDPOCz) of dibenzothiophene base for the multifunction of test three preparations, and described complex of iridium and multifunction are modified the two phosphine oxide compounds of dibenzothiophene base and are mixed in the adulterate body that forms pairs (4,6-difluorophenyl pyridine-N, C2) to close the mass ratio that iridium (FIrpic) and the multifunctions of test three preparations modify the two phosphine oxide compounds of dibenzothiophene base be 1:9 to the pyridine formyl.
The structure of the blue light electroluminescence device of this test preparation is: and ITO/MoOx (2nm)/m-MTDATA:MoOx (15%, 30nm)/m-MTDATA (10nm)/[Ir (ppz) 3] (10nm)/DBTDPOCz:FIrpic (10%, 10nm)/Bphen (40nm)/Cs 2CO 3(1nm)/Al (100nm).
Detect blue light electroluminescence device voltage and the current density relation of this test preparation, detected result such as Fig. 7, Fig. 7 is the voltage-to-current density relationship curve of the blue light electroluminescence device of this test preparation, the two phosphine oxide compounds of multifunction modification dibenzothiophene base that show test three preparations by Fig. 7 have characteristic of semiconductor, and the blue light electroluminescence device threshold voltage of this test preparation is 2.4V.
Detect blue light electroluminescence device voltage and the brightness relationship of this test preparation, detected result such as Fig. 8, Fig. 8 is the voltage-brightness relationship curve of the blue light electroluminescence device of this test preparation, and the bright voltage that opens of the blue light electroluminescence device for preparing of this test is 2.4V as shown in Figure 8, and is being higher than 1000cdm -2(1303cdm -2) brightness under, driving voltage still is lower than 3.2V.
Detect blue light electroluminescence device brightness and the current efficiency relation of this test preparation, detected result such as Fig. 9, Fig. 9 is the brightness-current efficiency relation curve of the blue light electroluminescence device of this test preparation, and the blue light electroluminescence device for preparing of this test is 148.9cdm in brightness as shown in Figure 9 -2The time, current efficiency reaches maximum value 18.5cdA -1
Detect blue light electroluminescence device brightness and the power efficiency relation of this test preparation, detected result such as Figure 10, Figure 10 is the brightness-power efficiency relation curve of the blue light electroluminescence device of this test preparation, and the blue light electroluminescence device for preparing of this test is 148.9cdm in brightness as shown in Figure 10 -2The time, power efficiency reaches maximum value 22.4lmW -1
Detect blue light electroluminescence device brightness and the external quantum efficiency relation of this test preparation, detected result such as Figure 11, Figure 11 is the brightness-external quantum efficiency relation curve of the blue light electroluminescence device of this test preparation, and the blue light electroluminescence device for preparing of this test is 148.9cdm in brightness as shown in Figure 11 -2The time, external quantum efficiency reaches maximum value 8.8%.
Detect the blue light electroluminescence device electroluminescent spectrum of this test preparation, detected result such as Figure 12, Figure 12 is the electroluminescent spectrum of the blue light electroluminescence device of this test preparation, the electroluminescent peak of the blue light electroluminescence device of this test preparation is at the 471nm place as shown in Figure 12, and has the acromion of following 495nm.
Test five: this test with test four difference is: the preparation method of electro-green light device: complex of iridium described in the step 3 mixes with multifunction modification dibenzothiophene base pair phosphine oxide compounds that complex of iridium is that three (2-phenylpyridines) close iridium (Ir (ppy) in the adulterate body of formation 3), multifunction is modified the two phosphine oxide compounds of dibenzothiophene base and is modified the two phosphine oxide compounds (DBTDPOCz) of dibenzothiophene base for the multifunctions of test three preparations, and described complex of iridium and multifunction to modify the massfraction that three (2-phenylpyridines) in the adulterate body that the two phosphine oxide compounds of dibenzothiophene base mix formation close iridium be 6%.Other are identical with test four.
The structure of the electro-green light device of this test preparation is: and ITO/MoOx (2nm)/m-MTDATA:MoOx (15%, 30nm)/m-MTDATA (10nm)/[Ir (ppz) 3] (10nm)/DBTDPOCz:Ir (ppy) 3(6%, 10nm)/Bphen (40nm)/Cs 2CO 3(1nm)/Al (100nm).
Detect electro-green light device voltage and the current density relation of this test preparation, detected result such as Figure 13, Figure 13 is the voltage-to-current density relationship curve of the electro-green light device of this test preparation, the two phosphine oxide compounds of multifunction modification dibenzothiophene base that show test three preparations by Figure 13 have characteristic of semiconductor, and the electro-green light device threshold voltage of this test preparation is 2.3V.
Detect electro-green light device voltage and the brightness relationship of this test preparation, detected result such as Figure 14, Figure 14 is the voltage-brightness relationship curve of the electro-green light device of this test preparation, and the bright voltage that opens of the electro-green light device for preparing of this test is 2.3V as shown in Figure 14, and is being higher than 1000cdm -2(1243cdm -2) brightness under, driving voltage still is lower than 2.9V.
Detect electro-green light device brightness and the current efficiency relation of this test preparation, detected result such as Figure 15, Figure 15 is the brightness-current efficiency relation curve of the electro-green light device of this test preparation, and the electro-green light device for preparing of this test is 132.4cdm in brightness as shown in Figure 15 -2The time, current efficiency reaches maximum value 45cdA -1
Detect electro-green light device brightness and the power efficiency relation of this test preparation, detected result such as Figure 16, Figure 16 is the brightness-power efficiency relation curve of the electro-green light device of this test preparation, and the electro-green light device for preparing of this test is 132.4cdm in brightness as shown in Figure 16 -2The time, power efficiency reaches maximum value 56.5lmW -1
Detect electro-green light device brightness and the external quantum efficiency relation of this test preparation, detected result such as Figure 17, Figure 17 is the brightness-external quantum efficiency relation curve of the electro-green light device of this test preparation, and the electro-green light device for preparing of this test is 132.4cdm in brightness as shown in Figure 17 -2The time, obtain maximum external quantum efficiency 12.3%.
Detect the electro-green light device electroluminescent spectrum of this test preparation, detected result such as Figure 18, Figure 18 is the electroluminescent spectrum of the electro-green light device of this test preparation, and the electroluminescent peak of the electro-green light device of this test preparation is at the 515nm place as shown in Figure 18.
Test six: this test with test four difference is: electricity causes the preparation method of gold-tinted device: complex of iridium described in the step 3 mixes with multifunction modification dibenzothiophene base pair phosphine oxide compounds that complex of iridium is 2-fluorophenyl benzothiazolyl in the adulterate body of formation)-methyl ethyl diketone iridium (Ir (F-BT) 2(acac)), multifunction is modified the two phosphine oxide compounds of dibenzothiophene base and is modified the two phosphine oxide compounds (DBTDPOCz) of dibenzothiophene base for the multifunctions of test three preparations, and described complex of iridium and multifunction are modified 2-fluorophenyl benzothiazolyl in the adulterate body that the two phosphine oxide compounds of dibenzothiophene base mix formation)-massfraction of methyl ethyl diketone iridium is 6%.Other are identical with test four.
The structure that the electricity of this test preparation causes the gold-tinted device is: and ITO/MoOx (2nm)/m-MTDATA:MoOx (15%, 30nm)/m-MTDATA (10nm)/[Ir (ppz) 3] (10nm)/DBTDPOCz:Ir (F-BT) 2 (acac) (6%, 10nm)/Bphen (40nm)/Cs 2CO 3(1nm)/Al (100nm).
The electricity that detects this test preparation causes gold-tinted device voltage and current density relation, detected result such as Figure 19, Figure 19 is the voltage-to-current density relationship curve that the electricity of this test preparation causes the gold-tinted device, the two phosphine oxide compounds of multifunction modification dibenzothiophene base that show test three preparations by Figure 19 have characteristic of semiconductor, and it is 2.4V that the electricity of this test preparation causes gold-tinted device threshold voltage.
The electricity that detects this test preparation causes gold-tinted device voltage and brightness relationship, detected result such as Figure 20, Figure 20 is the electricity of this test preparation voltage that causes the gold-tinted device-brightness relationship curve, and the bright voltage that opens of the electro-green light device for preparing of this test is 2.4V as shown in Figure 20, and is being higher than 1000cdm -2(1037cdm -2) brightness under, driving voltage still is lower than 3.4V.
The electricity that detects this test preparation causes gold-tinted device brightness and current efficiency relation, detected result such as Figure 21, Figure 21 is the electricity of this test preparation brightness that causes the gold-tinted device-current efficiency relation curve, by Figure 21 as can be known the electro-green light device for preparing of this test be 0.64mAcm in current density -2The time, current efficiency reaches maximum value 28.1cdA -1
The electricity that detects this test preparation causes gold-tinted device brightness and power efficiency relation, detected result such as Figure 22, Figure 22 is the electricity of this test preparation brightness that causes the gold-tinted device-power efficiency relation curve, by Figure 22 as can be known the electro-green light device for preparing of this test be 0.64mAcm in current density -2The time, power efficiency reaches maximum value 31.6lmW -1
The electricity that detects this test preparation causes gold-tinted device brightness and external quantum efficiency relation, detected result such as Figure 23, Figure 23 is the electricity of this test preparation brightness that causes the gold-tinted device-external quantum efficiency relation curve, by Figure 23 as can be known the electro-green light device for preparing of this test be 0.64mAcm in current density -2The time, obtain maximum external quantum efficiency 9.0%.
The electricity that detects this test preparation causes gold-tinted device electroluminescent spectrum, detected result such as Figure 24, Figure 24 is the electroluminescent spectrum that the electricity of this test preparation causes the gold-tinted device, the electroluminescent peak of the electro-green light device of this test preparation and there is the acromion of following 583nm at the 546nm place as can be known by Figure 24.
Test seven: this test with test four difference is: the preparation method of red electroluminescent device: complex of iridium described in the step 3 and multifunction modify that complex of iridium is couple (2-methyl-dibenzo quinoxalinyl)-methyl ethyl diketone iridium (Ir (MDQ) in the adulterate body that the two phosphine oxide compounds of dibenzothiophene base mix formation 2(acac)), it is that the multifunctions of testing three preparations are modified the two phosphine oxide compounds (DBTDPOCz) of dibenzothiophene base that multifunction is modified the two phosphine oxide compounds of dibenzothiophene base, and described complex of iridium is 6% with the massfraction that multifunction modification dibenzothiophene base pair phosphine oxide compounds mix two (2-methyl-dibenzo quinoxalinyl)-methyl ethyl diketone iridium in the adulterate body that forms.Other are identical with test four.
The structure of the red electroluminescent device of this test preparation is: and ITO/MoOx (2nm)/m-MTDATA:MoOx (15%, 30nm)/m-MTDATA (10nm)/[Ir (ppz) 3] (10nm)/DBTDPOCz:Ir (MDQ) 2(acac) (6%, 10nm)/Bphen (40nm)/Cs 2CO 3(1nm)/Al (100nm).
Detect red electroluminescent device voltage and the current density relation of this test preparation, detected result such as Figure 25, Figure 25 is the voltage-to-current density relationship curve of the red electroluminescent device of this test preparation, the two phosphine oxide compounds of multifunction modification dibenzothiophene base that show test three preparations by Figure 25 have characteristic of semiconductor, and the red electroluminescent device threshold voltage of this test preparation is 2.2V.
Detect red electroluminescent device voltage and the brightness relationship of this test preparation, detected result such as Figure 26, Figure 26 is the voltage-brightness relationship curve of the red electroluminescent device of this test preparation, by Figure 26 as can be known the bright voltage that opens of the red electroluminescent device for preparing of this test be 2.2V, and be higher than 1000cdm -2(1124cdm -2) brightness under, driving voltage still is lower than 4.6V.
Detect red electroluminescent device brightness and the current efficiency relation of this test preparation, detected result such as Figure 27, Figure 27 is the brightness-current efficiency relation curve of the red electroluminescent device of this test preparation, by Figure 27 as can be known the red electroluminescent device for preparing of this test be 7.6cdm in brightness -2The time, current efficiency reaches maximum value 7.6cdA -1
Detect red electroluminescent device brightness and the power efficiency relation of this test preparation, detected result such as Figure 28, Figure 28 is the brightness-power efficiency relation curve of the red electroluminescent device of this test preparation, by Figure 28 as can be known the red electroluminescent device for preparing of this test be 7.6cdm in brightness -2The time, power efficiency reaches maximum value 101mW -1
Detect red electroluminescent device brightness and the external quantum efficiency relation of this test preparation, detected result such as Figure 29, Figure 29 is the brightness-external quantum efficiency relation curve of the red electroluminescent device of this test preparation, by Figure 29 as can be known the red electroluminescent device for preparing of this test be 7.6cdm in brightness -2The time, obtain maximum external quantum efficiency 6.2%.
Detect the red electroluminescent device electroluminescent spectrum of this test preparation, detected result such as Figure 30, Figure 30 is the electroluminescent spectrum of the red electroluminescent device of this test preparation, by Figure 30 as can be known the electroluminescent peak of the red electroluminescent device for preparing of this test at the 621nm place.

Claims (8)

1. multifunction is modified the two phosphine oxide compounds of dibenzothiophene base, it is characterized in that it is 4,6-two (diphenylphosphine oxygen base) dibenzothiophene derivatives that multifunction is modified the chemical name of the two phosphine oxide compounds of dibenzothiophene base, and its structure is as follows:
Figure FDA00002349009400011
Wherein said X, Y is as follows: (1) as X is
Figure FDA00002349009400012
Y is-H or
Figure FDA00002349009400013
(2) as X be
Figure FDA00002349009400014
Y is-H or
Figure FDA00002349009400015
(3) as X be
Figure FDA00002349009400016
Y is-H or
Figure FDA00002349009400017
(4) as X be
Figure FDA00002349009400018
Y is-H or
Figure FDA00002349009400019
2. multifunction as claimed in claim 1 is modified the preparation method of the two phosphine oxide compounds of dibenzothiophene base, the preparation method who it is characterized in that the two phosphine oxide compounds of multifunction modification dibenzothiophene base finishes according to the following steps: one, bromo: at first with 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is dissolved in the vitriol oil, then press N-bromo-succinimide and 4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (1 ~ 1.2): 1 adds the N-bromo-succinimide, and at stirring reaction 2h ~ 4h, obtain the bromo-reaction product and adopt CH 2Cl 2And H 2O extracts, and the bromo organic layer that obtains adopts first siccative to carry out drying, adopts the rotary evaporation method to be spin-dried for again, and carries out at last column chromatography take ethyl acetate as eluent and purifies, and namely obtains 2-bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene; Described in the step 14, the ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene amount of substance and vitriol oil volume are 1mmol:(2mL ~ 4mL); Siccative described in the step 1 is anhydrous sodium sulphate or anhydrous magnesium sulfate; Two, replace: at first pinacol borate compound, Tetrabutyl amonium bromide and tetra-triphenylphosphine palladium are added 2-bromo-4, in 6-two (the diphenylphosphine oxygen base) dibenzothiophene, adding successively, tetrahydrofuran (THF) and concentration are the NaOH aqueous solution of 1mmol/mL ~ 3mmol/mL again, then be warming up to 80 ℃ ~ 100 ℃ from room temperature, and be stirring reaction 12h ~ 24h under 80 ℃ ~ 100 ℃ the condition in temperature, obtain the substitution reaction product and adopt CH 2Cl 2With saturated NH 4The Cl aqueous solution extracts, the replacement organic layer that obtains adopts first siccative to carry out drying, adopt again the rotary evaporation method to be spin-dried for, carry out at last column chromatography take ethyl acetate as eluent and purify, namely obtain multifunction and modify the two phosphine oxide compounds of dibenzothiophene base; Pinacol borate compound described in the step 2 is
Figure FDA000023490094000110
Or
Figure FDA000023490094000111
The pinacol borate compound that adds described in the step 2 and 2-bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (1 ~ 1.2): 1; The Tetrabutyl amonium bromide that adds described in the step 2 and 2-bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.08 ~ 0.12): 1; The tetra-triphenylphosphine palladium that adds described in the step 2 and 2-bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.08 ~ 0.12): 1; The tetrahydrofuran (THF) volume that adds described in the step 2 and 2-bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene molar ratio are (5mL ~ 10mL): 1mmol; Adding concentration described in the step 2 is the NaOH aqueous solution and the 2-bromo-4 of 1mmol/mL ~ 3mmol/mL, and 6-two (diphenylphosphine oxygen base) dibenzothiophene mass ratio is (2.5 ~ 3.5): 1; Siccative described in the step 2 is anhydrous sodium sulphate or anhydrous magnesium sulfate.
3. multifunction as claimed in claim 1 is modified the preparation method of the two phosphine oxide compounds of dibenzothiophene base, the preparation method who it is characterized in that the two phosphine oxide compounds of multifunction modification dibenzothiophene base finishes according to the following steps: one, bromo: at first with 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is dissolved in the vitriol oil, then press N-bromo-succinimide and 4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (2 ~ 2.5): 1 adds the N-bromo-succinimide, and at stirring reaction 2h ~ 4h, obtain the bromo-reaction product and adopt CH 2Cl 2And H 2O extracts, and the bromo organic layer that obtains adopts first siccative to carry out drying, adopts the rotary evaporation method to be spin-dried for again, carry out at last column chromatography purifies take ethyl acetate as eluent, namely obtain 2,8-, two bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene; Described in the step 14, the ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene amount of substance and vitriol oil volume are 1mmol:(2mL ~ 4mL); Siccative described in the step 1 is anhydrous sodium sulphate or anhydrous magnesium sulfate; Two, replace: at first pinacol borate compound, Tetrabutyl amonium bromide and tetra-triphenylphosphine palladium are added 2,8-two bromo-4, in 6-two (the diphenylphosphine oxygen base) dibenzothiophene, adding successively, tetrahydrofuran (THF) and concentration are the NaOH aqueous solution of 1mmol/mL ~ 3mmol/mL again, then be warming up to 80 ℃ ~ 100 ℃ from room temperature, and be stirring reaction 12h ~ 24h under 80 ℃ ~ 100 ℃ the condition in temperature, obtain the substitution reaction product and adopt CH 2Cl 2With saturated NH 4The Cl aqueous solution extracts, the replacement organic layer that obtains adopts first siccative to carry out drying, adopt again the rotary evaporation method to be spin-dried for, carry out at last column chromatography take ethyl acetate as eluent and purify, namely obtain multifunction and modify the two phosphine oxide compounds of dibenzothiophene base; Pinacol borate compound described in the step 2 is
Figure FDA00002349009400021
Or
Figure FDA00002349009400022
The pinacol borate compound that adds described in the step 2 and 2,8-, two bromo-4, the mol ratio (2 ~ 2.1) of 6-two (diphenylphosphine oxygen base) dibenzothiophene: 1; The Tetrabutyl amonium bromide that adds described in the step 2 and 2,8-, two bromo-4, the mol ratio (0.19 ~ 0.21) of 6-two (diphenylphosphine oxygen base) dibenzothiophene: 1; The tetra-triphenylphosphine palladium that adds described in the step 2 and 2,8-, two bromo-4, the mol ratio (0.19 ~ 0.21) of 6-two (diphenylphosphine oxygen base) dibenzothiophene: 1; The tetrahydrofuran (THF) volume that adds described in the step 2 and 2,8-, two bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene molar ratio are (5mL ~ 10mL): 1mmol; Adding concentration described in the step 2 is the NaOH aqueous solution and 2,8-, two bromo-4 of 1mmol/mL ~ 3mmol/mL, and 6-two (diphenylphosphine oxygen base) dibenzothiophene mass ratio is (5.5 ~ 6.5): 1; Siccative described in the step 2 is anhydrous sodium sulphate or anhydrous magnesium sulfate.
4. multifunction is modified the two phosphine oxide compounds of dibenzothiophene base, it is characterized in that it is 4,6-two (diphenylphosphine oxygen base) dibenzothiophene derivatives that multifunction is modified the chemical name of the two phosphine oxide compounds of dibenzothiophene base, and its structure is as follows:
Figure FDA00002349009400023
Wherein said X is
Figure FDA00002349009400024
Wherein said Y is-H or
5. multifunction as claimed in claim 4 is modified the preparation method of the two phosphine oxide compounds of dibenzothiophene base, the preparation method who it is characterized in that the two phosphine oxide compounds of multifunction modification dibenzothiophene base finishes according to the following steps: one, bromo: at first with 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is dissolved in the vitriol oil, then press N-bromo-succinimide and 4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (1 ~ 1.2): 1 adds the N-bromo-succinimide, and stirring reaction 2h ~ 4h, obtain the bromo-reaction product and adopt CH 2Cl 2And H 2O extracts, and the bromo organic layer that obtains adopts first siccative to carry out drying, adopts the rotary evaporation method to be spin-dried for again, and carries out at last column chromatography take ethyl acetate as eluent and purifies, and namely obtains 2-bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene; Described in the step 14, the ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene amount of substance and vitriol oil volume are 1mmol:(2mL ~ 4mL); Siccative described in the step 1 is anhydrous sodium sulphate or anhydrous magnesium sulfate; Two, replace: at first carbazole, salt of wormwood, cuprous iodide, 18-are preced with-6 ethers and 1,3-dimethyl-2-imidazolidone adds 2-bromo-4, in 6-two (the diphenylphosphine oxygen base) dibenzothiophene, then be stirring reaction 24h ~ 48h under 160 ℃ ~ 200 ℃ conditions in temperature, obtain the substitution reaction product and adopt CH 2Cl 2With saturated NH 4The Cl aqueous solution extracts, the replacement organic layer that obtains adopts first siccative to carry out drying, adopt again the rotary evaporation method to be spin-dried for, carry out at last column chromatography take ethyl acetate as eluent and purify, namely obtain multifunction and modify the two phosphine oxide compounds of dibenzothiophene base; The carbazole that adds described in the step 2 and 2-bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (1 ~ 1.2): 1; The salt of wormwood that adds described in the step 2 and 2-bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.8 ~ 1.2): 1; The cuprous iodide that adds described in the step 2 and 2-bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.08 ~ 0.12): 1; 18-hat-6 ethers and the 2-bromo-4 that add described in the step 2, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.08 ~ 0.12): 1; Add described in the step 21,3-dimethyl-2-imidazolidone volume and 2-bromo-4, the ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene amount of substance are (8mL ~ 12mL): 1mmol; Siccative described in the step 2 is anhydrous sodium sulphate or anhydrous magnesium sulfate.
6. multifunction as claimed in claim 4 is modified the preparation method of the two phosphine oxide compounds of dibenzothiophene base, the preparation method who it is characterized in that the two phosphine oxide compounds of multifunction modification dibenzothiophene base finishes according to the following steps: one, bromo: at first with 4,6-two (diphenylphosphine oxygen base) dibenzothiophene is dissolved in the vitriol oil, then press N-bromo-succinimide and 4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (2 ~ 2.5): 1 adds the N-bromo-succinimide, and stirring reaction 2h ~ 4h, obtain the bromo-reaction product and adopt CH 2Cl 2And H 2O extracts, and the bromo organic layer that obtains adopts first siccative to carry out drying, adopts the rotary evaporation method to be spin-dried for again, carry out at last column chromatography purifies take ethyl acetate as eluent, namely obtain 2,8-, two bromo-4,6-two (diphenylphosphine oxygen base) dibenzothiophene; Described in the step 14, the ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene amount of substance and vitriol oil volume are 1mmol:(2mL ~ 4mL); Siccative described in the step 1 is anhydrous sodium sulphate or anhydrous magnesium sulfate; Two, replace: at first carbazole, salt of wormwood, cuprous iodide, 18-are preced with-6 ethers and 1,3-dimethyl-2-imidazolidone adds 2,8-two bromo-4, in 6-two (the diphenylphosphine oxygen base) dibenzothiophene, then be stirring reaction 24h ~ 48h under 160 ℃ ~ 200 ℃ conditions in temperature, obtain the substitution reaction product and adopt CH 2Cl 2With saturated NH 4The Cl aqueous solution extracts, the replacement organic layer that obtains adopts first siccative to carry out drying, adopt again the rotary evaporation method to be spin-dried for, carry out at last column chromatography take ethyl acetate as eluent and purify, namely obtain multifunction and modify the two phosphine oxide compounds of dibenzothiophene base; The carbazole that adds described in the step 2 and 2,8-, two bromo-4, the mol ratio (2 ~ 2.1) of 6-two (diphenylphosphine oxygen base) dibenzothiophene: 1; The salt of wormwood that adds described in the step 2 and 2,8-, two bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (1.9 ~ 2.1): 1; The cuprous iodide that adds described in the step 2 and 2,8-, two bromo-4, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.19 ~ 0.21): 1; 18-hat-6 ethers and 2,8-, two bromo-4 that add described in the step 2, the mol ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene is (0.19 ~ 0.21): 1; Add described in the step 21,3-dimethyl-2-imidazolidone volume and 2,8-, two bromo-4, the ratio of 6-two (diphenylphosphine oxygen base) dibenzothiophene amount of substance are (8mL ~ 12mL): 1mmol; Siccative described in the step 2 is anhydrous sodium sulphate or anhydrous magnesium sulfate.
7. such as the application of claim 1 or the two phosphine oxide compounds of 4 described multifunctions modification dibenzothiophene bases, it is characterized in that the two phosphine oxide compounds of multifunction modification dibenzothiophene base are as the application of luminescent layer material of main part in the electro phosphorescent device.
8. the application of the two phosphine oxide compounds of described multifunction modification dibenzothiophene base according to claim 7, the preparation method who it is characterized in that described electro phosphorescent device finishes according to the following steps: 1, adopt vacuum vapour deposition tin indium oxide to be plated in to form thickness on the substrate material be the film of 1nm ~ 20nm, thickness be the film of 1nm ~ 20nm 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 2nm ~ 60nm, thickness is that the film of 2nm ~ 60nm is hole transmission layer, and wherein said hole transport layer material is a kind of in hole-injecting material, hole mobile material and hole transport/electronic blocking material or several mixture wherein; 3, adopt vacuum vapour deposition the luminescent layer material to be plated in to form thickness on the hole transmission layer be the film of 5nm ~ 60nm, thickness is that the film of 5nm ~ 60nm is luminescent layer, and wherein said luminescent layer material is that complex of iridium and multifunction are modified adulterate body or the two phosphine oxide compounds of multifunction modification dibenzothiophene base that the two phosphine oxide compounds of dibenzothiophene base are mixed by any ratio formation; 4, adopt vacuum vapour deposition the electric transmission 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 electron transfer layer, and wherein said electric transmission layer material is one or both the mixture in electron transport material and the electric transmission/hole barrier materials; 5, adopt vacuum vapour deposition second layer conductive to be plated in to form thickness on the electron transfer layer be the film of 0.5nm ~ 120nm, thickness is that the film of 0.5nm ~ 120nm is as the second layer conductive layer of negative electrode, namely obtain electro phosphorescent device, wherein said second layer conductive is calcium, calcium alloy, magnesium, magnesium alloy, silver, silver alloys, aluminum or aluminum alloy.
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