CN114106026A - Double-boron organic luminescent material and application of luminescent device - Google Patents

Double-boron organic luminescent material and application of luminescent device Download PDF

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CN114106026A
CN114106026A CN202111307718.1A CN202111307718A CN114106026A CN 114106026 A CN114106026 A CN 114106026A CN 202111307718 A CN202111307718 A CN 202111307718A CN 114106026 A CN114106026 A CN 114106026A
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许千千
马伟
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Abstract

The invention discloses a double-boron organic luminescent material, which has the following structure:
Figure DDA0003340744340000011
wherein Ar is1And Ar2Is six-membered benzene ring, six-membered aromatic heterocyclic ring, five-membered or six-membered condensed aromatic heterocyclic ring with carbon atom not more than 18 and R1 substituent of the rings, and Ar is Ar1And Ar2Ring c and/or R independently and adjacently adjacent to each othercRing d and/or RdLinked to form a ring or not linked to form a ring, wherein the linkage to form a ring may be through-O-, -S-, -CR2R3-orA single bond connection; the R is1、R2、R3、Ra、Rb、Rc、RdOne or more substitutions satisfying the number of benzene ring or aromatic heterocyclic bond can be selected from hydrogen, deuterium, fluorine, substituted or unsubstituted C1‑12Alkyl, substituted or unsubstituted C1‑12Alkoxy, substituted or unsubstituted C3‑12Cycloalkyl, substituted or unsubstituted C1‑12Alkylsilyl, substituted or unsubstituted C6‑16Aryl group of (2), substituted or unsubstituted C containing one or more heteroatoms4‑16Heteroaryl, substituted or unsubstituted C6‑16The fused heteroaryl group of (1). The invention has the beneficial effects that: the organic electroluminescent device prepared by the double-boron organic luminescent material has narrower half-peak width, higher luminous efficiency and longer device service life, and shows good application prospect.

Description

Double-boron organic luminescent material and application of luminescent device
Technical Field
The invention relates to the field of organic semiconductors, in particular to a novel double-boron organic luminescent material, application thereof and an organic electroluminescent device containing the organic luminescent material.
Background
Organic Light Emitting Diodes (OLEDs) are the most competitive next generation display and lighting technology due to their advantages of high color saturation, wide viewing field, high response speed, solid state, high brightness, low power consumption, and flexibility. Due to their excellent performance, the entire industry is focusing on the latest developments in OLED products, and to date, the multi-billion dollar display and lighting market has been penetrated by this very attractive OLED technology, and its enormous market demand has accelerated the pace of finding future high performance materials.
The core of the OLED is an organic light emitting material, and through continuous efforts of researchers, the organic light emitting material has been rapidly developed and has undergone conventional fluorescent materials (first generation organic light emitting material), organic metal complex phosphorescent materials (second generation organic light emitting material) and thermal activation delayed fluorescent materials (TADF material, third generation organic light emitting material).
The traditional fluorescent material has long service life and low price, and then because of the limitation of the electron spin statistical rule, the traditional fluorescent material can only utilize 25% of singlet excitons, so that the maximum internal quantum efficiency of a device based on the traditional fluorescent material is limited within 25%. The organometallic complex phosphorescent material realizes 100% exciton utilization rate due to the enhancement of spin-orbit coupling effect of heavy metal atoms. However, the blue light stability prepared from organic phosphorescent materials is far from the requirements of practical display and lighting technologies. In addition, since the preparation of the phosphorescent material requires the use of noble metals (e.g., iridium, etc.), the manufacturing cost is high.
The advent of TADF materials has provided a breakthrough for addressing and balancing OLED efficiency, lifetime, and cost. Compared with the traditional fluorescent material, the OLED device based on the TADF material has higher electroluminescent efficiency due to the capability of realizing 100% internal quantum efficiency; on the other hand, the TADF material has huge cost and stability advantages over the second generation organometallic complex phosphorescent materials because it does not require the use of expensive metals. Therefore, TADF materials have become a hot spot and a breakthrough spot for research by scientists and engineers in recent years in academia and industry. However, TADF materials tend to emit light with a broad emission spectrum, thereby affecting the color purity of the OLED.
The boron-nitrogen TADF material with multiple resonance effects can reduce the half-peak width of a luminescence spectrum to be below 30nm, but the light color of the material is always limited in a blue-deep blue region, so that the application of the material in the fields of high-resolution display, full-color display, white light illumination and the like is greatly limited.
Disclosure of Invention
In order to solve the technical problems, the invention provides a double-boron organic luminescent material and application thereof. The organic luminescent material has the characteristics of narrow half-peak width, high fluorescence quantum yield, high thermal stability and the like, and can be used as a doping agent or an auxiliary doping agent of a luminescent layer of an organic electroluminescent device, so that the luminescent color purity of the device is improved, and the service life of the device is prolonged. The specific chemical structural general formula of the double-boron organic luminescent material is shown as (I):
Figure BDA0003340744320000021
in the general formula (I), Ar1And Ar2Is six-membered benzene ring, six-membered aromatic heterocyclic ring, five-membered or six-membered condensed aromatic heterocyclic ring with carbon atom not more than 18 and R of the rings1A substituent;
ar is1And Ar2Ring c and/or R independently and adjacently adjacent to each othercRing d and/or RdConnected to form a ring or not connected to form a ringWhen it is used, it can be reacted with a compound represented by the formula-O-, -S-, -CR2R3-or a single bond connection;
the R is1、R2、R3、Ra、Rb、Rc、RdOne or more substitutions satisfying the number of benzene ring or aromatic heterocyclic bond can be selected from hydrogen, deuterium, fluorine, substituted or unsubstituted C1-12Alkyl, substituted or unsubstituted C1-12Alkoxy, substituted or unsubstituted C3-12Cycloalkyl, substituted or unsubstituted C1-12Alkylsilyl, substituted or unsubstituted C6-16Aryl group of (2), substituted or unsubstituted C containing one or more heteroatoms4-16Heteroaryl, substituted or unsubstituted C6-16A fused heteroaryl group of (a);
the substituent of the substitutable group is selected from deuterium, halogen, cyano, C1-12Alkyl radical, C3-12Cycloalkylmethyl group of (A), C1-12Alkoxy group of (C)6-16Aryl group of (2), substituted or unsubstituted C containing one or more heteroatoms4-16One or more of heteroaryl;
the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
As a further improvement of the invention, Ar as described in formula (I)1、Ar2Each independently represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted dimethylfluorenylene group, a substituted or unsubstituted diphenylfluorenylene group, a substituted or unsubstituted pyridinylene group, a substituted or unsubstituted benzofuranylene group, a substituted or unsubstituted benzothiophenylene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted carbazolyl group, or a substituted or unsubstituted naphthyridinylene group;
ar is1And Ar2Ring c and/or R independently and adjacently adjacent to each othercRing d and/or RdAre connected to formThe ring may be connected to form a ring through-O-, -S-, -CR2R3-or a single bond connection;
the R is1-R3、Ra-RdEach independently represents a hydrogen atom, deuterium, a fluorine atom, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, methoxy, trimethylsilyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenylyl, substituted or unsubstituted terphenylyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted furyl, substituted or unsubstituted benzofuryl, substituted or unsubstituted dibenzofuryl, substituted or unsubstituted thienyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted azacarbazolyl, substituted or unsubstituted benzindenyl, Substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted benzophenanthryl, substituted or unsubstituted azabenzophenanthryl;
the substituent of the substitutable group is selected from one or more of deuterium, fluorine atom, cyano group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, pentyl group, phenyl group, naphthyl group, biphenyl group, pyridyl group or furyl group.
As a further improvement of the present invention, the diboron organic luminescent material is any one of the following compounds, which are only representative:
Figure BDA0003340744320000041
Figure BDA0003340744320000051
Figure BDA0003340744320000061
Figure BDA0003340744320000071
Figure BDA0003340744320000081
Figure BDA0003340744320000091
the invention also provides an organic light-emitting device which comprises a cathode, an electron transport layer close to the cathode, an anode, a hole transport layer close to the anode and a light-emitting layer sandwiched between the electron transport layer and the hole transport layer, wherein the light-emitting layer comprises the double-boron organic light-emitting material shown in the general formula (I).
As a further improvement of the invention, the luminescent dopant in the luminescent layer is a double-boron organic luminescent material as shown in the general formula (I), and the proportion of the luminescent layer is 1-49% by weight.
As a further improvement of the invention, the sensitizing material for energy transfer in the luminescent layer is a diboron organic luminescent material shown in a general formula (I), and the proportion of the diboron organic luminescent material in the luminescent layer is 5-49% by weight.
According to the compound with the general formula (I), more boron atoms or nitrogen atoms are introduced through the expanding modification of a classical boron-nitrogen TADF material with multiple resonance effects, the red shift of a target boron-nitrogen TADF material is realized while the boron-nitrogen rigid framework and the small singlet state and triplet state energy level difference are kept, the emission of blue light, green light, yellow light and even red light is obtained, and the boron-nitrogen TADF material system with multiple resonance effects and the light-emitting color range are enriched.
The organic electroluminescent device prepared by the double-boron organic luminescent material has narrower half-peak width, lower starting voltage, higher luminous efficiency and longer device life, and shows good application prospect.
Drawings
Fig. 1 is a schematic structural diagram of the material applied to an organic electroluminescent device, where 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light emitting layer, 6 is an electron transport layer, 7 is an electron injection layer, and 8 is a cathode.
Detailed Description
The following describes the specific preparation method of the above-mentioned diboron organic light-emitting material of the present invention in detail with reference to the examples, but the present invention can be implemented in other ways than those described herein, and therefore the preparation method of the present invention is not limited to these specific examples.
The organic luminescent material containing double boron can be prepared by using various synthetic routes, wherein the compound is symmetrical to the center, namely Ar1＝Ar2,Ra＝Rb,Rc＝RdThe final target compound can be obtained by following the following reaction scheme:
Figure BDA0003340744320000111
for unsymmetrical compounds, i.e. Ar1≠Ar2Or R isa≠RbOr R isc≠RdThe final target compound can be obtained by following the following reaction scheme:
Figure BDA0003340744320000112
more specifically, the following gives a synthetic method of a representative specific compound of the present invention.
Synthesis example 1: preparation of Compound 6
Figure BDA0003340744320000121
Synthesis of intermediate 6-1
Figure BDA0003340744320000122
To a dry 250mL reaction flask were added 6-S1(10.03g,24mmol), 6-S2 (6.75g,24mmol), Pd in that order2(dba)3(440mg,0.48mmol), Xantphos (555 mg,0.96mmol), t-BuONa (6.92g,72mmol) and dry toluene (120mL), and the reaction mixture was heated to 90 ℃ under nitrogen for 17 h. The reaction was then cooled to room temperature, filtered through celite, and the filter cake was washed with dichloromethane, and the resulting filtrate was concentrated under reduced pressure and then purified by silica gel column (PE) to give 8.9g of intermediate 6-1 as a white solid in 65% yield.
Synthesis of intermediate 6-2
Figure BDA0003340744320000131
To a dry 250mL reaction flask were added magnesium (1.94g,80mmol), LiCl (3.39 g,80mmol), DMI (100mL) and chlorotrimethylsilane (17.38g,160mmol) in that order, stirred at room temperature under nitrogen for 15 minutes, then intermediate 6-1(5.71g,10mmol) was added and stirring continued for 4 hours. Then, a saturated aqueous solution of sodium hydrogencarbonate was added to the reaction mixture, and the mixture was filtered to remove solids, extracted with dichloromethane, the filtrate was concentrated, and purified with silica gel column (PE) to obtain intermediate 6-2 as a white solid with a yield of 72%.
Synthesis of Compound 6
Figure BDA0003340744320000132
To a solution of intermediate 6-2(3.5g,6.27mmol) in o-dichlorobenzene (50mL) under nitrogen blanket was added BBr3(25.08mmol), the reaction mixture was heated to 180 ℃ and reacted for 30 hours, then cooled to room temperature, and EtN (i-Pr) was added at zero degrees2(12.28g,95mmol), the solvent was distilled off under reduced pressure, and the residue was purified with silica gel column (PE/DCM ═ 10/1)) The target compound 6 was obtained as a yellow solid in 50% yield. C60H72B2N2The molecular formula calculated molecular weight is 842.59, mass spectrum detection M/z is 842.28, photoluminescence is blue light PL 468nm, and half-height peak width FWMH is 29 nm.
Synthesis example 2: synthetic preparation of Compound 84
Figure BDA0003340744320000141
Synthesis of intermediate 84-1
Figure BDA0003340744320000142
To a dry 250mL reaction flask were added sequentially o-bromoiodobenzene (10.18g,36mmol), diphenylamine (6.09g,36mmol), Pd2(dba)3(659mg,0.72mmol), Xantphos (833mg,1.44mmol), t-BuONa (10.38g,108mmol) and dry toluene (150mL) and the reaction mixture was heated to 90 ℃ under nitrogen for 16 h. The reaction was then cooled to room temperature, filtered through celite, and the filter cake was washed with dichloromethane, the resulting filtrate was concentrated under reduced pressure, and then purified by silica gel column (PE) to give intermediate 84-1 as a white solid in 75% yield.
Synthesis of intermediate 84-2
Figure BDA0003340744320000151
The flask containing 84-1(8.11g,25mmol) and dry THF (50mL) was cooled to-78 deg.C, a solution of n-BuLi (26.25mmol) in n-hexane was slowly added thereto, and the reaction was continued for 30min after dropping. Then, a solution of TMSCl (3.26g,30mmol) in dry THF (30mL) was added dropwise to the reaction solution, and after completion of the addition, the reaction was carried out at-78 ℃ for 1 hour, then warmed to room temperature, and the reaction was continued for 2 hours. Quenching with saturated ammonium chloride solution, extracting with ethyl acetate, concentrating, and passing through silica gel column (PE) to obtain intermediate 84-2 as white solid with yield of 86%.
Synthesis of intermediate 84-3
Figure BDA0003340744320000152
Cooling the dried reaction flask filled with 84-2(6.35g,20mmol) to-78 deg.C, adding BBr into the reaction flask under nitrogen protection3(60mmol), the reaction was warmed to room temperature for 30min, then heated to 150 ℃ and the reaction was continued for 3 days with the tube sealed. The volatiles were removed to give the crude product, which was used directly in the next step.
Synthesis of intermediate 84-4
Figure BDA0003340744320000161
To a dry 250mL reaction flask were added 1, 2-dibromo-3-iodobenzene (13.02g,36 mmol), carbazole (6.02g,36mmol), Pd in that order2(dba)3(659mg,0.72mmol), Xantphos (833mg,1.44mmol), t-BuONa (10.38g,108mmol) and dry toluene (150mL) and the reaction mixture was heated to 90 ℃ under nitrogen for 16 h. The reaction was then cooled to room temperature, filtered through celite, and the filter cake was washed with dichloromethane, the resulting filtrate was concentrated under reduced pressure, and then purified by silica gel column (PE) to give intermediate 84-4 as a white solid in 70% yield.
Synthesis of intermediate 84-5
Figure BDA0003340744320000162
The reaction flask containing 84-4(8.02g,20mmol) and dry ether (100mL) was cooled to-78 deg.C, to which a solution of n-BuLi (21mmol) in n-hexane was slowly added, and the reaction was continued at-78 deg.C for 30min after dropping. Then, 84-3 of a dry toluene (50mL) solution was added dropwise to the reaction solution, and after completion of the dropwise addition, the reaction was carried out at-78 ℃ for 1 hour, then the temperature was raised to room temperature, and the reaction was continued for 4 hours. The volatiles were removed under reduced pressure, saturated ammonium chloride solution was added, dichloromethane was extracted, the filtrate was concentrated and passed through silica gel column (PE) to afford intermediate 84-5 as a white solid in 62% yield.
Synthesis of Compound 84
Figure BDA0003340744320000171
An n-butyllithium-n-hexane solution (2.5M,9.6mmol) was slowly added to a solution of 84-5 (4.60g,8mmol) of t-butylbenzene (30mL) at-30 ℃ and then reacted at zero degrees for 30 min. Cooling to-30 deg.C, and slowly adding BBr3(2.4g,9.6mmol) and the reaction was continued at room temperature for 30 min. Diisopropylethylamine (2.07g,16mmol) was added at zero degrees and heated to 145 ℃ for 5 hours. The solvent was removed under reduced pressure and passed through a silica gel column (PE/DCM ═ 10/1) to give the title compound 84 as a pale yellow solid in 20% yield. C36H22B2N2Molecular formula calculated molecular weight is 504.20, mass spectrum detection M/z is 504.33, photoluminescence is light blue light PL is 480nm, and half-height peak width FWMH is 32 nm.
Synthetic example 3: synthetic preparation of other compound materials
Similarly, according to the above synthetic chemical route and similar procedures of example 1 and example 2, the following diboron organic luminescent material compounds were synthesized, and the listed compounds were verified by mass spectrometry, specifically as shown in table 1 below, without departing from the scope of the present invention:
table 1: compound synthesis and characterization
Figure BDA0003340744320000172
Figure BDA0003340744320000181
The double-boron organic luminescent material is mainly applied to organic electroluminescence as a luminescent layer compound material. The light-emitting layer generally contains a light-emitting dopant, and is mixed with one or more Host materials (Host) to form the light-emitting layer. The double-boron organic luminescent material has high luminescent efficiency and narrower emission spectrum, and is suitable for being used as a luminescent dopant. The luminescent dopant is mixed in the host material according to a certain proportion, which is beneficial to reducing self-quenching between luminescent dopant molecules and luminescent color change under different electric fields, thereby being beneficial to increasing the efficiency of organic electroluminescence and simultaneously reducing the dosage of expensive luminescent dopant. The mixed film can be formed by vacuum co-evaporation or by mixing and dissolving in solution for spin coating, spray coating or solution printing.
When green, yellow and red light emitting materials with lower energy are doped into the blue light emitting material, the low-energy material preferentially emits light due to the principle of energy transfer from high to low, and the higher-energy blue light emitting material only plays the role of a host material or a light-emitting sensitization effect. Therefore, the double-boron organic luminescent material can also be used as a main body material of a green light, yellow light and red light organic electroluminescent luminescent layer, namely, the luminescent layer contains the double-boron organic luminescent material as the main body material, and then other luminescent materials with longer wavelength and smaller energy such as green light, yellow light and red light are doped for application. When electrons and holes are injected into the light-emitting layer of this configuration, the generated excitons emit light with the light-emitting material having the lowest energy.
In another case, the light-emitting layer may use a conventional host material and a conventional red or green light-emitting dopant, and the light-emitting layer may also be doped with the diboron-containing organic light-emitting material of the present invention as an energy-transfer sensitizer. The sensitizing functional material has an energy level between the host material and the light emitting dopant, and the injected electrons and holes or formed excitons are sequentially transferred from the host material in the light emitting layer to the sensitizer and then to the light emitting dopant according to the principle of energy transfer. This stepped energy transfer often increases device efficiency and device lifetime.
The technical effects and advantages of the invention are shown and verified by testing the practical performance of the diboron organic luminescent material specifically applied to the organic electroluminescent device.
The organic electroluminescent device is a multilayer sandwich structure, and comprises a cathode, an anode and a functional layer sandwiched between the two layers. The functional layer may be divided into a plurality of regions, such as an electron injection layer EIL and an electron transport layer ETL near the cathode, a hole injection layer HIL and a hole transport layer HTL near the anode, and an emission layer EML interposed between the electron transport layer and the hole blocking layer. Sometimes, in order to improve device performance, a hole blocking layer is interposed between the electron transport layer and the light emitting layer, and an electron blocking layer is interposed between the hole transport layer and the light emitting layer to adjust charge balance in the light emitting layer.
An organic electroluminescent device is a complex multilayer structure, and fig. 1 is a typical configuration, but not the only application configuration. The following description of the fabrication process of the organic electroluminescent device is provided with reference to fig. 1: transparent conductive glass is generally adopted, or a layer of indium-tin oxide ITO is plated on a transparent substrate to serve as an anode, then a hole injection layer HIL, a hole transport layer HTL, a light emitting layer EML, an electron transport layer ETL and an electron injection layer EIL are sequentially evaporated on the anode, and finally a layer of metal, such as aluminum metal, is added to serve as a cathode conductive and sealing layer. Many other simple or complex organic electroluminescent device structures, either commercially or in the literature, may be equally suitable for use within the scope of the present invention.
The light emitting mechanism of the device is that when ITO is positively charged and aluminum is negatively charged to a certain electric field, holes (positive charges) are injected from ITO through HIL and HTL to EML, and electrons (negative charges) are injected from EIL connected with aluminum and then are transmitted to EML through ETL. The electrons and holes meet and recombine in the EML to form excitons (exitons), and then part of the excitons release energy in the form of light radiation and transition back to the ground state, with the emission wavelength determined by the energy gap of the emitting dopant in the EML layer.
The host materials are commonly used with carbazole or arylamine containing materials, one commonly used known green host material is mCBP, and the blue host material is BH1, DPEPO:
Figure BDA0003340744320000201
in order to inject charges (holes and electrons) into a device better and reduce the operating voltage of the device, HIL and EIL are generally added near the anode and the cathode respectively, such as the commonly used hole injection material HATCN, the electron injection material lithium hah, lithium fluoride or LiQ, etc.:
Figure BDA0003340744320000211
in order to achieve excellent performance of the light-emitting device, a hole transport layer and an electron transport layer may be further selected between the hole injection layer and the light-emitting layer and between the electron injection layer and the light-emitting layer, respectively, such as a hole transport material NPB, an electron transport material B3PyPB, TPBi:
Figure BDA0003340744320000212
in order to adjust the balance between holes and electrons in the light-emitting layer and improve the device performance, an electron blocking material or a hole blocking material may be respectively inserted between the hole transport layer and the light-emitting layer and between the electron transport layer and the light-emitting layer, such as an electron blocking material EB1, a hole blocking material HB 1:
Figure BDA0003340744320000213
many other hole injection materials, hole transport materials, electron blocking materials, host materials, hole blocking materials, electron transport materials, electron injection materials have been developed in the literature or commercially and may be equally suitable for use within the scope of the present invention.
The organic electroluminescent device according to the invention is further described below by means of specific device examples.
Device example 1
Evaporation OLED device application example-bisboron organic light emitting material of the invention as light emitting dopant material:
specifically, the preparation process of the OLED device of the invention is as follows: the transparent substrate coated with the ITO anode material was washed with a detergent and pure water in this order, further ultrasonically washed in pure water for 10 minutes, and pre-dried with an air gunThen, the mixture was dried in an oven at 100 ℃ for 5 minutes and then subjected to UV-ozone washing. After the above washing, the substrate with the ITO anode was placed in a background vacuum of 10 deg.C-5In multi-source evaporation OLED equipment of Pa, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and an aluminum layer serving as a cathode are sequentially evaporated on an ITO anode layer at different evaporation rates of 0.1-1 nm/s, wherein the light-emitting layer adopts a multi-source co-evaporation method, and all materials in the light-emitting layer reach a preset doping proportion by adjusting the evaporation rates of a main body material, a sensitizer material and a light-emitting doping agent.
The invention adopts the following device structure: anode
Figure BDA0003340744320000222
Figure BDA0003340744320000223
Luminescent dopant
Figure BDA0003340744320000224
And the cathode is used for evaluating the performance of each double-boron organic light-emitting material applied to the OLED device. The specific OLED device structure is
Figure BDA0003340744320000225
:dopant 5％
Figure BDA0003340744320000226
Figure BDA0003340744320000227
The different luminescent doping materials of the present invention were used in a different way than the comparative known BD1 luminescent material, wherein the luminescent doping agent used for the comparative device example was BD1 and no HBL was used in the OLED structure.
Table 2: organic materials of the types described above for use in the respective device embodiments
Figure BDA0003340744320000221
Figure BDA0003340744320000231
Figure BDA0003340744320000241
Specific performance data for the OLED devices prepared for each device example are detailed in table 3 below.
Table 3: performance of the obtained OLED device (room temperature @1000 nits):
Figure BDA0003340744320000242
Figure BDA0003340744320000251
for reference, the driving voltage of the comparative device a was 5.5V, the external quantum efficiency EQE was 8.9%, the EL emission spectrum CIE (x, y) was (0.12,0.13), and the lifetime was LT 95% at 1000nits, 132 hours at 1000 nits.
It can be seen from the comparison of A, B in the above table 3 that the double-boron organic light-emitting material of the present invention, as a light-emitting dopant, is applied to blue, green and yellow OLED devices, and has the effects of reducing the operating voltage, increasing the light-emitting efficiency and the operating life of the devices.
In conclusion, the double-boron organic luminescent material of the invention has the effects of obviously increasing the luminescent performance (EQE) of the device, reducing the working voltage and prolonging the service life LT 95%.
Device example 2: application example of evaporation OLED device-application of the inventive bisboron organic light-emitting material as a light-emitting layer sensitizing dopant:
the specific OLED device structure is ITO/HATCN
Figure BDA0003340744320000252
And (4) dopant: sensitizers (Compounds of the invention)
Figure BDA0003340744320000253
Figure BDA0003340744320000254
Table 4: the compound of the invention is used as a luminescent layer sensitizing doping agent to apply OLED performance @1000nit
Figure BDA0003340744320000255
Figure BDA0003340744320000261
Table 4 above shows that the materials of the present invention, such as 26 and 48, can be used as "sensitizing" dopants, and the DPEPO material is used as a host, and the high-luminescence-efficiency fluorescent dye GD1 is doped, and the singlet excitons in the TADF material of the present invention transfer energy to the fluorescent dye GD1 through efficient Forster transfer, and emit light from the fluorescent dye GD1, so that a device with improved luminescence efficiency performance can be obtained.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way. It will be apparent to those skilled in the art that many changes and modifications may be made, or equivalents modified, in the disclosure set forth above without departing from the scope of the invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the protection scope of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.

Claims (6)

1. A double boron organic luminescent material has a chemical structure shown as a general formula (I):
Figure FDA0003340744310000011
in the general formula (I), Ar1And Ar2Is six-membered benzene ring, six-membered aromatic heterocyclic ring, five-membered or six-membered condensed aromatic heterocyclic ring with carbon atom not more than 18 and R of the rings1A substituent;
ar is1And Ar2Ring c and/or R independently and adjacently adjacent to each othercRing d and/or RdLinked to form a ring or not linked to form a ring, wherein the linkage to form a ring may be through-O-, -S-, -CR2R3-or a single bond connection;
the R is1、R2、R3、Ra、Rb、Rc、RdOne or more substitutions satisfying the number of benzene ring or aromatic heterocyclic bond can be selected from hydrogen, deuterium, fluorine, substituted or unsubstituted C1-12Alkyl, substituted or unsubstituted C1-12Alkoxy, substituted or unsubstituted C3-12Cycloalkyl, substituted or unsubstituted C1-12Alkylsilyl, substituted or unsubstituted C6-16Aryl group of (2), substituted or unsubstituted C containing one or more heteroatoms4-16Heteroaryl, substituted or unsubstituted C6-16A fused heteroaryl group of (a);
the substituent of the substitutable group is selected from deuterium, halogen, cyano, C1-12Alkyl radical, C3-12Cycloalkylmethyl group of (A), C1-12Alkoxy group of (C)6-16Aryl group of (2), substituted or unsubstituted C containing one or more heteroatoms4-16One or more of heteroaryl;
the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
2. The general formula of a bisboron organic light-emitting material according to claim 1, wherein Ar is Ar1、Ar2Each independently represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted biphenylene group, a,A substituted or unsubstituted terphenylene group, a substituted or unsubstituted dimethylene fluorenyl group, a substituted or unsubstituted diphenylene fluorenyl group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted naphthyridinyl group;
ar is1And Ar2Ring c and/or R independently and adjacently adjacent to each othercRing d and/or RdLinked to form a ring or not linked to form a ring, wherein the linkage to form a ring may be through-O-, -S-, -CR2R3-or a single bond connection;
the R is1-R3、Ra-RdEach independently represents a hydrogen atom, deuterium, a fluorine atom, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, methoxy, trimethylsilyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenylyl, substituted or unsubstituted terphenylyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted furyl, substituted or unsubstituted benzofuryl, substituted or unsubstituted dibenzofuryl, substituted or unsubstituted thienyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted azacarbazolyl, substituted or unsubstituted benzindenyl, Substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted benzophenanthryl, substituted or unsubstituted azabenzophenanthryl;
the substituent of the substitutable group is selected from one or more of deuterium, fluorine atom, cyano group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, pentyl group, phenyl group, naphthyl group, biphenyl group, pyridyl group, furyl group or thienyl group.
3. The diboron organic light emitting material of claim 1, wherein said compound of formula (la) comprises the following specific structure:
Figure FDA0003340744310000021
Figure FDA0003340744310000031
Figure FDA0003340744310000041
Figure FDA0003340744310000051
Figure FDA0003340744310000061
。
4. an organic light-emitting device comprising a cathode, an electron transport layer adjacent to the cathode, an anode, a hole transport layer adjacent to the anode, and a light-emitting layer sandwiched between the electron transport layer and the hole transport layer, wherein the light-emitting layer comprises at least one bisboron organic light-emitting material as claimed in any one of claims 1 to 3.
5. The organic light-emitting device according to claim 4, wherein the light-emitting dopant in the light-emitting layer is the diboron organic light-emitting material according to any one of claims 1 to 3, and accounts for 1 to 49 wt% of the light-emitting layer.
6. The organic light-emitting device according to claim 4, wherein the energy-transfer sensitizing material in the light-emitting layer is the diboron organic light-emitting material according to any one of claims 1 to 3, and accounts for 5 to 49 wt% of the light-emitting layer.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115433217A (en) * 2022-08-12 2022-12-06 苏州大学 Carbonyl-fused boron-nitrogen derivative and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109679072A (en) * 2018-12-29 2019-04-26 武汉天马微电子有限公司 Polymer, display panel and display device
CN111377955A (en) * 2018-12-29 2020-07-07 江苏三月光电科技有限公司 Boron-containing compound and preparation method and application thereof
CN112679532A (en) * 2020-11-11 2021-04-20 西安交通大学 Boron-nitrogen-benzene shunt thiophene derivative, conjugated high-molecular polymer, preparation method of conjugated high-molecular polymer and application of conjugated high-molecular polymer in fluorine ion detection
CN112679531A (en) * 2019-10-18 2021-04-20 北京鼎材科技有限公司 Boron-containing compound and organic electroluminescent device containing same
CN113072568A (en) * 2020-01-04 2021-07-06 江苏三月光电科技有限公司 Organic electroluminescent material containing double boron and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109679072A (en) * 2018-12-29 2019-04-26 武汉天马微电子有限公司 Polymer, display panel and display device
CN111377955A (en) * 2018-12-29 2020-07-07 江苏三月光电科技有限公司 Boron-containing compound and preparation method and application thereof
CN112679531A (en) * 2019-10-18 2021-04-20 北京鼎材科技有限公司 Boron-containing compound and organic electroluminescent device containing same
CN113072568A (en) * 2020-01-04 2021-07-06 江苏三月光电科技有限公司 Organic electroluminescent material containing double boron and application thereof
CN112679532A (en) * 2020-11-11 2021-04-20 西安交通大学 Boron-nitrogen-benzene shunt thiophene derivative, conjugated high-molecular polymer, preparation method of conjugated high-molecular polymer and application of conjugated high-molecular polymer in fluorine ion detection

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115433217A (en) * 2022-08-12 2022-12-06 苏州大学 Carbonyl-fused boron-nitrogen derivative and preparation method and application thereof
CN115433217B (en) * 2022-08-12 2023-08-25 苏州大学 Carbazole-fused boron-nitrogen derivative and preparation method and application thereof
WO2024031919A1 (en) * 2022-08-12 2024-02-15 苏州大学 Carbazole fused boron-nitrogen derivative, preparation method therefor, and use thereof

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