CN111377905A - Organic electroluminescent material and device - Google Patents

Organic electroluminescent material and device Download PDF

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CN111377905A
CN111377905A CN201811606122.XA CN201811606122A CN111377905A CN 111377905 A CN111377905 A CN 111377905A CN 201811606122 A CN201811606122 A CN 201811606122A CN 111377905 A CN111377905 A CN 111377905A
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孙恩涛
曾礼昌
吴俊宇
任雪艳
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Beijing Eternal Material Technology Co Ltd
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Abstract

The invention relates to a novel organic compound having the structure of formula (I):
Figure DDA0001923584680000011
wherein: one of A and B is a group represented by formula a, and the other is a substituted or unsubstituted phenylene group; l is a single bond, C6～C30Arylene radical, C3～C30One of heteroarylenes; ar is substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30One of the heteroaryl groups of (a); r1～R3Selected from hydrogen, C1～C12Alkyl radical, C1～C12Alkoxy, halogen, cyano, nitro, hydroxy, silyl, amino, C6～C30Arylamino, C3～C30Heteroarylamino group, C6～C30Aryl radical, C3～C30One kind of heteroaryl, n and p are integers of 0-4, and m is an integer of 0-2; x1、X2Is independently selected from CR4R5、NR6One of O, or S, and when X is2When is S, X1Is not NR6. The compound of the present invention shows excellent device performance and stability when used as a light emitting material in an OLED device. The invention also protects the organic electroluminescent device adopting the compound with the general formula.

Description

Organic electroluminescent material and device
Technical Field
The present invention relates to an organic compound which can be used as a light-emitting layer material of an organic electroluminescent device; the invention also relates to the application of the compound in an organic electroluminescent device.
Background
In recent years, organic light emitting devices based on phosphorescent metal complexes have been rapidly developed. Different from the traditional organic micromolecules and conjugated polymer materials, the transition metal complex can simultaneously obtain singlet excitons and triplet excitons, and the maximum internal quantum efficiency of 100% in theory is realized.
In classical phosphorescent OLED devices, in addition to the luminescent dye, a host material is also indispensable. The phosphorescent dye is not used as a light emitting layer alone, but is doped in a suitable host material to form a host-guest light emitting system to weaken the high concentration quenching effect of triplet excitons. In order to achieve efficient energy transfer, it is generally required that the energy gap of the host material is larger than that of the dye and the triplet energy level ET is higher than that of the dye molecule. Therefore, the T1 state energy can be smoothly transferred from the host material to the phosphorescent dye or the triplet excitons are limited in the dye molecules, so that the high-efficiency phosphorescent emission is realized.
CBP is a widely used phosphorescent host material, and it has been reported that an OLED device having high efficiency is obtained using BCP, BAlq, or the like as a hole blocking material. Japanese pioneer corporation et al have also reported the use of BALq derivatives as host materials to obtain high efficiency OLED devices.
Figure BDA0001923584670000011
In addition, since power efficiency is (pi/voltage) current efficiency, power efficiency is inversely proportional to voltage. In practical use, although the phosphorescent material has higher current efficiency than the fluorescent material, the power efficiency of the OLED device is not significantly improved due to the high operating voltage when BAlq, CBP or the like is used as the phosphorescent host material.
In addition, the glass transition temperature Tg of the host material is related to the film formability and thermal stability of the material. The material with low Tg temperature has poor thermal stability and is easy to crystallize or agglomerate, the service life of the device is greatly shortened, the efficiency of the device is seriously reduced, the thermal stability is poor due to the low glass transition temperature of CBP, and the thermal decomposition is easy to occur in the process of preparing the device by high-temperature evaporation. With OLED devices using such materials as hosts, the device lifetime is shorter due to higher voltages. Therefore, the development of a novel host material with high thermal stability and high photoelectric property has important practical application value.
International patent publication No. WO2017164632a1 also discloses that an indole derivative is used as a light-emitting host material, which can significantly reduce the voltage of the device, improve the efficiency of the device, and substantially increase the lifetime of the device. However, although these conventional materials have good photoelectric properties, the photoelectric properties thereof are still unsatisfactory in the rapidly developed organic electroluminescence field, and development of better host materials for phosphorescent devices is expected.
Disclosure of Invention
In view of the problems of the prior art, the present invention aims to provide new compounds for organic electroluminescent devices to meet the increasing demand for the photoelectric properties of OLED devices.
The present invention provides a compound represented by the following general formula (I),
Figure BDA0001923584670000021
wherein the content of the first and second substances,
A. b is different, one of which is a group represented by formula a and the other is a substituted or unsubstituted phenylene group.
X1、X2Same or different, each is independently selected from CR4R5、NR6O, or S; and when X2When is S, X1Is not NR6。
Preferably, X1Selected from the group consisting of CR4R5、NR6One of O or S, X2Selected from the group consisting of CR4R5、NR6Or O.
R mentioned above4～R6Each independently selected from hydrogen, substituted or unsubstituted C1～C10Alkyl, substituted or unsubstituted C6～C30Aryl of (2), or substituted or unsubstituted C3～C30A heteroaryl group.
Further, X is preferable1、X2Are each independently selected from CR4R5Or NR6More preferably X1And X2Are all methyl.
L is a single bond, substituted or unsubstituted C6～C30Arylene, substituted or unsubstituted C3～C30One of heteroarylenes.
Further, the general formula (1) is represented by any one of the following formulae (2-1) to (2-4):
Figure BDA0001923584670000031
in formulae (2-1) to (2-4): l, Ar, R1～R3、m、n、p、X1And X2Are as defined in formula (1) and formula a;
R7independently selected from hydrogen, C1～C12Alkyl radical, C1～C12Alkoxy, halogen, cyano, nitro, hydroxy, silyl, amino, substituted or unsubstituted C6～C30Arylamino, substituted or unsubstituted C3～C30Heteroarylamino, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30One of heteroaryl; r7May be condensed with the benzene ring to which they are attached to form C9～C30Aryl or heteroaryl, the aryl or heteroaryl formed being optionally substituted or unsubstituted C with 0, 1, 2, 3,4 or 5 each independently1～C12Alkyl, halogen, cyano, nitro, hydroxy, silyl, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30Substituted with a substituent in the heteroaryl group;
q is an integer of 0 to 4.
Further, in formula (1) and the following formulae (2-1) to (2-4), L is preferably a single bond, phenylene, biphenylene, naphthylene or pyridylene, specifically represented by the following structures:
Figure BDA0001923584670000032
wherein, indicates the bonding position with nitrogen atom or Ar group, and the expression mode of the ring structure crossed indicates that the connecting site is positioned at any position capable of forming a bond on the ring structure;
further, L is more preferably a single bond or phenylene group.
Further, in the formula (1) and the following formulae (2-1) to (2-4), Ar is a substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30One of the heteroaryl groups of (a). Further preferably, Ar is a substituted or unsubstituted N atom-containing C3～C30The heteroaryl group of (a); more preferably, Ar is a substituted or unsubstituted C containing 1 to 3N atoms3～C30A pi electron deficient heteroaryl group of (a);
further, Ar is preferably one of pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, 1, 8-naphthyridinyl, 2, 7-naphthyridinyl, and derivatives thereof.
Ar is most preferably quinazolinyl, quinoxalinyl, pyrimidinyl, triazinyl.
Further, Ar is selected from the following structures A1-A32:
Figure BDA0001923584670000041
in the formula (1) and the following formulae (2-1) to (2-4), R1～R3Are identical or different from each other and are each independently hydrogen, C1～C12Alkyl radical, C1～C12Alkoxy, halogen, cyano, nitro, hydroxy, silyl, amino, substituted or unsubstituted C6～C30Arylamino, substituted or unsubstituted C3～C30Heteroarylamino, substituted or unsubstituted C6～C30Aryl, or substituted or unsubstituted C3～C30A heteroaryl group; r1～R3Each independently fused to the attached benzene ring to form C9～C30Aryl or heteroaryl, the aryl or heteroaryl formed being optionally substituted or unsubstituted C with 0, 1, 2, 3,4 or 5 each independently1～C12Alkyl, halogen, cyano, nitro, hydroxy, silyl, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30Heteroaromatic compoundsSubstituted by a substituent in the group;
further, R1～R3Each independently preferably being H, F, Cl, Br, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, perylene, and the like,
Figure BDA0001923584670000052
A phenyl group, a furyl group, a thienyl group, a pyrrolyl group, a pyridyl group, a benzofuryl group, a benzothienyl group, an isobenzofuryl group, an indolyl group, a dibenzofuryl group, a dibenzothienyl group, a carbazolyl group, and derivatives thereof.
Further, R1～R3Preferably methyl, ethyl, tert-butyl, phenyl, naphthyl, phenanthryl, triphenylene, pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, and derivatives thereof;
in the formula (1) and the following formulae (2-1) to (2-4), n and p are the same or different from each other and each independently is an integer of 0 to 4; preferably, n and p are each independently an integer of 0 to 2. m is an integer of 0 to 2.
Still further, preferable examples of the compound of the present invention include the following representative compounds C1 to C81:
Figure BDA0001923584670000051
Figure BDA0001923584670000061
Figure BDA0001923584670000071
Figure BDA0001923584670000081
Figure BDA0001923584670000091
Figure BDA0001923584670000101
the invention also provides, as another aspect thereof, the use of a compound as described above in an organic electroluminescent device. The compounds of the invention are preferably used as light-emitting host materials in organic electroluminescent devices.
As still another aspect of the present invention, the present invention also provides an organic electroluminescent device comprising a first electrode, a second electrode and an organic layer comprising at least one light-emitting layer interposed between the first electrode and the second electrode, characterized in that the organic layer contains a compound represented by the above general formula (i) or formulae (2-1) to (2-4).
The fluorene-containing or heteroatom-containing aromatic ring indole compound provided by the invention is found to be taken as a main material of a luminescent layer to be introduced into an organic electroluminescent device, and particularly the performance of the device can be remarkably improved in the organic electroluminescent device with a phosphorescence luminescent mechanism.
The specific reason why the above-mentioned compound of the present invention having a core of an aromatic ring-indole compound containing a fluorene or a heteroatom is excellent as a host material is not clear, and it is presumed that the reason is as follows:
firstly, fluorene or aromatic ring indole containing hetero atom is used as electron donating group, and is connected with pyrimidine, triazine and their derivatives with pi electron deficiency property, and the compound of the present invention can be understood as a bipolar host material by analyzing the molecular structure. In theory, bipolar materials are ideal host materials because the organic functional layer based on the bipolar materials not only simplifies the device structure, but also can properly balance the transmission of carriers, thereby enabling excitons to be uniformly distributed, avoiding the recombination of the carriers at the interface, and reducing the quenching of triplet state-triplet state under high exciton concentration. In the molecular design, an electron-deficient acceptor group and an electron-rich donor group are connected to form an acceptor-donor molecule, so that the energy gap and the triplet state energy level of the molecule are improved, and the excellent bipolar phosphorescent host material with a higher triplet state and a wider energy gap can be obtained.
Secondly, the compounds have larger space structures, so that the stacked quenching of doped objects in energy transmission can be avoided, and the glass transition temperature Tg of the materials is greatly improved due to the larger space structures, so that the materials also have higher thermal and chemical stability. In the organic electroluminescent device, the material can be used as a bipolar host material of a doped light-emitting device.
Meanwhile, the compound of the invention has better molecular planarity, which is beneficial to forming an excellent thin film during film formation, is very beneficial to prolonging the service life of a device and is also beneficial to exerting more excellent photoelectric efficiency.
In the present invention, L is preferably a single bond or phenylene group in view of further improving the efficiency of the organic electroluminescent device. The reason for this is considered to be: the fluorene-containing or heteroatom-containing aromatic ring indole structure is used as an electron donating group and is directly connected with a quinazoline group, a triazine group and derivatives thereof with the pi electron deficiency characteristic, so that an acceptor-donor type molecule can be better formed, the energy gap and the triplet state energy level of the molecule can be improved, and the excellent bipolar phosphorescent main body material with high triplet state and wide energy gap can be obtained.
In the above general formula (I), Ar is a substituted or unsubstituted C having 1 or more, preferably 1 to 3N atoms3～C30The pi-electron deficient heteroaryl group is more preferably a heteroaryl group having a Hammett value of more than 0. R1～R3The HOMO and LUMO energy levels of the mother nucleus can be adjusted as a substituent, the mother nucleus structure can realize good electron and hole conduction balance, and the good electron and hole conduction balance can be realized through R1～R3The adjustment of (a) enables fine tuning of the electron and hole conductivities, R1～R3The Tg and steric hindrance of the molecule can also be adjusted to improve the film-forming property.
In the present invention, the expression of Ca to Cb means that the group has carbon atoms a to b, and the carbon atoms do not include the carbon atoms of the substituents unless otherwise specified. In the present invention, the expression of chemical elements includes the concept of chemically identical isotopes, such as the expression of "hydrogen", and also includes the concept of chemically identical "deuterium" and "tritium".
The heteroatom in the present invention generally refers to an atom or an atomic group selected from B, N, O, S, P, P (═ O), Si, and Se.
The compounds of the invention have the advantages that: the compound has high glass transition temperature, high melting point, and high carrier transport and luminous efficiency. The compound is applied to an organic light-emitting functional layer as a main material of a light-emitting layer, and an organic electroluminescent device with low driving voltage and high light-emitting efficiency can be obtained.
Detailed Description
The specific production method of the above-mentioned novel compound of the present invention will be described in detail below by taking a plurality of synthesis examples as examples, but the production method of the present invention is not limited to these synthesis examples.
The basic chemical materials of various chemicals used in the present invention, such as petroleum ether, ethyl acetate, sodium sulfate, toluene, tetrahydrofuran, methylene chloride, acetic acid, potassium phosphate, sodium tert-butoxide, etc., are commercially available from Shanghai Tankatake technologies, Inc. and Xilongchemical, Inc. The mass spectrometer used for determining the following compounds was a ZAB-HS type mass spectrometer measurement (manufactured by Micromass, UK).
The synthesis of the compounds of the present invention is briefly described below.
Representative synthetic route:
Figure BDA0001923584670000111
Figure BDA0001923584670000121
more specifically, the following gives synthetic methods of representative compounds of the present invention.
Synthetic examples
Synthesis example 1:
synthesis of Compound C1
Preparation of intermediate compound M1
Figure BDA0001923584670000122
Preparation of intermediate M-3
1000 ml three-neck flask, mechanical stirring, oil bath, under nitrogen protection, equipped with condenser tube, into which M-1(50g, 0.189mol), M-2(50g, 0.208mol), potassium carbonate (79g, 0.57mol), 300ml toluene, 100ml ethanol and 100ml water were added, the reaction stirred until all components were dissolved, then Pd (PPh) was added3)4(2.2g, 1.9mmol), after the addition was completed, the reaction was heated under reflux for 8 hours. TLC showed the reaction was complete. After cooling, water was added for separation, the organic layer was decolorized with silica gel and concentrated to dryness to give 81g of a black oil with a yield of 100%.
Preparation of intermediate M-4
The preparation method comprises the following steps of adding M-3(55g, 0.145mol) and 100ml of tetrahydrofuran into a 1000 ml three-neck flask, stirring and dissolving, then cooling to-10 ℃, slowly adding 3M methyllithium solution (121ml, 0.363mol) dropwise at-20 to-10 ℃, consuming 30min, raising the temperature to 20 ℃ after adding, stirring for 18 h, slowly pouring the reaction solution into an ammonium chloride aqueous solution, separating, extracting with ethyl acetate, drying sodium sulfate, concentrating to dryness, adding 200ml of dichloromethane under nitrogen, stirring and dissolving, then adding methanesulfonic acid (22.5g, 0.261mol) dropwise at 0 ℃, quickly separating out a solid, and raising the temperature to room temperature for reacting for 1 h after adding. Water was added, suction filtered and washed with acetone to give 31.5g of a white solid in 66.3% yield.
Preparation of intermediate M-5
A1000 ml three-necked flask was stirred magnetically with nitrogen, and then the compound M-4(24g, 0.067mol) was added to 300ml of tetrahydrofuran, and the mixture was heated to reflux with stirring. NBS (17.8g, 0.1mol) was dissolved in 200mL tetrahydrofuran, added dropwise to the reaction over 1 hour, the reaction was stopped, cooled to room temperature, 300mL of water was added to the reaction, dichloromethane was extracted with 200mL by 3, the organic phases were combined, dried over anhydrous sodium sulfate, filtered and dried. And adding the product into 100mL of dichloromethane, pulping at normal temperature, performing suction filtration, and airing to obtain 27g of a yellow product with the yield of 92%.
Preparation of intermediate M-6
The compound M-5(21.9g, 50mmol), o-nitrobenzeneboronic acid (9.2g,55mmol), potassium carbonate (21g, 150mmol), 300ml of toluene, 50ml of ethanol and 50ml of water were stirred until all components were dissolved, and then Pd (PPh) was added3)4(0.57g, 0.5mmol), and after the addition, the reaction was heated under reflux for 8 hours. TLC showed the reaction was complete. Cooling, adding water for liquid separation, decoloring organic layer silica gel, and concentrating to dryness to obtain 23g of white solid powder with the yield of 95%.
Preparation of intermediate M1
300mL of o-dichlorobenzene was placed in a 500mL single-neck flask equipped with magnetic stirring at room temperature, and the mixture of Compound M-6(19.2g,40mmol) and triphenylphosphine (26.2 g,0.1mol, 2.5eq) was stirred for 3 times, and the temperature was raised to 180 ℃ for 36 hours. The reaction was complete by TLC. Cooling the reaction liquid to room temperature, performing oil pump decompression spin-drying on the solvent, dissolving DCM, mixing with silica gel column chromatography, and performing PE: DCM ═ 5:1 to 1:1 elution gave 13.1g of off-white solid in 73% yield.
Figure BDA0001923584670000131
Preparation of Compound C1
Intermediate compound M1(11.2g,25mmol), 2-chloro-4-phenylquinazoline (6g,25mmol) and potassium carbonate (10.3g,75mmol) were added to a flask containing 150mL of DMF and heated to 120 ℃ with stirring under nitrogen for 12 h reaction, TLC showed completion. Cooling to room temperature, adding 150mL of water to quench the reaction, filtering the precipitated solid, eluting with ethanol, and drying the column chromatography (eluent petroleum ether: dichloromethane: 10: 1-1: 1) to obtain a light yellow solid compound C1(13.2g, yield 81%).
Calculated molecular weight: 653.28, found m/Z: 653.3. Tg 138.2 ℃.
Synthesis example 2:
synthesis of Compound C19
Figure BDA0001923584670000141
Preparation of intermediate 3-1
Intermediate compound M1(11.2g,25mmol), 2, 3-dichloroquinoxaline (5g,25mmol) and potassium carbonate (10.3g,75mmol) were added to a flask containing 150mL of DMF, heated to 120 ℃ under nitrogen with stirring for 12 hours and TLC indicated completion of the reaction. Cooling to room temperature, adding 150mL of water to quench the reaction, filtering the precipitated solid, eluting with ethanol, and drying the column chromatography (eluent is petroleum ether: dichloromethane: 10: 1-5: 1) to obtain a light yellow solid compound 3-1(11.5g, yield 75%).
Preparation of Compound C19
Compound 3-1(11g,18mmol), 2-naphthaleneboronic acid (3.1g,18mmol) and potassium carbonate (7.5g,54mmol) were dissolved in a flask containing toluene/ethanol/water (150mL/30mL/30mL), nitrogen was replaced with stirring at room temperature, and Pd (PPh3)4(231mg,0.2mmol) was added. After the addition was completed, the reaction was refluxed with stirring for 6 hours, and the end of the reaction was monitored by TLC. After cooling to room temperature, the mixture was separated, the aqueous phase was extracted with toluene, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was dried by spin-drying under reduced pressure, and purified by column chromatography (eluent petroleum ether: dichloromethane: 10:1 to 3:1) to obtain compound C19(10.2g, yield 81%).
Calculated molecular weight: 703.30, found m/Z: 703.3. Tg 151.3 ℃.
Synthetic example 3:
synthesis of Compound C42
Figure BDA0001923584670000151
Preparation of Compound C42
Intermediate compound M1(11.2g,25mmol), compound 4-1(9.7g,25mmol) and sodium tert-butoxide (7.4g,75mmol) were added to a flask containing 200mL of toluene, the nitrogen was replaced and Pd was added2(dba)3(229mg,0.25mmol) and tri-tert-butylphosphine (303mg,0.75mmol, 50% in xylene). After the addition was complete, the reaction was heated to reflux under nitrogen with stirring for 18 hours and TLC indicated completion of the reaction. The solvent was removed under reduced pressure and 200mL of methylene chloride and 50mL of water were addedAfter stirring and dissolving, the mixture was separated, the aqueous phase was extracted with dichloromethane, the organic phases were combined, and the column chromatography was dried over anhydrous sodium sulfate (eluent: petroleum ether: dichloromethane: 10:1 to 1:1) to obtain compound C42 as an off-white solid (15.1g, yield 80%).
Calculated molecular weight: 756.33, found m/Z: 756.3. Tg 159.9 ℃.
Synthetic example 4:
synthesis of Compound C45
Figure BDA0001923584670000152
Preparation of Compound C45
Intermediate compound M1(11.2g,25mmol), compound 5-1(11.6g,25mmol) and sodium tert-butoxide (7.4g,75mmol) were added to a flask containing 200mL of toluene, the nitrogen was replaced and Pd was added2(dba)3(229mg,0.25mmol) and tri-tert-butylphosphine (303mg,0.75mmol, 50% in xylene). After the addition was complete, the reaction was heated to reflux under nitrogen with stirring for 18 hours and TLC indicated completion of the reaction. The solvent was removed by rotation under reduced pressure, 200mL of dichloromethane and 50mL of water were added, the mixture was stirred and dissolved, the aqueous phase was separated, the aqueous phase was extracted with dichloromethane, the organic phases were combined, and dry column chromatography was performed over anhydrous sodium sulfate (eluent: petroleum ether: dichloromethane: 10:1 to 1:1) to obtain compound C45 as an off-white solid (15.2g, yield 73%).
Calculated molecular weight: 832.36, found m/Z: 832.4. Tg 163.2 ℃.
Synthesis example 5:
synthesis of Compound C56
Preparation of intermediate compound M2
Figure BDA0001923584670000161
Preparation of intermediate M-7
Under the protection of nitrogen, a 1L three-necked flask equipped with a magnetic stirring, thermometer and condenser is charged with compound M-5(43.8g, 0.1mol), o-chloroaniline 12.7g (0.1mol), Pd2(dba)3(0.9g, 1%) Tri-tert-butylphosphine(0.6g, 2%), sodium t-butoxide 14.4g (0.36mol), toluene 500ml and the reaction mixture was refluxed at 70 ℃ for 4 h. After cooling to room temperature, water and EA were added for extraction, the organic phase was concentrated to give a dark brown solid, and PE was recrystallized to give 35.8g of a yellowish solid with a yield of 74%.
Preparation of intermediate M2
Under the protection of nitrogen, a 500ml three-necked flask equipped with a magnetic stirrer, a thermometer and a condenser was charged with intermediate M-7(15.3g, 0.0315mo), palladium acetate 0.35g (5% eq), tricyclohexylphosphine 1.15g (13%) potassium carbonate 13g (0.094mol, 3.0eq) and DMAC100ml, and the reaction mixture was refluxed at 135 ℃ to 145 ℃ for 2 hours. Cooling the reaction solution to room temperature, adding water EA for extraction, concentrating, and adding PE: the column was filtered with EA 50:1 and concentrated to give 9.2g of off-white solid in 65% yield.
Figure BDA0001923584670000171
Preparation of Compound C56
Intermediate compound M2(11.2g,25mmol), 2-chloro-4-phenylquinazoline (6g,25mmol) and potassium carbonate (10.3g,75mmol) were added to a flask containing 150mL of DMF and heated to 120 ℃ with stirring under nitrogen for 12 h reaction, TLC showed completion. Cooling to room temperature, adding 150mL of water to quench the reaction, filtering the precipitated solid, eluting with ethanol, and drying the column chromatography (eluent is petroleum ether: dichloromethane: 10: 1-1: 1) to obtain a light yellow solid compound C56(13.0g, yield 80%).
Calculated molecular weight: 653.28, found m/Z: 653.3. Tg 141.3 ℃.
Synthetic example 6:
synthesis of Compound C63
Preparation of intermediate compound M3
Figure BDA0001923584670000172
Intermediate M3 was prepared similarly to intermediate M2 except methyl 2-bromo-1-naphthoate was used instead of methyl 1-bromo-2-naphthoate. Intermediate M3 was obtained as a white solid in 62% yield.
Figure BDA0001923584670000181
Preparation of Compound 6-1
The compound 2-chloro-4-phenylquinazoline (24g,0.1mol), 4-chlorobenzeneboronic acid (17.2g,0.11mol) and potassium carbonate (41.4g,0.3mol) were dissolved in a flask containing toluene/ethanol/water (300mL/50mL/50mL), and Pd (PPh3)4(1.15g,0.001mol) was added after replacing nitrogen with stirring at room temperature. After the addition was complete, the reaction was refluxed with stirring for 4 hours, and the end of the reaction was monitored by TLC. Cooling to room temperature, filtering, washing the solid with toluene, water and ethanol, and air drying. Purification by column chromatography gave compound 6-1(29g, 92% yield).
Synthesis of Compound C63
Intermediate compound M3(11.2g,25mmol), compound 6-1(7.9g,25mmol) and sodium tert-butoxide (7.4g,75mmol) were charged in a flask containing 200mL of toluene, after displacement of nitrogen, Pd2(dba)3(229mg,0.25mmol) and tri-tert-butylphosphine (303mg,0.75mmol, 50% in xylene) were added. After the addition was complete, the reaction was heated to reflux under nitrogen with stirring for 18 hours and TLC indicated completion of the reaction. The solvent was removed by evaporation under reduced pressure, 200mL of dichloromethane and 50mL of water were added, the mixture was dissolved with stirring, the aqueous phase was separated, the aqueous phase was extracted with dichloromethane, the organic phases were combined, and the column chromatography was dried over anhydrous sodium sulfate to give off-white solid compound C63(12.9g, yield 71%).
Calculated molecular weight: 729.31, found m/Z: 729.3. Tg 161.3 ℃.
Synthetic example 7:
synthesis of Compound C70
Preparation of intermediate compound M4
Figure BDA0001923584670000191
Intermediate M3 was prepared similarly to intermediate M1 except methyl 2-bromo-1-naphthoate was used instead of methyl 1-bromo-2-naphthoate. Intermediate M4 was obtained as a white solid in 66% yield.
Figure BDA0001923584670000192
Preparation of Compound 7-1
The compound 2-chloro-4- (4-pyridin) ylquinazoline (24.1g,0.1mol), 3-chlorobenzeneboronic acid (17.2g,0.11mol) and potassium carbonate (41.4g,0.3mol) were dissolved in a flask containing toluene/ethanol/water (300mL/50mL/50mL), nitrogen was replaced with stirring at room temperature, and Pd (PPh) was added3)4(1.15g,0.001 mol). After the addition was complete, the reaction was refluxed with stirring for 4 hours, and the end of the reaction was monitored by TLC. Cooling to room temperature, filtering, washing the solid with toluene, water and ethanol, and air drying. Purification by column chromatography gave compound 7-1(26.9g, 85% yield).
Synthesis of Compound C70
Intermediate compound M4(11.2g,25mmol), compound 7-1(7.9g,25mmol) and sodium tert-butoxide (7.4g,75mmol) were added to a flask containing 200mL of toluene, the nitrogen was replaced and Pd was added2(dba)3(229mg,0.25mmol) and tri-tert-butylphosphine (303mg,0.75mmol, 50% in xylene). After the addition was complete, the reaction was heated to reflux under nitrogen with stirring for 18 hours and TLC indicated completion of the reaction. The solvent was removed by evaporation under reduced pressure, 200mL of dichloromethane and 50mL of water were added, the mixture was dissolved with stirring, the aqueous phase was separated, the aqueous phase was extracted with dichloromethane, the organic phases were combined, and the column chromatography was dried over anhydrous sodium sulfate to give off-white solid compound C71(11.9g, yield 65%).
Calculated molecular weight: 730.31, found m/Z: 730.3. Tg 161.7 ℃.
Device embodiments
The implementation mode is as follows:
the OLED includes first and second electrodes, and an organic material layer between the electrodes. The organic material may in turn be divided into a plurality of regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.
In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a Thin Film Transistor (TFT) may be provided on a substrate for a display.
The first electrode may be formed by sputtering or depositing a material used as the first electrode on the substrate. When the first electrode is used as an anode, an oxide transparent conductive material such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), or any combination thereof may be used. When the first electrode is used as a cathode, a metal or an alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof can be used.
The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, printing, or the like. The compound used as the organic material layer may be an organic small molecule, an organic large molecule, and a polymer, and a combination thereof.
The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer containing only one compound and a single layer containing a plurality of compounds. The hole transport region may also be a multilayer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL).
The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenevinylene, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives such as compounds shown below in HT-1 to HT-34; or any combination thereof.
Figure BDA0001923584670000201
Figure BDA0001923584670000211
Figure BDA0001923584670000221
The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of a plurality of compounds. For example, the hole injection layer may employ one or more compounds of HT-1 to HT-34 described above, or one or more compounds of HI1-HI3 described below; one or more of the compounds HT-1 to HT-34 may also be used to dope one or more of the compounds HI1-HI3 described below.
Figure BDA0001923584670000222
The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit different wavelength spectra, and may also include a Host material (Host). The light emitting layer may be a single color light emitting layer emitting a single color of red, green, blue, or the like. The single color light emitting layers of a plurality of different colors may be arranged in a planar manner in accordance with a pixel pattern, or may be stacked to form a color light emitting layer. When the light emitting layers of different colors are stacked together, they may be spaced apart from each other or may be connected to each other. The light-emitting layer may be a single color light-emitting layer capable of emitting red, green, blue, or the like at the same time.
According to different technologies, the luminescent layer material can be different materials such as fluorescent electroluminescent material, phosphorescent electroluminescent material, thermal activation delayed fluorescent luminescent material, and the like. In an OLED device, a single light emitting technology may be used, or a combination of a plurality of different light emitting technologies may be used. These technically classified different luminescent materials may emit light of the same color or of different colors.
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The phosphorescent dopant of the light emitting layer thereof may be selected from, but not limited to, a combination of one or more of RPD-1 to RPD-28 listed below.
Figure BDA0001923584670000231
The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single-layer structure including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).
In one aspect of the invention, the electron transport layer material may be selected from, but is not limited to, the combination of one or more of ET-1 through ET-57 listed below.
Figure BDA0001923584670000241
Figure BDA0001923584670000251
Figure BDA0001923584670000261
An electron injection layer may also be included in the device between the electron transport layer and the cathode, the electron injection layer materials including, but not limited to, combinations of one or more of the following.
LiQ,LiF,NaCl,CsF,Li2O,Cs2CO3,BaO,Na,Li,Ca。
The technical effects and advantages of the present invention are demonstrated and verified by testing practical use performance by specifically applying the compound of the present invention to an organic electroluminescent device.
For the purpose of comparing device application properties of the light emitting material of the present invention, CBP and H1 compounds shown below were used as comparative materials.
Figure BDA0001923584670000271
The preparation process of the organic electroluminescent device in the embodiment is as follows:
the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to less than 1 × 10-5Pa, regulating the evaporation rate of a hole transport material HT-33 to be 0.1nm/s and the evaporation rate of a hole injection material HT-32 to be 7% by using a multi-source co-evaporation method on the anode layer film, wherein the total film thickness of evaporation is 10 nm;
evaporating HT-33 on the hole injection layer in vacuum to serve as a first hole transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 95 nm;
evaporating HT-34 on the first hole transport layer in vacuum to serve as a second hole transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 20 nm;
the luminescent layer of the device is evaporated in vacuum on the second hole transport layer, the luminescent layer comprises a main material and a dye material, the evaporation rate of the main material C1-C81 or the contrast material H1 and CBP is adjusted to be 0.1nm/s by using a multi-source co-evaporation method, the evaporation rate of the dye RPD-9 is set in a proportion of 5%, and the total evaporation film thickness is 36 nm;
evaporating ET-17 on the second light-emitting layer in vacuum to be used as a hole blocking layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness is 5 nm;
adjusting the evaporation rate of an electron transport material ET-46 to be 0.1nm/s by using a multi-source co-evaporation method on the hole blocking layer, setting the evaporation rate to be 100% of the evaporation rate of ET-57, and setting the total film thickness of evaporation to be 24 nm;
LiF with the thickness of 1nm is vacuum-evaporated on the Electron Transport Layer (ETL) to be used as an electron injection layer, and an Al layer with the thickness of 80nm is used as a cathode of the device.
The following performance measurements were performed on the organic electroluminescent devices prepared in the above examples and comparative examples:
PR 75 from Photo Research was used at the same brightnessThe driving voltage and current efficiency of the organic electroluminescent devices prepared in examples 1 to 4 and comparative examples 1 and 2 were measured by a model 0 photoradiometer ST-86LA luminance meter (photoelectric instrument factory, university of beijing) and a Keithley4200 test system. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent device reached 5000cd/m2The current density is measured at the same time as the driving voltage; the ratio of the luminance to the current density is the current efficiency. The life test of LT95 is as follows: using a luminance meter at 10000cd/m2The luminance drop of the organic electroluminescent device was measured to be 9500cd/m by maintaining a constant current at luminance2Time in hours.
The following OLED devices of the various examples were prepared according to the above procedure, specifically the device in each example having the following structure:
example 1
An electroluminescent device was prepared according to the above-described process for the preparation of an organic electroluminescent device of the present invention using the compound C1 of the present invention as a light-emitting host material, and device performance tests were carried out according to the device test method of the present invention described below.
Example 2
An organic electroluminescent device was produced in the same manner as in example 1, except that compound C1 was replaced with C19.
Example 3
An organic electroluminescent device was produced in the same manner as in example 1, except that compound C1 was replaced with C42.
Example 4
An organic electroluminescent device was produced in the same manner as in example 1, except that compound C1 was replaced with C45.
Example 5
An organic electroluminescent device was produced in the same manner as in example 1, except that compound C1 was replaced with C56.
Example 6
An organic electroluminescent device was produced in the same manner as in example 1, except that compound C1 was replaced with C63.
Example 7
An organic electroluminescent device was produced in the same manner as in example 1, except that compound C1 was replaced with C70.
Comparative example 1
An organic electroluminescent device was produced in the same manner as in example 1, except that compound C1 was replaced with CBP.
Comparative example 2
An organic electroluminescent device was produced in the same manner as in example 1, except that compound C1 was replaced with H1.
The properties of the organic electroluminescent devices prepared in the above examples are shown in table 1 below.
Table 1:
Figure BDA0001923584670000291
for examples 1 to 7 and comparative example 1, in the case where other materials in the organic electroluminescent device structure are the same, the voltage of the compound according to the present invention is significantly reduced, and the current efficiency and the lifetime are greatly improved, as compared to the host material CBP in comparative example 1. The voltage was also reduced, and the current efficiency and lifetime were improved compared to the host material H1 in comparative example 2.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (12)

1. A compound of the general formula (I):
Figure FDA0001923584660000011
wherein:
one of A and B is a group represented by formula a, and the other is a substituted or unsubstituted phenylene group;
l is a single bond, substituted or unsubstituted C6～C30Arylene, substituted or unsubstituted C3～C30One of heteroarylenes;
ar is substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30One of the heteroaryl groups of (a);
R1～R3are the same or different from each other and are each independently selected from hydrogen and C1～C12Alkyl radical, C1～C12Alkoxy, halogen, cyano, nitro, hydroxy, silyl, amino, substituted or unsubstituted C6～C30Arylamino, substituted or unsubstituted C3～C30Heteroarylamino, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30One of the heteroaryl groups, and R1～R3Each independently may be fused to the attached phenyl ring to form C9～C30Aryl or C9～C30Heteroaryl, the aryl or heteroaryl fused as described above may be optionally substituted independently with 0, 1, 2, 3,4 or 5 of the following groups: c1～C12Alkyl, halogen, cyano, nitroRadical, hydroxy, silyl, C6～C30Aryl or C3～C30A heteroaryl group;
n and p are the same or different from each other and are each independently an integer of 0 to 4, preferably 0 to 2;
m is an integer of 0-2;
X1、X2same or different, each is independently selected from CR4R5、NR6One of O, or S, and when X is2When is S, X1Is not NR6；
R mentioned above4～R6Each independently selected from hydrogen, substituted or unsubstituted C1～C10Alkyl, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30One of heteroaryl;
when the above groups have substituents, the substituents are respectively and independently selected from halogen and C1-C10Alkyl or cycloalkyl of, C2-C10Alkenyl radical, C1-C6Alkoxy or thioalkoxy group of (C)6-C30Monocyclic aromatic hydrocarbon or condensed ring aromatic hydrocarbon group of (A), C3-C30One of the monocyclic heteroaromatic group or the condensed ring heteroaromatic group of (a).
2. The compound of general formula (la) according to claim 1, represented by any one of the following formulae (2-1) to (2-4):
Figure FDA0001923584660000021
in formulae (2-1) to (2-4):
L、Ar、R1～R3、m、n、p、X1and X2Are as defined in formula (1) and formula a;
R7independently selected from hydrogen, C1～C12Alkyl radical, C1～C12Alkoxy, halogen, cyano, nitro, hydroxy, silyl, amino, substitutedOr unsubstituted C6～C30Arylamino, substituted or unsubstituted C3～C30Heteroarylamino, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30One of heteroaryl;
R7may be condensed with the benzene ring to which they are attached to form C9～C30Aryl or heteroaryl, the aryl or heteroaryl formed being optionally substituted or unsubstituted C with 0, 1, 2, 3,4 or 5 each independently1～C12Alkyl, halogen, cyano, nitro, hydroxy, silyl, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30Substituted with a substituent in the heteroaryl group;
q is an integer of 0 to 4.
3. A compound of formula (la) according to claim 1 or 2, wherein X1Selected from the group consisting of CR4R5、NR6One of O or S, X2Selected from the group consisting of CR4R5、NR6Or O;
wherein R is4～R6Are as defined in formula a.
4. A compound of formula (la) according to claim 1 or 2, wherein L is selected from a single bond or from the following substituents:
Figure FDA0001923584660000031
wherein, indicates the bonding position with nitrogen atom or Ar group, and the expression mode of the ring structure crossed indicates that the connecting site is positioned at any position capable of forming a bond on the ring structure;
preferably, L is selected from a single bond or phenylene.
5. A compound of formula (la) according to claim 1 or 2, wherein:
ar is substituted or unsubstituted N atom-containing C3～C30The heteroaryl group of (a);
preferably, Ar is substituted or unsubstituted C containing 1 to 3N atoms3～C30The heteroaryl group of (a).
6. A compound of formula (la) according to claim 1 or 2, wherein:
ar is selected from the following substituted or unsubstituted groups: one of pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, 1, 8-naphthyridinyl, or 2, 7-naphthyridinyl;
R1～R3independently selected from H, F, Cl, Br, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl, fluoranthryl, triphenylenyl, pyrenyl, perylenyl, perylene, and mixtures thereof,
Figure FDA0001923584660000032
One of a group, furyl, thienyl, pyrrolyl, pyridyl, benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl or carbazolyl.
7. A compound of formula i according to claim 1 or 2 wherein Ar is selected from the following structures a1-a 32:
Figure FDA0001923584660000041
wherein denotes a bonding site.
8. A compound of formula (la) according to any one of claims 1 to 7, wherein X1、X2Are each independently selected from CR4R5Or NR6Wherein R is4～R6Are as defined in formula a.
9. A compound of formula (la) according to any one of claims 1 to 7, wherein X1And X2Are all CR4R5Wherein R is4And R5Is methyl.
10. A compound of formula (la) according to claim 1, selected from the compounds of the following specific structures:
Figure FDA0001923584660000042
Figure FDA0001923584660000051
Figure FDA0001923584660000061
Figure FDA0001923584660000071
Figure FDA0001923584660000081
Figure FDA0001923584660000091
11. use of a compound of formula (la) according to claim 1 as a light-emitting host material in an organic electroluminescent device.
12. An organic electroluminescent device comprising a first electrode, a second electrode and one or more organic layers interposed between said first and second electrodes, characterized in that said organic layers comprise at least one compound according to any one of claims 1 to 10.
CN201811606122.XA 2018-12-27 2018-12-27 Organic electroluminescent material and device Pending CN111377905A (en)

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