CN116655666A - Boron-containing organic compound and light-emitting device - Google Patents

Boron-containing organic compound and light-emitting device Download PDF

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CN116655666A
CN116655666A CN202310539776.XA CN202310539776A CN116655666A CN 116655666 A CN116655666 A CN 116655666A CN 202310539776 A CN202310539776 A CN 202310539776A CN 116655666 A CN116655666 A CN 116655666A
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boron
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崔林松
朱向东
叶志峰
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University of Science and Technology of China USTC
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    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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Abstract

The application provides a boron-containing organic compound and a light-emitting device, wherein the boron-containing organic compound is a compound shown as a formula (III):wherein R is 1 ～R 14 Any one selected from hydrogen atoms and substituted or unsubstituted C1-C20 alkyl groups; m is a substituted or unsubstituted aryl of C6 to C40.

Description

Boron-containing organic compound and light-emitting device
The application is a divisional application of Chinese patent application (application day: 2021, 11, 26, title: boron-containing organic compound and light-emitting device) with application number 202111418443.9.
Technical Field
The application relates to the technical field of organic photoelectricity, in particular to a boron-containing organic compound and a light-emitting device.
Background
The organic electroluminescent device has a series of advantages of autonomous luminescence, low-voltage driving, full solidification, wide viewing angle, simple composition and process and the like; in contrast to liquid crystal displays, organic electroluminescent devices do not require a backlight. Therefore, the organic electroluminescent device has wide application prospect.
The organic electroluminescent device generally includes an anode, a metal cathode, and an organic layer sandwiched therebetween. The organic layer mainly comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer. In addition, the light-emitting layer mostly adopts a host-guest structure. That is, the light emitting material is doped in the host material at a concentration to avoid concentration quenching and triplet-triplet annihilation, thereby improving light emitting efficiency. In the structure of the organic electroluminescent device, if a voltage is applied between two electrodes, electrons and holes are injected and transported from the cathode and anode, respectively, into the light emitting layer to form excitons, and light is emitted when the excitons fall to the ground state again.
In recent years, some properties specific to boron elements have led to great research interest in boron-containing pi-conjugated materials. In molecular design, by reasonably utilizing the characteristics of boron element and introducing the boron element into different positions of a pi-conjugated system, organic pi-conjugated new materials with different structural types and unique photoelectric properties can be obtained, such as electron transport materials and luminescent materials in organic electroluminescent devices, chemical sensor materials, organic photovoltaic materials and the like.
The blue light boron nitrogen material is a relatively popular multi-resonant thermally excited delayed fluorescent material (MR-TADF), and although the material can theoretically utilize triplet states to improve the utilization ratio of excitons to 100%, the currently commercially available blue light boron nitrogen triplet state excitons have long service life, so that the service life of the device is shorter and the efficiency roll-off is larger under high current density, so that a plurality of panel manufacturers mostly select a method for improving the service life of the device to reduce the efficiency of the device, namely only the singlet state luminescence of the material is used. How to industrially use triplet excitons of such materials to improve device efficiency and ensure longer device lifetime still faces a number of key issues; in addition, the blue light boron nitrogen molecules which are commercialized at present have a better plane structure, so that the self-quenching effect is very serious under high-concentration doping, devices are usually required to be prepared under extremely low doping concentration, and the operability of the process is seriously affected.
Disclosure of Invention
The application provides a boron-containing organic compound and a light-emitting device, wherein a steric hindrance group and a low triplet state group are introduced: 1) The steric hindrance group is introduced to form a torsion three-dimensional structure, so that the concentration quenching effect of the multi-resonance thermally-excited delayed fluorescent material caused by the self-plane structure can be effectively avoided; 2) The introduction of the low triplet state group can effectively reduce the triplet state energy of the boron-containing organic compound, increase the energy difference between the singlet state and the triplet state of the material, effectively inhibit the triplet state excitons with long service life from returning to the singlet state through the process of crossing between the opposite systems, prevent the formation of the excitons with long service life, and further improve the performance of the device and ensure the service life of the device.
In order to achieve the above object, as an embodiment of one aspect of the present application, there is provided a boron-containing organic compound comprising a compound represented by any one of the formulas (I) to (III):
R 1 ～R 14 and is selected from any one of the following groups: hydrogen atom, deuterium atom, halogen, cyano group, NO 2 、N(R) 2 、OR、SR、C(＝O)R、P(＝O)R、Si(R) 3 Substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C5-C40 heteroaryl, whereinR is selected from any one of the following groups: a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C5-C30 heteroaryl group; m is a substituted or unsubstituted aryl of C6-C48; x is X 1 、X 2 And is selected from any one of the following groups: o, S, N-Y, C (Y) 2 Wherein Y is selected from any one of the following groups: substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C40 aryl, or substituted or unsubstituted C5-C40 heteroaryl.
As an embodiment of another aspect of the present application, there is provided a light emitting device including a first electrode, a second electrode, and an organic layer provided between the first electrode and the second electrode, the organic layer containing at least one of the above-described boron-containing organic compounds.
According to the application, the aromatic group is introduced into the para position of the boron element, so that the exciton utilization rate of the compound is improved through the triplet-triplet quenching (TTA) effect under the conditions of no change of the luminescence peak of the boron-containing compound, high thermal stability, good transmission performance and high fluorescence quantum yield, and the device efficiency is finally improved.
Drawings
FIG. 1 is a fluorescence spectrum of compounds 1-1 and BD2 in toluene solution in an example of the present application;
FIG. 2 is a fluorescence spectrum of compounds 2-6, 2-1 and BD1 in toluene solution in examples of the present application;
fig. 3 is a construction diagram of an organic electroluminescent device in an embodiment of the present application.
Reference numerals:
1-base plate, 2-anode, 3-hole injection layer, 4-hole transport layer, 5-electron blocking layer, 6-luminescent layer, 7-hole blocking layer, 8-electron transport layer, 9-electron injection layer, 10-cathode.
Detailed Description
The present application will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present application more apparent.
The p pi-pi conjugation effect between the empty p orbitals of boron atoms and pi orbitals of pi-conjugated systems, and the introduction of boron into pi-conjugated systems can impart some unique photoelectric properties to the systems. The construction of pi-conjugated photoelectric functional material by using boron is mainly based on the characteristics of boron: (1) specific orbital interactions: the empty p orbitals of the outermost layer of boron element and pi orbitals of a pi-conjugated system can form pi-pi conjugation, so that the lowest unoccupied orbital (LUMO) energy level of the system is reduced; (2) Lewis acidity: due to the existence of an empty p orbit, boron is easy to complex with Lewis base (such as fluoride ion) and break p pi-pi conjugation, so that the photoelectric performance of a corresponding system is obviously changed; (3) large steric hindrance effect: due to the existence of empty p orbitals, it is often necessary to introduce a bulky aromatic group on the boron atom in order to increase the stability of organoboron pi-conjugated compounds.
According to one aspect of the present general inventive concept, there is provided a boron-containing organic compound comprising a compound represented by any one of formulas (I) to (III):
R 1 ～R 14 and is selected from any one of the following groups: hydrogen atom, deuterium atom, halogen, cyano group, NO 2 、N(R) 2 、OR、SR、C(＝O)R、P(＝O)R、Si(R) 3 A substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C40 aryl group, a substituted or unsubstituted C5-C40 heteroaryl group, wherein R is selected from any one of the following groups: a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C5-C30 heteroaryl group; m is a substituted or unsubstituted aryl of C6-C48;X 1 、X 2 and is selected from any one of the following groups: o, S, N-Y, C (Y) 2 Wherein Y is selected from any one of the following groups: substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C40 aryl, or substituted or unsubstituted C5-C40 heteroaryl.
According to the application, the aromatic group is introduced into the boron element, and the conjugated system has photoelectric property through p pi-pi conjugation formed between the p orbit of the outermost layer and pi-pi orbit of the pi-conjugated system, so that the boron-containing compound has the advantages of narrow luminous peak, high thermal stability, good transmission performance and high fluorescence quantum yield.
In the present application, the term "substituted or unsubstituted" means that a group or ring system may be substituted with one or more groups or ring systems, or may remain unsubstituted.
According to an embodiment of the present application, the boron-containing organic compound may have structures represented by the following general formulae (S-1) to (S-6) (not limited thereto), wherein when N-Y is simultaneously present in the general formula (S-6), two Y' S may be the same or different. Preferably, Y is independently selected from any one of the following groups: substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C5-C18 heteroaryl.
According to an embodiment of the application, R 1 ～R 14 A group selected from any one of the following: substituted or unsubstituted alkyl, preferably C1-C6; substituted or unsubstituted alkenyl, preferably C2-C6; substituted or unsubstituted alkynyl, preferably C2 to C6; substituted or unsubstituted aryl, preferably C6-C18; substituted or unsubstituted heteroaryl, preferably C5-C18.
According to an embodiment of the application, the heteroatom in the C5-C40 heteroaryl is selected from any one of the following: n, O, S, P, as, si, preferably N, O, S; the number of heteroatoms in the C5-C40 heteroaryl groups is 1 to 10, preferably 1 to 5.
According to an embodiment of the application, the aryl group of C6-C48 in M is selected from any one of the following: benzene ring of a monocyclic system, biphenyl ring of a bicyclic system, naphthalene ring of a condensed bicyclic system, terphenyl ring of a tricyclic system (m-terphenyl, o-terphenyl, p-terphenyl), acenaphthene ring of a condensed tricyclic system, fluorene ring, phenalene ring, phenanthrene ring, fluoranthene, triphenylene ring of a condensed tetracyclic system, pyrene ring, tetracene ring, perylene ring of a condensed pentacyclic system, pentacene ring.
According to an embodiment of the present application, the boron-containing organic compound of the present application is selected from any one of the following compounds:
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according to an embodiment of the application, M is selected from any one of the following groups:
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wherein A is 1 ～A 6 ，B 1 ～B 9 ，C 1 ～C 8 ，D 1 ～D 9 ，E 1 ～E 6 ，F 1 ～F 7 ，G 1 ～G 10 ，H 1 ～H 9 ，K 1 ～K 12 ，L 1 ～L 6 ，M 1 ～M 12 ，N 1 ～N 10 ，O 1 ～O 17 ，P 1 ～P 15 ，Q 1 ～Q 15 ，I i ～I 15 ，R 1 ～R 15 ，S 1 ～S 13 ，T 1 ～T 13 ，U 1 ～U 12 ，V 1 ～V 12 ，W 1 ～W 17 ，X 1 ～X 15 ，Y 1 ～Y 15 ，Z 1 ～Z 15 ，J 1 ～J 15 ，Aa 1 ～Aa 15 ，Bb 1 ～Bb 15 ，Cc l ～Cc 16 ，Dd 1 ～Dd 15 ，Ee 1 ～Ee 15 ，Ff 1 ～Ff 15 ，Gg 1 ～Gg 15 ，Hh 1 ～Hh 17 ，Ii 1 ～Ii 15 ，Jj 1 ～Jj 15 And is selected from any one of the following groups: a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C5-C30 heteroaryl group.
According to the embodiment of the application, the "position of the dotted line can be moved" means that a group has a plurality of different positions, such as one position and two positions, which can be connected to the main body portion.
According to an embodiment of the application, the C1-C20 alkyl group is selected from any one of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, n-decyl, hexadecyl, octadecyl, eicosyl, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl.
According to embodiments of the application, the C1-C20 alkyl groups are linear, branched or cyclic.
According to an embodiment of the application, the C2-C20 alkenyl group is selected from any one of the following groups: ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, 2-ethylhexyl, allyl or cyclohexenyl.
According to embodiments of the application, the C2-C20 alkenyl group is linear, branched or cyclic.
According to an embodiment of the application, the C2-C20 alkynyl group is selected from any one of the following groups: ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl.
According to embodiments of the application, the C2-C20 alkynyl group is linear, branched or cyclic.
According to an embodiment of the application, the C6-C40 aryl is selected from any one of the following groups: phenyl, naphthyl, anthryl, benzanthraceyl, phenanthryl, benzophenanthryl, pyrenyl, perylenyl, fluoranthryl, benzofluoranthryl, naphthaceneyl, pentacenyl, benzopyrenyl, biphenyl, terphenyl, tetrabiphenyl, pentabiphenyl, terphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis or trans indenofluorenyl, cis or trans mono-benzindenyl fluorenyl, cis or trans dibenzoindenofluorenyl, trimeric indenyl, heterotrimeric indenyl, spirotrimeric indenyl, spiroheterotrimeric indenyl.
According to an embodiment of the application, the C6-C40 aryl is preferably phenyl, naphthyl, anthryl, phenanthryl, benzanthraceyl, benzophenanthryl.
According to an embodiment of the application, the heteroaryl group of C5 to C40 is selected from any one of the following groups: furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, pyridyl, quinolinyl, isoquinolinyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolinyl, benzo-6, 7-quinolinyl, benzo-7, 8-quinolinyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthazolyl, anthraceneoxazolyl, phenanthrooxazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-naphthyridine, 1, 5-nitrogen-3, 5-dipyrene, 1, 4-dipyrene, 5-dipyrene, 1, 5-naphthyridine, 4-dipyrene, 10-tetrazole perylene group, pyrazinyl group, phenazinyl group, phenoxazinyl group, phenothiazinyl group, fluoroyl group, naphthyridinyl group, azacarbazolyl group, benzocarboline group, phenanthroline group, 1,2, 3-triazolyl group, 1,2, 4-triazolyl group, benzotriazole group, 1,2, 3-oxadiazolyl group, 1,2, 4-oxadiazolyl group, 1,2, 5-oxadiazolyl group, 1,3, 4-oxadiazolyl group, 1,2, 3-thiadiazolyl group, 1,2, 4-thiadiazolyl group, and, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, and the like, preferably phenyl, naphthyl, anthracenyl, phenanthrenyl, benzoxanthenyl, benzophenanthryl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, and the like.
According to an embodiment of the present application, the heteroaryl group of C6 to C40 is preferably furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, more preferably carbazolyl.
According to an embodiment of the application, the substituents in the substituted C6-C40 aryl and substituted C5-C40 heteroaryl groups are selected from any one of the following groups: deuterium atom, halogen, amino, hydroxyl, cyano, C1-C6 alkyl.
According to embodiments of the present application, the number of substituents in the C6-C40 aryl and C5-C40 heteroaryl groups is 1 to 5, preferably 1 to 3.
According to an embodiment of the application, the C1-C6 alkyl group is selected from any one of the following groups: methyl, t-butyl.
The application will be described in detail with reference to specific examples.
Synthesis of Compound 1-1 Using the following synthetic route
Step one: synthetic intermediate 1-1
To a three-necked flask equipped with a reflux condenser was successively added 5-bromo-1, 3-difluoro-2-iodobenzene (15.9 g,50.0 mmol), 3, 6-di-tert-butylcarbazole (27.86 g,100.0 mmol), sodium hydride (3.00 g,125.0 mmol) and DMF (200 mL) under nitrogen atmosphere, and heated under reflux for 6h. After the reaction was completed, the system was cooled to room temperature. Adding a large amount of water, generating white precipitate, and suction filtering and collecting. The precipitate was washed successively with water and 50% by volume methanol solution. Finally, the obtained filter cake was dissolved in a proper amount of dichloromethane and further purified by column chromatography (petroleum ether and dichloromethane with a volume ratio of 3:1 as mobile phase) to obtain 37.6g of white solid with a yield of 90%.
The mass spectrum detection result of the obtained sample is as follows: MS (EI): m/z 836.22[ M + ]；C 46 H 50 BIN 2 Calculated values (%): c,65.95; h,6.02; n,3.34; actual measurement value: c,65.92; h,5.99; n,3.31.
Step two: synthetic intermediate 1-1-2
To a three-necked flask equipped with a reflux condenser was added sequentially intermediate 1-1-1 (37.6 g,50.0 mmol) and anhydrous meta-xylene (m-xylene) (300 mL) under nitrogen atmosphere, and the system was cooled to-40 ℃. N-butyllithium (25 mL,60mmol, 2.4M) was added dropwise to the system, and after the completion of the addition, stirring was continued at that temperature for 2 hours, boron tribromide (19.0 g,75 mmol) was added dropwise. After the completion of the dropwise addition, the reaction was continued at 50℃for 4 hours. The system was then cooled to 0deg.C, N-ethyldiisopropylamine (13.5 g,100 mmol) was added, after which the temperature was gradually increased to 125deg.C and the reaction continued at that temperature for 12h. After the reaction was completed, the solvent was distilled off under reduced pressure, and the crude product was purified by column chromatography (petroleum ether and methylene chloride in a volume ratio of 9:1 as mobile phases) to give 19.4g of a yellow solid in 60% yield.
The mass spectrum detection result of the obtained sample is as follows: MS (EI): m/z 720.31[ M + ]；C 46 H 48 BBrN 2 Calculated values (%): c,76.78; h,6.72; n,3.89; actual measurement value: c,76.73; h,6.69; n,3.84.
Step three: synthesis of Compound 1-1
To a clean 100mL three-necked flask under nitrogen atmosphere were successively added 3.6g (5.0 mmol) of the intermediate 1-1-2, 1.3g (12.4 mmol) of anhydrous sodium carbonate, 2.5g (5.3 mmol) of deuterated phenylanthracene boron-lipid, 68.3mg (0.06 mmol) of tetrakis (triphenylphosphine) palladium and 45mL of a mixed solvent (toluene: water: ethanol in a volume ratio of 30:8:7), and the system was warmed to reflux and reacted overnight under reflux. After the reaction is completed, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200mL of water and extracted with methylene chloride. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, petroleum ether and methylene chloride in a volume ratio of 3:2 as mobile phase) to give 3.5g of a yellow solid in 80% yield.
The mass spectrum detection result of the obtained sample is as follows: MS (EI): m/z 897.53[ M + ]. Calculated value of elemental analysis C 66 H 56 D 5 BN 2 (%): c,88.27; h,7.41; b,1.20; n,3.12; actual measurement value: c,88.23; h,7.37; b,1.15; n,3.07.
Compounds 2-6 were synthesized using the following scheme
Step one: synthetic intermediate 2-6-1
To a three-necked flask equipped with a reflux condenser was successively added 5-bromo-1, 3-difluoro-2-iodobenzene (15.9 g,50.0 mmol), bis (4-t-butylphenyl) amine (28.07 g,100.0 mmol), sodium hydride (3.00 g,125.0 mmol) and DMF (200 mL) under nitrogen atmosphere, and heated under reflux for 6h. After the reaction was completed, the system was cooled to room temperature. Adding a large amount of water, generating white precipitate, and suction filtering and collecting. The precipitate was washed successively with water and 50% by volume methanol solution. Finally, the obtained filter cake was dissolved in a proper amount of dichloromethane and further purified by column chromatography (petroleum ether and dichloromethane with a volume ratio of 3:1 as mobile phase) to obtain 39g of white solid with a yield of 95%.
The mass spectrum detection result of the obtained sample is as follows: MS (EI): m/z 840.25[ M + ]；C 46 H 54 BrIN 2 Calculated values (%): c,65.64; h,6.47; n,3.33; actual measurement value: c,65.59; h,6.45; n,3.31.
Step two: synthesis of intermediate 2-6-2
To a three-necked flask equipped with a reflux condenser was added sequentially intermediate 2-6-1 (39 g,46.33 mmol) and anhydrous meta-xylene (m-xylene) (300 mL) under nitrogen atmosphere, and the system was cooled to-40 ℃. N-butyllithium (25 mL,60mmol, 2.4M) was added dropwise to the system, and after the completion of the addition, stirring was continued at that temperature for 2 hours, boron tribromide (19.0 g,75 mmol) was added dropwise. After the completion of the dropwise addition, the reaction was continued at 50℃for 4 hours. The system was then cooled to 0deg.C, N-ethyldiisopropylamine (13.5 g,100 mmol) was added, after which the temperature was gradually increased to 125deg.C and the reaction continued at that temperature for 12h. After the reaction was completed, the solvent was distilled off under reduced pressure, and the crude product was purified by column chromatography (petroleum ether and methylene chloride in a volume ratio of 9:1 as mobile phases) to give 20.11g of a yellow solid in 60% yield.
The mass spectrum detection result of the obtained sample is as follows: MS (EI): m/z 722.34[ M + ]；C 46 H 52 BBrN 2 Calculated values (%): c,76.78; h,6.72; n,3.89; actual measurement value: c,76.75; h,6.65; n,3.87.
Step three: synthesis of Compounds 2-6
To a clean 100mL three-necked flask under nitrogen atmosphere were successively added 3.62g (5.0 mmol) of intermediate 2-6-2, 1.3g (12.4 mmol) of anhydrous potassium carbonate, 1.9g (5.00 mmol) of 1-perylene boron ester, 68.3mg (0.06 mmol) of tetrakis (triphenylphosphine) palladium and 45mL of a mixed solvent (toluene: water: ethanol in a volume ratio of 30:8:7), and the system was warmed to reflux and reacted overnight under reflux. After the reaction is completed, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200mL of water and extracted with methylene chloride. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether and dichloromethane in a volume ratio of 3:2) to give 2.7g of a yellow solid in 60% yield.
The mass spectrum detection result of the obtained sample is as follows: MS (EI): m/z 890.23[ M + ]. Calculated value of elemental analysis C 66 H 59 BN 2 (%): c,88.97; h,6.67; n,3.14; actual measurement value: c,88.80; h,6.61; n,3.10.
Synthesis of Compound 2-1 Using the following scheme
To a clean 100mL three-necked flask under nitrogen atmosphere were successively added 3.62g (5.0 mmol) of intermediate 2-6-2, 1.3g (12.4 mmol) of anhydrous sodium carbonate, 1.64g (5.00 mmol) of 1-pyrenylboronic acid, 68.3mg (0.06 mmol) of tetrakis (triphenylphosphine) palladium and 45mL of a mixed solvent (toluene: water: ethanol in a volume ratio of 30:8:7), and the system was warmed to reflux and reacted overnight in a reflux state. After the reaction is completed, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200mL of water and extracted with methylene chloride. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent: petroleum ether: dichloromethane in a volume ratio of 3:2) to give 2.5g of a yellow solid in 60% yield.
The mass spectrum detection result of the obtained sample is as follows: MS (EI): m/z 844.49[ M + ]. Calculated value of elemental analysis C 62 H 61 BN 2 (%): c,88.13; h,7.28; n,3.32; actual measurement value: c,88.10; h,7.26; n,3.27.
Compounds 2-7 were synthesized using the following scheme
To a clean 100mL three-necked flask under nitrogen atmosphere were successively added 3.62g (5.0 mmol) of intermediate 2-6-2, 1.3g (12.4 mmol) of anhydrous sodium carbonate, 1.80g (5.00 mmol) of 9,9' -spirobifluorene-3-boric acid, 68.3mg (0.06 mmol) of tetrakis (triphenylphosphine) palladium and 45mL of a mixed solvent (toluene: water: ethanol in a volume ratio of 30:8:7), and the system was warmed to reflux and reacted overnight in a reflux state. After the reaction is completed, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200mL of water and extracted with methylene chloride. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent: petroleum ether: dichloromethane in a volume ratio of 3:2) to give 3.1g of a yellow solid in 65% yield.
The mass spectrum detection result of the obtained sample is as follows: MS (EI): m/z 958.49[ M + ]. Calculated value of elemental analysis C 71 H 67 BN 2 (％)：C，88.91; h,7.04; n,2.92; actual measurement value: c,88.90; h,7.02; n,2.90.
According to another aspect of the present general inventive concept, there is provided a light emitting device including a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, the organic layer containing at least one of the above-described boron-containing organic compounds.
The boron-containing organic compound can be used for aspects such as organic electroluminescent devices, organic solar cells, organic diodes and the like. The organic light-emitting device prepared from the polycyclic boron-containing compound has the advantages of high light-emitting efficiency, long service life, low driving voltage, narrow half-peak width, high color purity and the like, is an organic electroluminescent material with excellent performance, and finally in an OLED device, the device performance of the material is further improved.
Fig. 3 is a construction diagram of an organic electroluminescent device in an example of the present application. As shown in fig. 3, an anode 2, a hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9, and a cathode 10 are sequentially disposed on a substrate 1.
According to an embodiment of the present application, an organic electroluminescent device may be manufactured by sequentially stacking a first electrode, an organic layer, and a second electrode on a substrate. The specific manufacturing process is as follows: an anode is formed by vapor deposition of a metal or a metal oxide having conductivity or an alloy thereof on a substrate by PVD (physical vapor deposition) method such as sputtering or electron beam evaporation, then an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed on the anode, and then a substance that can function as a cathode is vapor deposited on the organic layer.
According to the embodiment of the present application, the structure of the organic electroluminescent device may omit the hole injection layer 3 between the anode 2 and the hole transport layer 4, the hole blocking layer 7 between the light emitting layer 6 and the electron transport layer 8, and the electron injection layer 9 between the electron transport layer 8 and the cathode 10, into a configuration in which the anode 2, the hole transport layer 4, the light emitting layer 6, the electron transport layer 8, and the cathode 10 are sequentially disposed on the substrate 1.
According to an embodiment of the present application, the anode material of the organic electroluminescent device is selected from any one of the following: (1) Metals such as vanadium, chromium, copper, zinc, gold, and the like, or alloys thereof, for example, zinc oxide, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), znO: al, snO 2 : sb; (2) Electroconductive polymers, e.g. poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDOT), polypyrrole and polyaniline. Preferably Indium Tin Oxide (ITO).
According to an embodiment of the present application, the hole injection layer of the organic electroluminescent device is made of a material selected from any one of the following: porphyrin compounds represented by copper phthalocyanine, naphthalene diamine derivatives, star-shaped triphenylamine derivatives, arylamine compounds having a structure in which 3 or more triphenylamine structures are linked by a single bond or a divalent group containing no hetero atom in the molecule, triphenylamine trimers, tetramers, hexacyanoazabenzophenanthrene receptor-type heterocyclic compounds, and coated polymer materials. The hole injection layer material of the organic electroluminescent device may be formed into a thin film by vapor deposition, spin coating, or ink jet.
According to an embodiment of the present application, the hole transport layer of the organic electroluminescent device is made of a material selected from any one of the following: (1) M-carbazolylphenyl-containing compounds such as N, N ' -diphenyl-N, N ' -di (m-tolyl) benzidine (TPD), N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), (2) benzidine derivatives such as N, N ' -tetrabiphenyl benzidine; (3) 1, 1-bis [ (di-4-tolylamino) phenyl ] cyclohexane (TAPC); (4) various triphenylamine trimers and tetramers; (4) 9,9',9 "-triphenyl-9H, 9' H, 9" H-3,3':6', 3' -tricarbazole (Tris-PCz). The above materials may be used alone, in the form of a single layer formed by mixing with other materials, or may be formed into a laminated structure of layers formed alone, a laminated structure of layers formed by mixing, or a laminated structure of layers formed alone and layers formed by mixing. The above material may be formed into a thin film by vapor deposition, spin coating, ink jet method, or the like.
According to the embodiment of the present application, a substance obtained by p-doping a material commonly used for the hole injection layer or the hole transport layer of the organic electroluminescent device with tribromoaniline hexachloride, an axial alkene derivative, or the like, a polymer compound having a structure of a benzidine derivative such as TPD in a part of the structure, or the like may be used.
According to an embodiment of the present application, the material of the electron blocking layer of the organic electroluminescent device is selected from any one of the following: carbazole derivatives such as 3,3' -bis (N-carbazolyl) -1,1' -biphenyl (mCBP), 4',4 "-tris (N-carbazolyl) triphenylamine (TCTA), 9-bis [4- (carbazol-9-yl) phenyl ] fluorene, 1, 3-bis (carbazol-9-yl) benzene (mCP), 2-bis (4-carbazol-9-ylphenyl) adamantane (Ad-Cz); a compound having a triphenylsilyl and triarylamine structure represented by 9- [4- (carbazol-9-yl) phenyl ] -9- [4- (triphenylsilyl) phenyl ] -9H-fluorene; monoamine compounds having high electron blocking properties, various triphenylamine dimers, and the like. The above materials may be used alone or in a single layer form by mixing with other materials, or may be formed into a laminated structure of layers formed alone, a laminated structure of layers formed by mixing, or a laminated structure of layers formed alone and layers formed by mixing. These materials may be formed into thin films by vapor deposition, spin coating, ink jet, or the like.
According to an embodiment of the present application, the material of the light emitting layer of the organic electroluminescent device is selected from any one of the following: luminescent material comprising organic electroluminescent compounds (boron-containing organic compounds) represented by the formula (I) to (III) and Alq 3 Various metal complexes such as metal complexes of the first hydroxyquinoline derivatives, compounds having a pyrimidine ring structure, anthracene derivatives, bisstyrylbenzene derivatives, pyrene derivatives, oxazole derivatives, and polyparaphenylene vinylene derivatives.
According to an embodiment of the present application, the light emitting layer of the organic electroluminescent device may be composed of a host material and a doping material. The host material may be selected from any one of the following: mCBP, mCP, anthracene derivatives, thiazole derivatives, benzimidazole derivatives, polydialkyl fluorene derivatives, heterocyclic compounds having an indole ring as a partial structure of a condensed ring, and the like. The doping material may be selected from any one of the following: preferably, the luminescent material contains an organic electroluminescent compound (boron-containing organic compound) represented by the formula (I) to (III). The doping weight ratio of the organic electroluminescent compound according to the application is preferably 0.1 to 50%, more preferably 0.2 to 20%, particularly preferably 0.5 to 10%.
According to an embodiment of the present application, the hole blocking layer of the organic electroluminescent device is made of any one of the following materials: metal complexes of quinolinol derivatives such as 2,4, 6-tris (3-phenyl) -1,3, 5-triazine (T2T), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), aluminum (III) bis (2-methyl-8-hydroxyquinoline) -4-phenylphenol salt (BAlq), various rare earth complexes, oxazole derivatives, triazole derivatives, triazine derivatives, and the like. The above materials may be used alone or in a single layer form by mixing with other materials, or may be formed into a laminated structure of layers formed alone, a laminated structure of layers formed by mixing, or a laminated structure of layers formed alone and layers formed by mixing. These materials may be formed into thin films by vapor deposition, spin coating, ink jet, or the like.
According to an embodiment of the present application, the material of the electron transport layer of the organic electroluminescent device is selected from any one of the following: alq 3 Metal complexes of hydroxyquinoline derivatives, including BAlq; various metal complexes; triazole derivatives; triazine derivatives; oxadiazole derivatives; pyridine derivatives; bis (10-hydroxybenzo [ H ]]Quinoline) beryllium (Be (bq 2)); such as 2- [4- (9, 10-dinaphthyl-2-anthracen-2-yl) phenyl]-benzimidazole derivatives such as 1-phenyl-1H-benzimidazole (ZADN); thiadiazole derivatives; an anthracene derivative; a carbodiimide derivative; quinoxaline derivatives; pyridoindole derivatives; phenanthroline derivatives; silole derivatives, and the like. The above materials may be used singly or in the form of a single layer formed by mixing with other materials, or may be usedThe laminated structure of the layers formed by the independent film formation, the laminated structure of the layers formed by the mixed film formation, or the laminated structure of the layers formed by the independent film formation and the layers formed by the mixed film formation is formed. These materials may be formed into thin films by vapor deposition, spin coating, ink jet, or the like.
According to an embodiment of the present application, the material of the electron injection layer of the organic electroluminescent device is selected from any one of the following: alkali metal salts such as lithium fluoride and cesium fluoride; alkaline earth metal salts such as magnesium fluoride; metal complexes of hydroxyquinoline derivatives such as lithium hydroxyquinoline; metal oxides such as alumina, and the like.
According to the embodiment of the present application, as a material that is generally used for the electron injection layer or the electron transport layer of the organic electroluminescent device, a material that is further N-doped with a metal such as cesium, a triarylphosphine oxide derivative, or the like can be used.
According to the embodiment of the application, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer and the electron transport layer of the organic electroluminescent device
According to the embodiment of the application, the cathode material of the organic electroluminescent device is selected from any one of the following materials: electrode materials having a low work function such as aluminum, magnesium, or alloys having a low work function such as magnesium silver alloy, magnesium indium alloy, aluminum magnesium alloy are used as the electrode materials.
According to the embodiment of the application, the substrate of the organic electroluminescent device can be used as the substrate in the traditional organic electroluminescent device, for example, glass or plastic, and glass substrate is preferred.
The organic electroluminescent device according to the present application will be described in detail with reference to specific examples.
Preparation of organic electroluminescent device 1 (organic EL device 1)
A hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9, and a cathode 10 were sequentially formed on a transparent anode 2 previously formed on a glass substrate 1 to prepare an organic electroluminescent device as shown in fig. 3. The preparation process comprises the following steps: glass base with ITO film with film thickness of 100nmThe plate was sonicated in a Decon 90 alkaline rinse, rinsed in deionized water, rinsed three times in each of acetone and ethanol, baked in a clean environment to completely remove water, rinsed with uv light and ozone, and bombarded with a low energy cation beam. Placing the glass substrate with ITO electrode into a vacuum chamber, and vacuumizing to 4×10 -4 ～2×10 -5 Pa. Then, 50% HIL1/50% HTL1 was vapor-deposited on the glass substrate with the ITO electrode at a vapor deposition rate of 0.2nm/s to form a layer having a film thickness of 10nm as a hole injection layer. On the hole injection layer, an HTL1 was vapor-deposited at a vapor deposition rate of 2.0nm/s to form a layer having a film thickness of 30nm as a hole transport layer. Three-source co-evaporation was performed on the hole transport layer at vapor deposition rates of BH1 and 5Cz-TRZ as host materials of 1.6nm/s and 0.4nms, respectively, and at vapor deposition rate of 1-1 as dopant material of 0.04nm/s, to form a layer having a film thickness of 20nm as a light-emitting layer, with a doping weight ratio of 1-1 of 2wt%. HBL1 was vapor-deposited on the light-emitting layer at a vapor deposition rate of 2.0nm/s to form a layer having a film thickness of 20nm as a hole blocking layer. On the hole stopper, 50% ETL1/50% Liq was vapor-deposited at a vapor deposition rate of 2.0nm/s to form a layer having a film thickness of 40nm as an electron transport layer. 8-hydroxyquinoline-lithium (Liq) was vapor-deposited on the electron transport layer at a vapor deposition rate of 0.2nm/s to form a layer having a film thickness of 2nm as an electron injection layer. Finally, aluminum was deposited at a deposition rate of 3.0nm/s or more to form a cathode having a film thickness of 100 nm.
Preparation of organic electroluminescent devices 2 to 3 (organic EL devices 2 to 3)
Organic EL devices 2 to 3 were fabricated under the same conditions as the organic EL device 1, except that the compounds in the following tables 1 and 2 were used in place of the compounds in each layer of the organic electroluminescent device 1 (organic EL device 1), respectively
Preparation of comparative organic electroluminescent device comparative examples 1 to 2
Comparative organic EL device comparative examples 1 to 2 were produced under the same conditions as the organic EL device 1 except that the compounds in table 1 below were used instead of the compounds in each layer of the organic EL device 1 (organic EL device 1), respectively.
TABLE 1
The structures of the compounds involved in the examples are as follows:
when a direct current voltage was applied to the organic EL devices 1 to 3 and the organic EL devices 1 to 2 fabricated in comparative examples 1 to 2 were measured for light emission characteristics in the atmosphere at normal temperature. The measurement results are shown in tables 2 and 3.
TABLE 2
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TABLE 3 Table 3
The current-luminance-voltage characteristics of the device were completed by the Keithley source measurement system (Keithley 2400 Sourcemeter, keithley 2000 Currentmeter) with corrected silicon photodiodes, the electroluminescence spectra were measured by the Photo research company PR655 spectrometer, and the external quantum efficiency of the device was calculated by the method of literature adv.
As can be seen from Table 2 and FIG. 1, compared with BD2, the boron-containing compound 1-1 of the application has no obvious change in fluorescence luminescence peak and half-peak width of the material by introducing low-triplet deuterated phenyl anthracene on the benzene ring in the B para position, and finally, the starting voltage of the device is obviously reduced in the device, the service life and efficiency of the device are improved, and the efficiency roll-off of the device under high current density is reduced.
As can be seen from Table 2 and FIG. 2, compared with BD1, the boron-containing compounds 2-6 and 2-1 of the application have no obvious change in fluorescence luminescence peak and half-peak width of the material by introducing low-triplet pyrene group perylene group on benzene ring in the para position B, and finally, the starting voltage of the device is obviously reduced in the device, the service life and efficiency of the device are improved, and the efficiency roll-off of the device under high current density is reduced.
As can be seen from Table 3, compared with BD1, the boron-containing compounds 2-7 of the application have significantly improved device performance and significantly reduced device turn-on voltage by introducing a steric group with large steric hindrance. Meanwhile, under the condition of different doping concentrations, the device efficiency is not obviously changed, and compared with the device efficiency of the comparative example material BD1, the quenching is serious along with the increase of the doping concentration.
According to the application, by introducing groups such as anthracene, pyrene and the like on the boron para-position aromatic ring, the generation of long-life triplet excitons is avoided, meanwhile, the fluorescence peak of the material does not generate obvious blue shift or red shift, and finally, the device performance of the material is further improved in an OLED device. In addition, the preparation method of the polycyclic boron-containing compound is simple, raw materials are easy to obtain, no isomer is generated, the purification process is simple, and the industrial development requirement can be met.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the application, and is not meant to limit the application thereto, but to limit the application thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the application.

Claims (6)

1. A boron-containing organic compound represented by the formula (III):
wherein R is 1 ～R 14 Any one selected from hydrogen atoms and substituted or unsubstituted C1-C20 alkyl groups; m is a substituted or unsubstituted aryl of C6 to C40.
2. The compound according to claim 1, wherein the C1-C20 alkyl is selected from any one of the following groups:
methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl;
the M is a substituted or unsubstituted aryl of C6-C40, and is selected from any one of the following groups:
phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthryl, benzophenanthryl, perylene.
3. A compound according to claim 1, wherein R 2 、R 5 、R 10 、R 13 Is tert-butyl, R 1 、R 3-4 、R 6-9 、R 11-12 、R 14 Is a hydrogen atom;
m is selected from any one of the following groups:
4. the compound according to claim 1, wherein the boron-containing organic compound is selected from any one of the following:
5. a light-emitting device comprising a first electrode, a second electrode, and an organic layer provided between the first electrode and the second electrode, wherein the organic layer contains at least one compound according to any one of claims 1 to 4 or compounds 2 to 7;
wherein the structures of the compounds 2-7 are as follows:
6. the light-emitting device according to claim 5, wherein the organic layer is a light-emitting layer comprising BH1 and optionally 5Cz-TRZ as host materials and at least one compound according to any one of claims 1 to 4 or compound 2-7 as doping material.
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