CN108276445B - Thermal excitation delayed fluorescence main body material and preparation and application thereof - Google Patents

Thermal excitation delayed fluorescence main body material and preparation and application thereof Download PDF

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CN108276445B
CN108276445B CN201711058921.3A CN201711058921A CN108276445B CN 108276445 B CN108276445 B CN 108276445B CN 201711058921 A CN201711058921 A CN 201711058921A CN 108276445 B CN108276445 B CN 108276445B
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delayed fluorescence
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CN108276445A (en
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许辉
高飞飞
韩春苗
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Heilongjiang University
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    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
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Abstract

The invention provides a thermal excitation delayed fluorescence main body material and preparation and application thereof, wherein the thermal excitation delayed fluorescence main body material is prepared by taking a thermal excitation delayed fluorescence material based on 9, 10-dihydro-9, 10-o-benzo-9, 10-diphospha anthracene-9, 10-dioxide as a matrix and modifying the matrix by using fluorine atoms with different quantities, the starting voltage of a thermal excitation delayed fluorescence electroluminescent device prepared by taking the thermal excitation delayed fluorescence main body material as an electroluminescent material is within 3.0V, the maximum external quantum efficiency is higher than 12%, and the maximum value of the current efficiency is larger than 25 cd.A‑1The maximum power efficiency is greater than 20 lm.W‑1。

Description

Thermal excitation delayed fluorescence main body material and preparation and application thereof
Technical Field
The invention belongs to the field of organic electroluminescent materials, and relates to a thermal excitation delayed fluorescence main body material, and a preparation method and application thereof.
Background
The 21 st century into the "information age" has been the display of information closely coupled with the increase in human knowledge and the improvement in quality of life. Information display relies on displays, and the rapid development of information technology has made the demand for flat panel displays higher and higher. Among the various displays at present, Liquid Crystal Displays (LCDs) occupy a large share of the entire flat panel Display market, but have insurmountable disadvantages of narrow viewing angle, weak contrast, low brightness, long response time, poor temperature characteristics, and the fact that self-light-emission does not depend on a backlight. Because the existing display can not meet the requirements of people, people are continuously looking for novel and efficient display devices. Organic Light Emitting Diodes (OLEDs) have been produced as an emerging display technology and have attracted considerable attention from researchers. Electroluminescent and electrophosphorescent are referred to as first and second generation OLEDs. Currently, thermally-excited delayed fluorescence is of more widespread interest, and is referred to as a third generation OLED.
However, Thermally Activated Delayed Fluorescence (TADF) host materials are lacking and quenching effects may also exist between the host and guest, resulting in device inefficiencies.
Therefore, it is highly desirable to develop a thermally-excited delayed fluorescence host material having a steric configuration and not prone to quenching effect.
Disclosure of Invention
In order to solve the above problems, the present inventors have conducted intensive studies and, as a result, have found that: based on the 9, 10-dihydro-9, 10-ortho-benzo-9, 10-diphosphatanthracene-9, 10-dioxide thermal excitation delay fluorescent material of the formula I as a matrix, the matrix is modified by fluorine atoms with different numbers to form four thermal excitation delay fluorescent main body materials with different structures, the starting voltage of blue and white thermal excitation delay fluorescent electroluminescent devices prepared by taking the thermal excitation delay fluorescent main body materials as electroluminescent materials is within 3.0V, the maximum external quantum efficiency is higher than 12 percent, and the maximum current efficiency is larger than 25 cd.A-1The maximum power efficiency is greater than 20 lm.W-1. The parent is packed by isometric compact spheres, and the three-dimensional structure can effectively inhibit pi-pi interaction between molecules and prevent emission quenching caused by the interaction between host and guest molecules. And intermolecular hydrogen bonds are formed between phosphine oxide groups and fluorine atoms between the parent bodies, and the occurrence of the hydrogen bonds can promote the transmission of carriers, thereby realizing high-efficiency ultralow-voltage driving, and completing the invention.
The object of the present invention is to provide the following:
in a first aspect, the present invention provides a thermally-excited delayed fluorescence host material based on a compound of one or more structures obtained by modifying a 9, 10-dihydro-9, 10-ortho-benzo-9, 10-diphosphanthryl-9, 10-dioxide of formula I as a precursor with a different number of fluorine atoms, preferably 1 to 4 fluorine atoms per benzene ring, more preferably 2 to 4 fluorine atoms, formula I and having the following structure after modification with fluorine atoms:
Figure BDA0001454288210000021
in a second aspect, the present invention further provides a method for preparing the thermally-excited delayed fluorescence host material according to the first aspect, the method comprises:
(1) mixing o-dibromobenzene or fluoro-o-dibromobenzene with a solvent I, stirring at 0-120 ℃, dropwise adding a lithium reagent, reacting for 12-24 h, adding a phosphating agent, stirring for reacting for 6-12 h, and performing post-treatment to obtain an intermediate;
(2) dissolving the intermediate in a solvent II, stirring at 0-120 ℃, dropwise adding a lithium reagent, reacting for 12-24 h, adding a phosphating agent, stirring for reacting for 6-12 h, and quenching the reaction;
(3) adding an oxidant to continue reacting to obtain a crude product, and treating the crude product to obtain a product.
In the step (1), the solvent I is tetrahydrofuran, the lithium reagent is n-butyllithium, and the phosphating agent is phosphorus trichloride;
in the step (2), the solvent II is diethyl ether, the lithium reagent is n-butyllithium, the phosphating agent is phosphorus trichloride, and the reaction is quenched by water.
In the step (3), the oxidant is hydrogen peroxide, and the reaction is carried out for 0.5 to 6 hours, preferably 1 to 3 hours, such as 2 hours; the treatment is recrystallization.
According to the above preparation method, the preparation method comprises the following steps:
(1) mixing 3mmol of o-dibromobenzene, 1, 2-dibromo-4, 5-difluorobenzene, 1, 2-dibromo-3, 4, 5-trifluorobenzene, 2, 3-dibromo-1, 4, 5-trifluorobenzene or 1, 2-dibromo-3, 4,5, 6-tetrafluorobenzene with 10-30 mL of tetrahydrofuran respectively, stirring at 0-120 ℃, dropwise adding 1-8 mmol of n-butyllithium, reacting for 12-24 h, adding 1-5 mmol of phosphorus trichloride, stirring for 6-12 h, and performing post-treatment to obtain an intermediate;
(2) dissolving the intermediate in 10-30 mL of diethyl ether, stirring at 0-120 ℃, dropwise adding 1-8 mmol of n-butyllithium, reacting for 12-24 h, adding 1-5 mmol of phosphorus trichloride, stirring, reacting for 6-12 h, and quenching with water;
(3) adding hydrogen peroxide to continue reacting for 2h to obtain a crude product, and recrystallizing the crude product to respectively obtain the compounds with the structures of formula I, formula II, formula III, formula IV or formula V.
In the step (1), the post-treatment comprises quenching the reaction with water, followed by extraction with an organic solvent, concentrating the extract, and then purifying the resulting concentrate by column chromatography.
The solvent for column chromatography purification is petroleum ether: and the volume ratio of the dichloromethane is 5: 1.
In the step (3), the solvent used for recrystallization is methanol.
In a third aspect, the present invention further provides a use of the thermally-excited delayed fluorescence host material of the first aspect or the thermally-excited delayed fluorescence host material prepared by the second aspect in electroluminescence, and the thermally-excited delayed fluorescence host material having the structure of formula I, formula II, formula III, formula IV and/or formula V is applied to a thermally-excited delayed fluorescence electroluminescent device as a host material.
The cracking temperature of the thermal excitation delay fluorescence host material with the structures of formula I, formula II, formula III, formula IV and formula V reaches above 300 ℃.
The obtained electroluminescent device with blue and/or white thermally-excited delayed fluorescence preferably has a lighting voltage within 3.0V, a maximum external quantum efficiency higher than 12%, and a maximum current efficiency higher than 25 cd.A-1The maximum power efficiency is greater than 20 lm.W-1。
Drawings
The thermal excitation delay fluorescent material with the structure of formula I is marked as TPDPO;
a thermally excited delayed fluorescence material having the structure of formula II is denoted as TPDPOF 6;
a thermally-excited delayed fluorescence material having the structure of formula III is denoted as o-TPDPOF 9;
the thermally excited delayed fluorescence material with the structure of formula IV is marked as p-TPDPOF 9;
the thermally excited delayed fluorescence material with the structure of formula V is marked as TPDPOF 12;
FIG. 1 is a UV fluorescence spectrum of TPDPO synthesized in example 1, wherein the UV absorption spectrum and the fluorescence emission spectrum of TPDPO/dichloromethane are represented by curve ■;
FIG. 2 is a thermogravimetric analysis spectrum of TPDPO synthesized in example 1;
FIG. 3 is a UV fluorescence spectrum of TPDPOF6 synthesized in example 2, wherein a UV absorption spectrum and a fluorescence emission spectrum of TPDPOF 6/dichloromethane are represented by a ■ curve, and FIG. 4 is a thermogravimetric analysis spectrum of TPDPOF6 synthesized in example 2;
FIG. 5 is a UV fluorescence spectrum of o-TPDPOF9 synthesized in example 3, wherein the UV absorption spectrum and the fluorescence emission spectrum of o-TPDPOF 9/dichloromethane are represented by ■ curves;
FIG. 6 is a thermogravimetric analysis spectrum of o-TPDPOF9 synthesized in example 3;
FIG. 7 is a UV fluorescence spectrum of p-TPDPOF9 synthesized in example 4, wherein the UV absorption spectrum and the fluorescence emission spectrum of p-TPDPOF 9/dichloromethane are represented by ■ curves;
FIG. 8 is a thermogravimetric analysis spectrum of p-TPDPOF9 synthesized in example 4;
FIG. 9 is a UV fluorescence spectrum of TPDPOF12 synthesized in example 5, wherein the UV absorption spectrum and the fluorescence emission spectrum of TPDPOF 12/dichloromethane are represented by ■ curves;
FIG. 10 is a thermogravimetric analysis spectrum of TPDPOF12 synthesized in example 5;
11a-11b, 12a-12b, 13a-13b, 14a-14b, 15a-15b, and 16a-16b, wherein TPDPO is represented by ■, TPDPOF6 is represented by ●, o-TPDPOF9 is represented by ▲, p-TPDPOF9 is represented by T, and TPDPOF12 is represented by ◆;
FIGS. 11a-11b are graphs of voltage-current density relationships for blue and white thermally-activated delayed fluorescence devices fabricated using examples;
FIGS. 12a-12b are graphs of voltage-luminance relationships for blue and white thermally-excited delayed fluorescence devices prepared using examples;
FIGS. 13a-13b are graphs of luminance versus current efficiency for blue and white thermally-activated delayed fluorescence devices prepared using examples;
FIGS. 14a-14b are graphs of luminance versus power efficiency for blue and white thermally-activated delayed fluorescence devices prepared using examples; (ii) a
FIGS. 15a-15b are graphs of luminance versus external quantum efficiency for blue and white thermally-excited delayed fluorescence devices prepared using examples;
FIGS. 16a-16b are electroluminescence spectra of blue and white thermally-excited delayed fluorescence devices prepared by using examples;
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The present invention is described in detail below.
In a first aspect, the present invention provides a thermally-excited delayed fluorescence material based on a compound of one or more structures obtained by modifying a 9, 10-dihydro-9, 10-ortho-benzo-9, 10-diphosphanthryl-9, 10-dioxide of formula I as a precursor with a different number of fluorine atoms, preferably 1 to 4 fluorine atoms per benzene ring, more preferably 2 to 4 fluorine atoms, formula I and having the following structure after modification with fluorine atoms:
Figure BDA0001454288210000061
in a second aspect, the present invention further provides a method for preparing the thermally-excited delayed fluorescence material according to the first aspect, the method comprises:
(1) mixing o-dibromobenzene or fluoro-o-dibromobenzene with a solvent I, stirring at 0-120 ℃, dropwise adding a lithium reagent, reacting for 12-24 h, adding a phosphating agent, stirring for reacting for 6-12 h, and performing post-treatment to obtain an intermediate;
(2) dissolving the intermediate in a solvent II, stirring at 0-120 ℃, dropwise adding a lithium reagent, reacting for 12-24 h, adding a phosphating agent, stirring for reacting for 6-12 h, and quenching the reaction;
(3) adding an oxidant to continue reacting to obtain a crude product, and treating the crude product to obtain a product.
In the step (1), the solvent I is tetrahydrofuran, the lithium reagent is n-butyllithium, and the phosphating agent is phosphorus trichloride;
in the step (2), the solvent II is diethyl ether, the lithium reagent is n-butyllithium, the phosphating agent is phosphorus trichloride, and the reaction is quenched by water.
In the step (3), the oxidant is hydrogen peroxide, and the reaction is carried out for 0.5 to 6 hours, preferably 1 to 3 hours, such as 2 hours; the treatment is recrystallization.
According to the above preparation method, the preparation method comprises the following steps:
(1) mixing 3mmol of o-dibromobenzene, 1, 2-dibromo-4, 5-difluorobenzene, 1, 2-dibromo-3, 4, 5-trifluorobenzene, 2, 3-dibromo-1, 4, 5-trifluorobenzene or 1, 2-dibromo-3, 4,5, 6-tetrafluorobenzene with 10-30 mL of tetrahydrofuran respectively, stirring at 0-120 ℃, dropwise adding 1-8 mmol of n-butyllithium, reacting for 12-24 h, adding 1-5 mmol of phosphorus trichloride, stirring for 6-12 h, and performing post-treatment to obtain an intermediate;
(2) dissolving the intermediate in 10-30 mL of diethyl ether, stirring at 0-120 ℃, dropwise adding 1-8 mmol of n-butyllithium, reacting for 12-24 h, adding 1-5 mmol of phosphorus trichloride, stirring, reacting for 6-12 h, and quenching with water;
(3) adding hydrogen peroxide to continue reacting for 2h to obtain a crude product, and recrystallizing the crude product to respectively obtain the compounds with the structures of formula I, formula II, formula III, formula IV or formula V.
In the step (1), the post-treatment comprises quenching the reaction with water, followed by extraction with an organic solvent, concentrating the extract, and then purifying the resulting concentrate by column chromatography.
The solvent for column chromatography purification is petroleum ether: and the volume ratio of the dichloromethane is 5: 1.
In the step (3), the solvent used for recrystallization is methanol.
In a third aspect, the present invention further provides a use of the thermal excitation delayed fluorescence host material of the first aspect or the thermal excitation delayed fluorescence host material prepared by the second aspect in electroluminescence, and the thermal excitation delayed fluorescence host material having the structure of formula I, formula II, formula III, formula IV and/or formula V is respectively used as a host material in a thermal excitation delayed fluorescence electroluminescent device.
The cracking temperature of the thermal excitation delay fluorescence host material with the structures of formula I, formula II, formula III, formula IV and formula V reaches above 300 ℃.
The preparation method of the thermal excitation delayed fluorescence main body material applied to the thermal excitation delayed fluorescence electroluminescent device is realized according to the following steps:
firstly, putting the glass or plastic substrate cleaned by deionized water into a vacuum evaporation plating instrument with the vacuum degree of1 multiplied by 10- 6mbar, evaporation rate set at 0.1nm s-1An anode conducting layer which is made of indium tin oxide and has the thickness of 100nm is evaporated on a glass or plastic substrate;
secondly, evaporating a material MoO on the anode conducting layer3A hole injection layer with a thickness of 5-30 nm;
thirdly, evaporating a hole transport layer which is made of NPB (nitrogen-phosphorus) material and has the thickness of 40-70 nm on the hole injection layer;
evaporating an electron blocking layer which is made of mCP and is 10nm thick on the hole transport layer;
fifthly, continuously evaporating a host material which is 20-40 nm thick and based on the formula I as a matrix and a light-emitting layer of a blue light object material doped with DMAC-DPS/a white light object material doped with 4CzPNPh on the electron blocking layer; the doping concentration of the guest material is 5-15%;
sixthly, evaporating a hole blocking layer which is made of DPEPO and has the thickness of 15nm on the luminescent layer;
seventhly, evaporating an electron transport layer which is made of Bphen and has the thickness of 50nm on the hole blocking layer;
eighthly, evaporating an electron injection layer on the electron transport layer, wherein the evaporation material is LiF, and the thickness of the electron injection layer is 0.5 nm;
and ninthly, evaporating a cathode conducting layer which is made of metal Al and has the thickness of 150nm on the electron injection layer, and packaging to obtain the thermal excitation delay fluorescence electroluminescent device.
The invention discloses a 9, 10-dihydro-9, 10-ortho-benzo-9, 10-diphosphatanthracene-9, 10-dioxide thermal excitation delayed fluorescence host material based on formula I, which comprises a glass or plastic substrate, an anode conducting layer attached on the glass or plastic substrate, a hole injection layer attached on the anode conducting layer, a hole transport layer attached on the hole injection layer, a material NBP, an electron blocking layer attached on the hole transport layer, a material mCP, a light-emitting layer attached on the electron blocking layer, wherein the light-emitting layer host material is the thermal excitation delayed fluorescence host material based on 9, 10-dihydro-9, 10-ortho-benzo-9, 10-diphosphatanthracene-9, 10-dioxide as a matrix in the patent, the guest material is DMAC-DPS/4CzPNPh, the doping concentration of the guest material is 5% -15%, the hole blocking layer is attached to the light emitting layer, the DPEPO material is a hole transmission layer attached to the hole blocking layer, the Bphen material is a electron injection layer attached to the electron transmission layer, the LiF material is a cathode conducting layer attached to the electron injection layer, and the metal Al material is selected; wherein the thickness of each layer is respectively as follows: the thickness of indium tin oxide is 100 nm; the MoOx thickness is 10 nm; NPB thickness is 50 nm; the thickness of mCP is 15 nm; the thickness of the luminescent layer is 30nm, and the doping concentration of the object is 20%; the thickness of DPEPO is 20 nm; the thickness of the Bphen is 50 nm; the thickness of LiF is 0.5 nm; the thickness of the metal Al is 150 nm.
The obtained electroluminescent device with blue and/or white thermally-excited delayed fluorescence preferably has a lighting voltage within 3.0V, a maximum external quantum efficiency higher than 12%, and a maximum current efficiency higher than 25 cd.A-1The maximum power efficiency is greater than 20 lm.W-1。
In the invention, the inventor believes that the thermal excitation delayed fluorescence material has better performance mainly due to (1) that the matrix is packed by isovolumetric compact spheres, and the stereo structure can effectively inhibit pi-pi interaction between molecules and prevent emission quenching caused by the interaction between host molecules and guest molecules; (2) intermolecular hydrogen bonds are formed between phosphine oxide groups and fluorine atoms between the parent bodies, and the occurrence of the hydrogen bonds can promote the transmission of current carriers, thereby realizing high-efficiency ultralow-voltage driving.
According to the thermal excitation delayed fluorescence host material and the preparation method and the application thereof provided by the invention, the following beneficial effects are achieved:
(1) the thermal stability of the thermal excitation delay fluorescence main body material is high, and the thermal cracking temperature is higher than 300 ℃;
(2) the blue and white thermal excitation delay fluorescence electroluminescent device prepared by the thermal excitation delay fluorescence main body material has the advantages that the starting voltage is within 3.0V, the maximum external quantum efficiency is higher than 12 percent, and the maximum current efficiency is larger than 25 cd.A-1The maximum power efficiency is greater than 20 lm.W-1；
(3) The parent is packed by isovolumetric compact spheres, and the stereo structure can effectively inhibit pi-pi interaction between molecules and prevent emission quenching caused by strong interaction between host and guest molecules;
(4) intermolecular hydrogen bonds are formed between phosphine oxide groups and fluorine atoms between the parent bodies, and the occurrence of the hydrogen bonds can promote the transmission of current carriers, thereby realizing high-efficiency overvoltage driving;
examples
EXAMPLE 1 preparation of TPDPO having the Structure of formula I
(1) Placing 3mmol of o-dibromobenzene and 15ml of tetrahydrofuran in a 50ml three-neck round-bottom flask which is baked to remove water, cooling to-120 ℃ by using a mixture of liquid nitrogen and n-propanol, stirring, slowly dropwise adding 3.6mmol of n-butyllithium during stirring, reacting for 20min, slowly dropwise adding 1mmol of phosphorus trichloride, stirring for 12h, quenching with water, extracting with dichloromethane, and extracting an organic layer with anhydrous Na2SO4Drying, removing the solvent by a rotary evaporator, and purifying the concentrate by column chromatography with petroleum ether and dichloromethane in a volume ratio of 5:1 to obtain an intermediate tri (2-bromophenyl) phosphine;
(2) stirring 3mmol of tris (2-bromophenyl) phosphine and 20ml of diethyl ether at 0 ℃, dropwise adding 3.6mmol of n-butyllithium, reacting for 1h, adding 1mmol of phosphorus trichloride, stirring for 12h, quenching with water, adding hydrogen peroxide, stirring for 2h, recrystallizing the crude product with methanol to obtain 9, 10-dihydro-9, 10-o-benzo-9, 10-diphospha-anthracene-9, 10-dioxide, and marking the product as TPDPO.
The intermediate prepared in example 1 has the structural formula:
Figure BDA0001454288210000101
the nuclear magnetic resonance hydrogen spectrum data are as follows: 1H NMR (TMS, CDCl)3,400MHz):δ＝7.66-7.627(m,3H),7.282-7.214(m,6H),6.768-6.739ppm(m,3H)；
The compound TPDPO prepared in example 1 has the structural formula:
Figure BDA0001454288210000102
the nuclear magnetic resonance hydrogen spectrum data are as follows: 1H NMR (TMS, CDCl)3,400MHz):δ＝8.25-8.166(m,6H),7.2569-7.538ppm(m,6H)。
Example 2 preparation of TPDPOF6 having the structure of formula II
The experimental procedure was the same as in example 1, except that the starting fluorinated o-dibromobenzene was 1, 2-dibromo-4, 5-difluorobenzene, and the intermediate obtained was tris (2-bromo-4, 5-difluorophenyl) phosphine; the product is 2,3,7,8,14, 15-hexafluoro-5, 10- [1,2] -phenylphosphine-5, 10-dioxide, and is noted as TPDPOF 6.
The intermediate prepared in example 2 has the structural formula:
Figure BDA0001454288210000111
the compound TPDPOF6 prepared in example 2 has the structural formula:
Figure BDA0001454288210000112
the mass spectrometer measured data for TPDPOF6 was: m/z 429.97 (100.0%), 430.98 (19.6%), 431.98 (2.2%) elementary Analysis C, 50.26; h, 1.41; f, 26.50; o, 7.44; p, 14.40.
Example 3 preparation of o-TPDPOF9 having the structure of formula III
The experimental procedure was the same as in example 1, except that the starting fluorinated o-dibromobenzene was 1, 2-dibromo-3, 4, 5-trifluorobenzene, and the intermediate obtained was tris (2-bromo-3, 4, 5-trifluorophenyl) phosphine; the product is 1,2,3,7,8,9,14,15, 16-nonafluoro-5, 10- [1,2] phenylphosphine 5, 10-dioxide, noted as o-TPDPOF 9.
The intermediate prepared in example 3 has the structural formula:
Figure BDA0001454288210000113
the compound o-TPDPOF9 prepared in example 3 has the structural formula:
Figure BDA0001454288210000121
the mass spectrometer measured data of O-TPDPOF9 are: m/z 483.95 (100.0%), 484.95 (19.6%), 485.95 (2.2%) elementary Analysis C, 44.65; h, 0.62; f, 35.32; o, 6.61; p,12.80
Example 4 preparation of p-TPDPOF9 having the structure of formula IV
The experimental procedure was the same as in example 1, except that the starting fluorinated o-dibromobenzene was 2, 3-dibromo-1, 4, 5-trifluorobenzene, and the intermediate obtained was tris (2-bromo-3, 4, 6-trifluorophenyl) phosphine; the product is 1,2,4,6,8,9,13,15, 16-nonafluoro-5, 10- [1,2] phenylphosphine 5, 10-dioxide, and the product is marked as p-TPDPOF 9.
The intermediate prepared in example 4 has the structural formula:
Figure BDA0001454288210000122
the compound p-TPDPOF9 prepared in example 4 has the structural formula:
Figure BDA0001454288210000123
mass spectrometer measurements of P-TPDPOF9 were m/z 483.95 (100.0%), 484.95 (19.6%), 485.95 (2.2%) elementary Analysis: C, 44.65; h, 0.62; f, 35.32; o, 6.61; p, 12.80.
EXAMPLE 5 preparation of TPDPOF12 having the Structure of formula V
The experimental procedure was the same as in example 1, except that the starting fluorinated o-dibromobenzene was 1, 2-dibromo-3, 4,5, 6-tetrafluorobenzene, and the intermediate obtained was tris (2-bromo-3, 4,5, 6-tetrafluorophenyl) phosphine; the product is perfluoro-5, 10- [1,2] phenylphosphine 5, 10-dioxide; the product is noted as TPDPOF 12.
The intermediate prepared in example 5 has the structural formula:
Figure BDA0001454288210000131
the compound TPDPOF12 prepared in example 5 has the structural formula:
Figure BDA0001454288210000132
mass spectrometer measurements of TPDPOF12 were m/z 537.92 (100.0%), 538.92 (19.5%), 539.92 (2.2%) elementary Analysis: C, 40.18; f, 42.37; o, 5.95; p, 11.51.
Examples of the experiments
Experimental example 1 ultraviolet fluorescence spectrum of thermally excited delayed fluorescence host material
Respectively dissolving the thermally-excited delayed fluorescence main body materials synthesized in the embodiments 1-5 in a dichloromethane solvent, and then performing an ultraviolet fluorescence spectrum test on the thermally-excited delayed fluorescence main body materials to obtain an ultraviolet fluorescence spectrum:
the ultraviolet fluorescence spectrum of TPDPO is shown in figure 1;
the ultraviolet fluorescence spectrum of TPDPOF6 is shown in FIG. 3;
the ultraviolet fluorescence spectrum of o-TPDPOF9 is shown in FIG. 5;
the ultraviolet fluorescence spectrum of p-TPDPOF9 is shown in FIG. 7;
the ultraviolet fluorescence spectrum of TPDPOF12 is shown in FIG. 9;
as can be seen from the above graph, the UV absorption spectrum starts to have an absorption peak at 300-400nm, which indicates that there is charge transfer between molecules; the fluorescence spectrum generally shows peaks around 470-500nm, which indicates that the luminescence colors are blue and blue-green.
Experimental example 2 thermogravimetric analysis spectrum of thermally-excited delayed fluorescence host material
Performing thermogravimetric analysis test on the thermally-excited delayed fluorescence main body material synthesized in the embodiment 1-5 to obtain a thermogravimetric analysis spectrogram:
the thermogravimetric analysis spectrum of TPDPO is shown in figure 2;
the thermogravimetric analysis spectrum of TPDPOF6 is shown in fig. 4;
the thermogravimetric analysis spectrum of o-TPDPOF9 is shown in FIG. 6;
the thermogravimetric analysis spectrum of p-TPDPOF9 is shown in FIG. 8;
the thermogravimetric analysis spectrum of TPDPOF12 is shown in fig. 10;
from FIG. 2, it can be seen that the cracking temperature of TPDPO prepared in example 1 reaches 308 ℃;
from FIG. 4, it can be seen that the cracking temperature of TPDPOF6 prepared in example 2 is up to 310 ℃;
from FIG. 6 it can be seen that the cracking temperature of o-TPDPOF9 obtained in example 3 reached 313 ℃;
from FIG. 8, it can be seen that the cracking temperature of p-TPDPOF9 obtained in example 4 reached 320 ℃;
from FIG. 10, it is understood that TPDPOF12 obtained in example 5 has a cracking temperature of 347 ℃.
From the above data, it can be seen that the thermo-chemical stability of each thermally-excited delayed fluorescence host material is good.
Application examples
Application example 1 preparation of electroluminescent yellow phosphorescent device with TPDPO as main material and performance measurement thereof
This application example 1 an electrophosphorescent device of yellow electroluminescent light was prepared based on the 9, 10-dihydro-9, 10-ortho-benzo-9, 10-diphosphatanthracene-9, 10-dioxide thermally-excited delayed fluorescence material TPDPO having the structure of formula I prepared in example 1 as host material, said device being prepared by the following steps:
putting a glass or plastic substrate cleaned by deionized water into a vacuum evaporation instrument, wherein the vacuum degree is 1 x 10 < -6 > mbar, the evaporation rate is 0.1nm s < -1 >, the glass or plastic substrate is evaporated by indium tin oxide, and an anode conducting layer with the thickness of 100nm is formed;
secondly, evaporating a hole injection layer with the material of MoOx and the thickness of 10nm on the anode conducting layer;
thirdly, evaporating a hole transport layer with the thickness of 50nm, wherein the material is NPB on the hole injection layer;
evaporating an electron blocking layer which is made of mCP and is 15nm thick on the hole transport layer;
fifthly, continuously evaporating a light-emitting layer with the thickness of 30nm on the electron blocking layer, wherein the host material is TPDPO prepared in example 1, the guest material is DMAC-DPS/4CzPNPh, and the doping concentration of the guest material is 15%;
sixthly, evaporating a hole blocking layer which is made of DPEPO and has the thickness of 20nm on the luminescent layer;
seventhly, evaporating an electron transport layer which is made of Bphen and has the thickness of 50nm on the hole blocking layer;
eighthly, evaporating an electron injection layer on the electron transport layer, wherein the evaporation material is LiF, and the thickness of the electron injection layer is 0.5 nm;
and ninthly, evaporating a cathode conducting layer with the thickness of 150nm on the electron injection layer by using metal Al, and packaging to obtain the thermally-excited delayed fluorescence (TADF) electroluminescent device.
The electrophosphorescent device of the present application example 1 has a structure of ITO/MoO3(10nm)/NPB (50nm)/mCP (15nm)/TPDPO, DMAC-DPS (15%, 30nm)/DPEPO (20nm)/Bphen (50nm)/LiF (0.5nm)/Al (150 nm).
The performance test curves for the electrophosphorescent devices prepared in application example 1 based on TPDPO are shown in the following figures as ■:
11a-11b are graphs of voltage versus current density;
fig. 12a-12b are voltage-luminance graphs showing that the turn-on voltage of the device is 2.4V, 2.3V.
FIGS. 13a-13b are graphs showing the relationship between luminance and current efficiency, and the current efficiency of the device reaches the maximumThe value 29.8 cd. A-1，44.3cd·A-1。
FIGS. 14a-14b are graphs showing the relationship between luminance and power efficiency, and it can be seen that the power efficiency of the device reaches the maximum value of 23.8 lm.W-1，39.7lm·W-1。
Fig. 15a-15b are graphs of luminance-external quantum efficiency relationship, and it can be seen that the maximum external quantum efficiency of the device is 15.2%, 14.2%.
FIGS. 16a-16b are electroluminescence spectra showing the device electroluminescence peaks at 480nm, 476 nm.
It can be seen from the electroluminescence spectrum that the color was blue at around 476nm and red-shifted to 480nm, which was caused by the difference in the number of substituent groups, and that the half width of the emission peak was narrow, indicating high color purity.
Application example 2 preparation of electroluminescent yellow phosphorescent device with TPDPOF6 as main material and performance measurement thereof
This application example 2 is based on the fact that the TPDPOF6 with the structure of formula II prepared in example 2 is the host material to prepare the electrophosphorescent device, and the preparation steps are the same as those of application example 1, except that the host material is different;
the structure of the electrophosphorescent device prepared in application example 2 is ITO/MoO3(10nm)/NPB (50nm)/mCP (15nm)/TPDPOF6, DMAC-DPS (15%, 30nm)/DPEPO (20nm)/Bphen (50nm)/LiF (0.5nm)/Al (150 nm).
Application example 2 various performance test curves for electrophosphorescent devices prepared on the basis of TPDPOF6, all indicated at ● in the following figures:
11a-11b are graphs of voltage versus current density;
fig. 12a-12b are voltage-luminance graphs showing that the turn-on voltage of the device is 2.6V, 2.8V.
FIGS. 13a-13b are graphs showing the relationship between luminance and current efficiency, from which it can be seen that the current efficiency of the device reaches a maximum of 30.9 cd.A-1，34.7cd·A-1。
FIGS. 14a-14b are graphs of luminance vs. power efficiency showing that the power efficiency of the device is achievedMaximum value of 24.8lm W-1，27.3lm·W-1。
Fig. 15a-15b are graphs of luminance versus external quantum efficiency, from which it can be seen that the maximum external quantum efficiency of the device is 16.7%, 14.6%.
FIGS. 16a-16b are electroluminescence spectra showing the electroluminescence peaks at 488nm and 556 nm.
Application example 3 preparation of electro-phosphorescent yellow light device by using o-TPDPOF9 as main material and performance measurement thereof
Application example 3 is an electro-phosphorescent yellow light device prepared based on o-TPDPOF9 having the structure of formula III prepared in example 3 as a host material, and the preparation steps are the same as those of application example 1 except that the host material is different;
the structure of the electrophosphorescent device prepared in the application example 3 is ITO/MoO3(10nm)/NPB(50nm)/mCP(15nm)/o-TPDPOF9:DMAC-DPS(15％,30nm)/DPEPO(20nm)/Bphen(50nm)/LiF(0.5nm)/Al(150nm)。
Application example 3 various performance test curves for an electrophosphorescent device prepared on the basis of o-TPDPOF9, all indicated at ▲ in the following figures:
11a-11b are graphs of voltage versus current density;
fig. 12a-12b are voltage-luminance graphs showing that the turn-on voltage of the device is 3.0V, 2.9V.
FIGS. 13a-13b are graphs showing the relationship between luminance and current efficiency, from which it can be seen that the current efficiency of the device reaches a maximum of 32.1 cd.A-1，50.2cd·A-1。
FIGS. 14a-14b are graphs showing the relationship between luminance and power efficiency, and it is understood from these graphs that the power efficiency of the device reaches the maximum value of 30.9lm W-1,45.1lm·W-1。
Fig. 15a-15b are graphs of luminance versus external quantum efficiency, from which it can be seen that the device has maximum external quantum efficiency of 20.2%, 16.2%.
FIGS. 16a-16b are electroluminescence spectra showing the electroluminescence peaks at 503nm and 560 nm.
Application example 4 preparation of electroluminescent yellow phosphorescent device with p-TPDPOF9 as main material and performance measurement thereof
This application example 4 is based on p-TPDPOF9 with formula IV structure prepared in example 4 as host material to prepare electrophosphorescent device with yellow light, and the preparation steps are the same as application example 1, except that the host material is different;
the structure of the electrophosphorescent device prepared in the application example 4 is ITO/MoO3(10nm)/NPB(50nm)/mCP(15nm)/p-TPDPOF9:DMAC-DPS(15％,30nm)/DPEPO(20nm)/Bphen(50nm)/LiF(0.5nm)/Al(150nm)。
Application example 4 various performance test curves for an electrophosphorescent device prepared based on p-TPDPOF9 are shown in a xxx in the following figures:
11a-11b are graphs of voltage versus current density;
fig. 12a-12b are voltage-luminance graphs showing that the turn-on voltage of the device is 2.7V, 2.2V.
FIGS. 13a-13b are graphs showing the relationship between luminance and current efficiency, from which it can be seen that the current efficiency of the device reaches the maximum value of 30.9 cd-A-1，47.9cd·A-1。
FIGS. 14a-14b are graphs showing the relationship between luminance and power efficiency, from which it can be seen that the power efficiency of the device reaches the maximum value of 27.5 lm.W-1，43lm·W-1。
Fig. 15a-15b are luminance-external quantum efficiency graphs, from which it can be seen that the maximum external quantum efficiency of the device is 18.4%, 15.4%.
FIGS. 16a-16b are electroluminescence spectra, from which it can be seen that the electroluminescence peaks of the device are at 499nm, 484 nm.
Application example 5 preparation of electroluminescent yellow phosphorescent device with TPDPOF12 as main material and performance measurement thereof
Application example 5 is an electrophosphorescent device prepared based on TPDPOF12 having a structure of formula V prepared in example 5 as a host material, and the preparation steps are the same as application example 1 except that the host material is different;
application example 5The prepared electrophosphorescent device has the structure of ITO/MoO3(10nm)/NPB(50nm)/mCP(15nm)/TPDPOF12:DMAC-DPS(15％,30nm)/DPEPO(20nm)/Bphen(50nm)/LiF(0.5nm)/Al(150nm)。
Application example 5 various performance test curves for an electrophosphorescent device prepared on the basis of TPDPOF12, all indicated at ◆ in the following figures:
11a-11b are graphs of voltage versus current density;
fig. 12a-12b are voltage-luminance graphs showing that the turn-on voltage of the device is 2.8V, 2.7V.
FIGS. 13a-13b are graphs showing the relationship between luminance and current efficiency, from which it can be seen that the current efficiency of the device reaches a maximum of 30.9 cd.A-1，46.4cd·A-1。
FIGS. 14a-14b are graphs showing the relationship between luminance and power efficiency, and it can be seen that the power efficiency of the device reaches the maximum value of 25.2lm W-1，41.7lm·W-1。
Fig. 15a-15b are graphs of luminance versus external quantum efficiency, from which it can be seen that the maximum external quantum efficiency of the device is 17.7%, 14.9%.
FIGS. 16a-16b are electroluminescence spectra, from which it can be seen that the electroluminescence peaks of the device are at 495nm and 552 nm.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (8)

1. A thermally-activated delayed fluorescence host material based on a 9, 10-dihydro-9, 10-ortho-benzo-9, 10-diphospha-anthracene-9, 10-dioxide of the structure of formula I:
Figure DEST_PATH_IMAGE001
，
the parent compound of formula I is modified with 1 to 4 fluorine atoms per phenyl ring.
2. A thermally-excited delayed fluorescence host material according to claim 1, wherein the parent compound of formula I is modified with 2 to 4 fluorine atoms per benzene ring.
3. A thermally-excited delayed fluorescence host material according to claim 1 or 2, wherein the fluorescence host material has a specific structure as follows:
Figure DEST_PATH_IMAGE002
。
4. a method for preparing a thermally-excited delayed fluorescence host material according to one of claims 1 to 3, comprising the steps of:
(1) mixing o-dibromobenzene or fluoro-o-dibromobenzene with a solvent I, stirring at 0 to-120 ℃, dropwise adding a lithium reagent, reacting for 12-24 h, adding a phosphating agent, stirring for reacting for 6-12 h, and performing post-treatment to obtain an intermediate, wherein the solvent I is tetrahydrofuran, the lithium reagent is n-butyllithium, and the phosphating agent is phosphorus trichloride;
(2) dissolving the intermediate in a solvent II, stirring at 0 to-120 ℃, dropwise adding a lithium reagent, reacting for 12-24 h, adding a phosphating agent, stirring and reacting for 6-12 h, wherein the solvent is
Figure DEST_PATH_IMAGE003
The reaction solution is diethyl ether, the lithium reagent is n-butyllithium, the phosphating agent is phosphorus trichloride, and the reaction solution is quenched by water;
(3) adding an oxidant, namely hydrogen peroxide, and continuing to react for 0.5-6h to obtain a crude product, and treating the crude product, namely recrystallizing to obtain the product.
5. The method according to claim 4, wherein in the step (3), the reaction is carried out for 1 to 3 hours.
6. The method of claim 4 or 5, comprising the steps of:
(1) mixing 3mmol of o-dibromobenzene, 1, 2-dibromo-4, 5-difluorobenzene, 1, 2-dibromo-3, 4, 5-trifluorobenzene, 2, 3-dibromo-1, 4, 5-trifluorobenzene or 1, 2-dibromo-3, 4,5, 6-tetrafluorobenzene with 10-30 mL of tetrahydrofuran respectively, stirring at 0-120 ℃, dropwise adding 1-8 mmol of n-butyllithium, reacting for 12-24 h, adding 1-5 mmol of phosphorus trichloride, stirring for 6-12 h, and performing post-treatment to obtain an intermediate;
(2) dissolving the intermediate in 10-30 mL of diethyl ether, stirring at 0-120 ℃, dropwise adding 1-8 mmol of n-butyllithium, reacting for 12-24 h, adding 1-5 mmol of phosphorus trichloride, stirring, reacting for 6-12 h, and quenching with water;
(3) adding hydrogen peroxide to continue reacting for 2h to obtain a crude product, and recrystallizing the crude product to respectively obtain a product with a formula I and a product with a formula II
Figure 557949DEST_PATH_IMAGE003
A and B type
Figure DEST_PATH_IMAGE004
A and B type
Figure DEST_PATH_IMAGE005
Or formula
Figure DEST_PATH_IMAGE006
A compound of structure (la).
7. The production method according to claim 4 or 5,
the post-treatment in the step (1) comprises quenching the reaction with water, extracting with an organic solvent, concentrating, and purifying by column chromatography using a petroleum ether: a mixed solvent with the volume ratio of dichloromethane being 5: 1;
and (3) using methanol as a solvent for recrystallization.
8. Use of a thermally-excited delayed fluorescence host material according to any one of claims 1 to 3 or produced by the method according to any one of claims 4 to 7 as a host material in a thermally-excited delayed fluorescence electroluminescent device, in which the following specific application methods are used:
firstly, putting the glass or plastic substrate cleaned by deionized water into a vacuum evaporation plating instrument with the vacuum degree of1 multiplied by 10-6mbar, evaporation rate set at 0.1nm s-1An anode conducting layer which is made of indium tin oxide and has the thickness of 100nm is evaporated on a glass or plastic substrate;
secondly, evaporating a material MoO on the anode conducting layer3A hole injection layer with a thickness of 5-30 nm;
thirdly, evaporating a hole transport layer which is made of NPB (nitrogen-phosphorus) material and has the thickness of 40-70 nm on the hole injection layer;
evaporating an electron blocking layer which is made of mCP and is 10nm thick on the hole transport layer;
fifthly, continuously evaporating a host material which is 20-40 nm thick and based on the formula I as a matrix and a light-emitting layer of a blue light object material doped with DMAC-DPS/a white light object material doped with 4CzPNPh on the electron blocking layer; the doping concentration of the guest material is 5% -15%;
sixthly, evaporating a hole blocking layer which is made of DPEPO and has the thickness of 15nm on the luminescent layer;
seventhly, evaporating an electron transport layer which is made of Bphen and has the thickness of 50nm on the hole blocking layer;
eighthly, evaporating an electron injection layer on the electron transport layer, wherein the evaporation material is LiF, and the thickness of the electron injection layer is 0.5 nm;
and ninthly, evaporating a cathode conducting layer which is made of metal Al and has the thickness of 150nm on the electron injection layer, and packaging to obtain the thermal excitation delay fluorescence electroluminescent device.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102503980A (en) * 2011-11-01 2012-06-20 黑龙江大学 Photoelectric functional aromatic phosphine oxide compound, and preparation method and application thereof
WO2015080182A1 (en) * 2013-11-28 2015-06-04 国立大学法人九州大学 Light-emitting material, organic light-emitting element, and compound
CN105121428A (en) * 2013-02-07 2015-12-02 国立大学法人九州大学 Compound having diazatriphenylene ring structure, and organic electroluminescent element
CN105367603A (en) * 2015-12-04 2016-03-02 河南省科学院化学研究所有限公司 Anthracene-based diphosphonic hetero six-membered ring organic electroluminescent compound, synthetic method therefor and application thereof
CN106632480A (en) * 2017-02-08 2017-05-10 黑龙江大学 n-type thermal excitation delayed fluorescence aromatic phosphine oxide main body materials based on dibenzofuran groups as well as synthetic method and application thereof
CN106831874A (en) * 2017-02-15 2017-06-13 黑龙江大学 Thermal excitation delayed fluorescence material of main part based on phosphine heteroaryl derivative and its preparation method and application
CN106831875A (en) * 2017-02-15 2017-06-13 黑龙江大学 Thermal excitation delayed fluorescence material of main part based on phosphine heteroaryl derivative and its preparation method and application
CN106905366A (en) * 2017-02-20 2017-06-30 黑龙江大学 Triazines exciplex material based on phosphine oxygen and its preparation method and application
CN107236003A (en) * 2017-06-29 2017-10-10 黑龙江大学 The blue light of branch containing carbazole thermal excitation delayed fluorescence aromatic material and its warm white optical device preparation method and application

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102503980A (en) * 2011-11-01 2012-06-20 黑龙江大学 Photoelectric functional aromatic phosphine oxide compound, and preparation method and application thereof
CN105121428A (en) * 2013-02-07 2015-12-02 国立大学法人九州大学 Compound having diazatriphenylene ring structure, and organic electroluminescent element
WO2015080182A1 (en) * 2013-11-28 2015-06-04 国立大学法人九州大学 Light-emitting material, organic light-emitting element, and compound
CN105367603A (en) * 2015-12-04 2016-03-02 河南省科学院化学研究所有限公司 Anthracene-based diphosphonic hetero six-membered ring organic electroluminescent compound, synthetic method therefor and application thereof
CN106632480A (en) * 2017-02-08 2017-05-10 黑龙江大学 n-type thermal excitation delayed fluorescence aromatic phosphine oxide main body materials based on dibenzofuran groups as well as synthetic method and application thereof
CN106831874A (en) * 2017-02-15 2017-06-13 黑龙江大学 Thermal excitation delayed fluorescence material of main part based on phosphine heteroaryl derivative and its preparation method and application
CN106831875A (en) * 2017-02-15 2017-06-13 黑龙江大学 Thermal excitation delayed fluorescence material of main part based on phosphine heteroaryl derivative and its preparation method and application
CN106905366A (en) * 2017-02-20 2017-06-30 黑龙江大学 Triazines exciplex material based on phosphine oxygen and its preparation method and application
CN107236003A (en) * 2017-06-29 2017-10-10 黑龙江大学 The blue light of branch containing carbazole thermal excitation delayed fluorescence aromatic material and its warm white optical device preparation method and application

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Bromine Adducts of 9,10-Diheteratriptycene Derivatives";Yosuke U.et al;《Bull.Chem.Soc.Jpn》;20091231;第82卷(第7期);第822页 *
"Synthesis of Arylphosphonous Dichlorides, Diarylphosphinous Chlorides, and 1,6-Diphosphatriptycene from Elemental Phosphorus";Kurt G W. et al;《J. Org. Chem》;19751231;第40卷(第24期);第3588页 *
"大共轭高能隙电致磷光主体材料的研究进展";张珍等;《黑龙江大学自然科学学报》;20160630;第33卷(第3期);第351-369页 *

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