CN118027076A - Organic electroluminescent material containing B-N structure and electroluminescent device - Google Patents

Organic electroluminescent material containing B-N structure and electroluminescent device Download PDF

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CN118027076A
CN118027076A CN202311379349.6A CN202311379349A CN118027076A CN 118027076 A CN118027076 A CN 118027076A CN 202311379349 A CN202311379349 A CN 202311379349A CN 118027076 A CN118027076 A CN 118027076A
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carbon atoms
heteroaryl
aryl
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alkyl
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白科研
戴雷
蔡丽菲
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Guangdong Aglaia Optoelectronic Materials Co Ltd
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Guangdong Aglaia Optoelectronic Materials Co Ltd
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight

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Abstract

The invention provides an organic electroluminescent material containing a B-N structure and an electroluminescent device. Based on the traditional B-N resonance structure, the aromatic ring which does not participate in resonance is connected to the B-N framework through alkyl, so that the electron donating property of N is enhanced, the multiple resonance effect is enhanced, and a large steric hindrance group is introduced into a benzyl position, so that the non-radiative transition vibration of the B-N framework is reduced, the half-peak width of an emission spectrum is reduced, and the efficiency is improved. The structural general formula of the organic electroluminescent material is shown as formula (A1):

Description

Organic electroluminescent material containing B-N structure and electroluminescent device
Technical Field
The application relates to the field of luminescent materials, in particular to an organic electroluminescent material containing a B-N structure and an electroluminescent device.
Background
The organic electroluminescent (OLED: organic Light Emission Diodes) device has been widely used in display and lighting industries, especially in mobile phone display, and the latest mobile phone products such as Apple, sumsang, huacheng and millet are all provided with OLED screens, which is mainly attributed to the excellent characteristics of self-luminescence, wide viewing angle, high contrast ratio, fast response speed, and capability of preparing flexible devices.
The current commercial OLED devices are multi-layered sandwich structures including an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode, and the like. The anode generates holes and enters the light emitting layer through the hole injection layer and the transport layer, and electrons move from the cathode to the light emitting layer through the electron injection layer and the transport layer, and the holes and the electrons recombine in the light emitting layer to generate excitons. These excitons transition from an excited state to a ground state, thereby emitting visible light. In order to realize color display, the OLED device uses the principle of additive color, namely the light-emitting layer is divided into a blue light-emitting layer, a green light-emitting layer and a red light-emitting layer, and organic materials with different light-emitting colors are used for different light-emitting layers.
When the OLED device is applied to a display, it is required to have a low driving voltage, high luminous efficiency, and long life, and thus, in achieving a gradual increase in display performance, the organic material undergoes development from a fluorescent material to a phosphorescent material to a thermally activated delayed fluorescent material (TADF). At present, green light and red light materials are phosphorescent materials, which can emit light by utilizing singlet excitons and triplet excitons, so that the internal quantum efficiency can reach 100%, but the phosphorescent materials contain heavy metals, and the problems of high price, poor material stability and the like exist; the blue light material is a fluorescent material, only singlet exciton luminescence can be adopted, although the theory of TTA (conversion of two triplet excitons into one singlet exciton) is applied, the theoretical efficiency is only 40%, and the theoretical efficiency is far lower than the market demand. The TADF material utilizes small singlet-triplet state energy level difference (delta EST), triplet state excitons can be converted into singlet state excitons by reverse intersystem crossing, so that the internal quantum efficiency of 100% can be achieved, however, the TADF material has stronger charge transfer Characteristic (CT), and the spectrum half wave width is too wide, which is unfavorable for high color purity display.
Disclosure of Invention
Aiming at the existing problems of the organic materials, the application provides an organic electroluminescent material containing a B-N structure, which is characterized in that an aromatic ring which does not participate in resonance is connected to a B-N framework through alkyl on the basis of the traditional B-N resonance structure, the electron donating property of N is enhanced, the multiple resonance effect is enhanced, and a large steric hindrance group is introduced into a benzyl position, so that the non-radiative transition vibration of the B-N framework is reduced, the half-peak width of an emission spectrum is reduced, and the efficiency is improved.
The application provides an organic electroluminescent material containing a B-N structure, the structural general formula of which is shown as formula (A1):
Wherein: ar 1-Ar3 and Cy1 are independently selected from substituted or unsubstituted aryl groups having 6-30 carbon atoms, substituted or unsubstituted heteroaryl groups having 5-30 carbon atoms; or Ar 2 and Ar 3 or Ar 1 and Cy 1 independently have O, S, se, te atoms or a single bond 、-C(R4)2-C(R5)2-、-C R4＝C R5-、-C R4＝N-、-C R4＝P-、-C≡C-、 Any one of which is bonded to form a ring;
R 1-R5 is independently selected from the group consisting of hydrogen, deuterium, cyano, nitro, halo, hydroxy, alkylthio of 1 to 4 carbon atoms, alkyl of 1 to 30 carbon atoms, cycloalkyl of 1 to 20 carbon atoms, aryloxy of 6 to 30 carbon atoms, alkoxy of 1 to 30 carbon atoms, alkylamino of 1 to 30 carbon atoms, arylamino of 6 to 30 carbon atoms, aralkylamino of 6 to 30 carbon atoms, heteroarylamino of 2 to 24 carbon atoms, alkylsilane of 1 to 30 carbon atoms, alkoxysilane of 1 to 30 carbon atoms, arylsilane of 6 to 30 carbon atoms, alkenyl of 2 to 30 carbon atoms, alkynyl of 2 to 24 carbon atoms, aralkyl of 7 to 30 carbon atoms, aryl of 6 to 30 carbon atoms, heteroaryl of 5 to 60 carbon atoms, and heteroarylalkyl of 6 to 30 carbon atoms,
The substitution is substituted by deuterium, cyano, nitro, halogen, C1-C8 alkyl, C6-C20 aryl, C5-C20 heteroaryl,
The hetero atoms in the heteroaryl and the heteroaralkylamino are one or more of O, S, N, se, te.
In some embodiments, wherein: ar 1-Ar3, cy1 are independently selected from substituted or unsubstituted aryl groups having 6-30 carbon atoms, substituted or unsubstituted heteroaryl groups having 5-30 carbon atoms; either Ar 2 and Ar 3 or Ar 1 and Cy 1 independently have O, S, se atoms or single bonds,Any one of which is bonded to form a ring;
R 1-R5 is independently selected from the group consisting of hydrogen, deuterium, cyano, nitro, halo, hydroxy, alkylthio of 1 to 4 carbon atoms, alkyl of 1 to 20 carbon atoms, cycloalkyl of 1 to 10 carbon atoms, aryloxy of 6 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, alkylamino of 1 to 20 carbon atoms, arylamino of 6 to 20 carbon atoms, aralkylamino of 6 to 20 carbon atoms, heteroarylamino of 2 to 20 carbon atoms, alkylsilane of 1 to 20 carbon atoms, arylsilane of 6 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, heteroaryl of 5 to 20 carbon atoms, and heteroarylalkyl of 6 to 20 carbon atoms,
The substitution is substituted by deuterium, cyano, nitro, halogen, C1-C8 alkyl, C6-C20 aryl, C5-C20 heteroaryl,
The hetero atoms in the heteroaryl and the heteroaralkylamino are one or more of O, S, N, se, te.
The aryl is selected from one or more of phenyl, naphthyl, anthryl, binaphthyl, phenanthryl, dihydrophenanthryl, pyrenyl, perylenyl, naphthacene, pentacene, benzoperylene, benzocyclopentadienyl, spirofluorenyl and fluorenyl;
the heteroaryl is selected from the group consisting of pyrrolyl, imidazolyl, thienyl, furyl, 1, 2-thiazolyl, 1, 3-thiazolyl, 1, 2-selenazolyl, 1, 3-selenazolyl, 1, 2-tellurium oxazolyl, 1, 3-tellurium oxazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, thiadiazolyl, selenadiazolyl, tellurium diazolyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, pyridyl, pyrazinyl, pyrimidinyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, indole, isoindole, indole (3, 2, 1-JK) carbazole, benzimidazole, naphthoimidazole, phenanthroimidazole, benzotriazole, purine, benzoxazole, naphthooxazole, phenanthreneoxazoles, benzothiadiazoles, benzoselenadiazoles, benzotelluridiazoles, benzotriazoles, quinolines, isoquinolines, benzopyrazines, benzothiophenes, benzoselenophenes, benzotellurophenones, benzofurans, benzopyrroles, carbazoles, acridines, dibenzothiophenes, dibenzofurans, dibenzoselenophenes, dibenzotellurophenones, dibenzothiophenes-5, 5-dioxys, naphtolthiodiazoles, naphtolselenadiazoles, and 10, 15-dihydro-5H-diindoles [3,2-a:3',2' -c ] carbazolyl.
In some embodiments the heteroaryl is selected from the group consisting of pyrrolyl, imidazolyl, thienyl, furanyl, 1, 2-thiazolyl, 1, 3-thiazolyl, 1, 2-selenazolyl, 1, 3-selenazolyl, 1, 2-tellurizolyl, 1, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, thiadiazolyl, selenadiazolyl, telluridiazolyl 1,2, 3-triazolyl, 1,2, 4-triazolyl, pyridinyl, pyrazinyl, pyrimidinyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, indole, isoindole, benzimidazole, naphthymidazole, phenanthroimidazole, benzotriazole, purine, benzoxazole, naphthazole, phenanthroaxazoles, benzothiadiazoles, benzoselenadiazoles, benzotelluridiazoles, benzotriazoles, quinolines, isoquinolines, benzopyrazines, benzothiophenes, benzoselenophenes, benzotellurophenones, benzofurans, benzopyrroles, carbazoles, acridines, dibenzothiophenes, dibenzoselenophenes, dibenzotellurophenones, dibenzofurans, dibenzothiophenes-5, 5-dioxys, naphthathiadiazoles, naphthaselenadiazoles, and 10, 15-dihydro-5H-diindoles [3,2-a:3',2' -c ] carbazolyl.
In some embodiments of the present invention, in some embodiments, R 1-R5 is independently selected from the group consisting of hydrogen, deuterium, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, cyclopentyl, cyclohexyl, vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-diphenylvinyl-1-yl, methoxy, ethoxy, propoxy, and isobutoxy, sec-butoxy, pentyloxy, isopentyloxy, hexyloxy, trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, dimethylfuranylsilylphenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, perylenyl, tetracenyl, fluorenyl, acenaphthylenyl (ACENAPHATHCENYL), triphenyland fluoranthenyl, thienyl, furyl, pyrrolyl, imidazolyl, triazolyl, diazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, pyridazinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, benzofuranyl, dibenzofuranyl, phenanthrolinyl, thiazolyl, isoxazolyl, thiadiazolyl and phenothiazinyl.
In some embodiments, the general structural formula is shown in one of the structures of formulas (B1) to (B5):
Wherein X 1 is selected from O, S, se, Any one of them;
Ar 1 and Cy1 are selected from substituted or unsubstituted aryl with 6-20 carbon atoms, substituted or unsubstituted heteroaryl with 5-20 carbon atoms, or Ar 1 and Cy 1 can independently have O, S, se atoms or a single bond, Any one of which is bonded to form a ring;
R 1-R5 is independently selected from the group consisting of hydrogen, deuterium, cyano, nitro, halo, hydroxy, alkylthio of 1 to 4 carbon atoms, alkyl of 1 to 10 carbon atoms, cycloalkyl of 1 to 6 carbon atoms, aryloxy of 6 to 20 carbon atoms, alkoxy of 1 to 10 carbon atoms, alkylamino of 1 to 10 carbon atoms, arylamino of 6 to 10 carbon atoms, aralkylamino of 6 to 20 carbon atoms, heteroarylamino of 2 to 20 carbon atoms, alkylsilane of 1 to 10 carbon atoms, arylsilane of 6 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, heteroaryl of 5 to 20 carbon atoms, and heteroarylalkyl of 6 to 20 carbon atoms,
The substitution is substitution by deuterium, cyano, nitro, halogen, C1-C8 alkyl, C6-C20 aryl, C5-C20 heteroaryl,
The hetero atom in the heteroaryl and the heteroaralkylamino is one or more of O, S, N, se, te,
R 6-R7、R9 is independently selected from hydrogen, deuterium, cyano, nitro, halo, C1-C8 alkyl, C6-C20 aryl, C5-C20 heteroaryl.
In some embodiments: x 1 is selected from O, S,Any one of the following.
In some embodiments, the general structural formula is shown in one of the structures (C1) to (C36),
Wherein X 1 is selected from O, S, se,Any one of them;
R 1-R5 is independently selected from hydrogen, deuterium, cyano, nitro, halo, alkyl of 1 to 10 carbon atoms, cycloalkyl of 1 to 6 carbon atoms, aralkyl of 7 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, heteroaryl of 5 to 20 carbon atoms, or heteroarylalkyl of 6 to 20 carbon atoms,
The substitution is substituted by deuterium, cyano, nitro, halogen, C1-C8 alkyl, C6-C20 aryl, C5-C20 heteroaryl,
The hetero atoms in the heteroaryl group are one or more of O, S, N, se,
R 6-R10 is independently selected from hydrogen, deuterium, cyano, nitro, halogen, C1-C8 alkyl, C6-C20 aryl, C5-C20 heteroaryl,
Ar 1 is independently selected from substituted or unsubstituted aryl groups having from 6 to 20 carbon atoms, or Ar 1 and R8 substituted aryl or heteroaryl groups can be independently substituted with O, S, se atoms or a single bond,Any of which are bonded to form a ring.
Ar1 is selected from structures D1-D17.
Further in some embodiments, wherein R 1–R10 is independently selected from hydrogen, deuterium, linear or branched C1-C4 alkyl, phenyl, naphthyl, carbazole, carbazolocarbazole, indole (3, 2, 1-JK) carbazole, respectively.
In some embodiments: r 1–R10 is independently selected from hydrogen atom, deuterium atom, linear or branched C1-C4 alkyl.
In some embodiments, the structures are shown in the following formulas, but are not limited to the listed formulas:
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The second application provides an electroluminescent device, which comprises at least one functional layer containing the organic electroluminescent material;
in some embodiments, the organic electroluminescent material described above is used as the light-emitting layer material;
In some embodiments, the organic electroluminescent material is used as a doping material of the light-emitting layer;
an OLED display element comprises the electroluminescent device.
The application provides a B-N containing organic electroluminescent material, which is characterized in that an aromatic ring which does not participate in resonance is connected to a B-N framework through alkyl on the basis of the traditional B-N resonance structure, the electron donating property of N is enhanced, the multiple resonance effect is enhanced, and a large steric hindrance group is introduced into a benzyl position to reduce the non-radiative transition vibration of the B-N framework, so that the half-peak width of an emission spectrum is reduced, and the material is favorable for obtaining excellent color purity and higher efficiency of an emission device in an electroluminescent device, so as to achieve more excellent display effect.
Drawings
Fig. 1 is a structural view of an electroluminescent device according to the present application, in which 10 is represented by a glass substrate, 20 is represented by an anode, 30 is represented by a hole injection layer, 40 is represented by a hole transport layer, 50 is represented by an electron blocking layer, 60 is represented by a light emitting layer, 70 is represented by an electron transport layer, 80 is represented by an electron injection layer, and 90 is represented by a cathode.
Detailed Description
The method of synthesizing the material is not required in the present application, but the following examples are given for the purpose of describing the present application in more detail, but are not limited thereto. The raw materials used in the following synthesis are commercially available products unless otherwise specified.
Example 1:
Synthesis of Compound Structure 1
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Synthesis of compound (1 c):
1L of a single-necked flask was charged with magneton, compound (1 a) (15.0 g,55 mmol), (1 b) (5.6 g,60 mmol) and K 2CO3 (16.6 g,120 mmol), and then 400mL of DMF was added thereto, followed by stirring and heating to 80℃for reaction for 12 hours. Cooling to room temperature, adding 400mL of deionized water, extracting with dichloromethane, draining the organic phase, and then column separation using PE: dcm=10:1, to give 12.7g of white powdery solid in 81% yield. ESI-MS (M/z): 286 (M+1).
Synthesis of compound (1 d):
1L of a single-necked flask was taken, and magneton and compound (1 c) (5.0 g,17 mmol) were added thereto, and 50mL of Eton's reagent was poured thereinto, followed by stirring and heating to 100℃and reacting for 12 hours. Cooling to room temperature, adding 400mL of deionized water, and drying in a vacuum oven. Column separation was then performed using PE: dcm=20:1 to give 4.5g of white powdery solid in yield 90％.1H NMR(400MHz,Chloroform-d)δ7.34(m,10H),7.18–7.08(m,2H),6.98(td,J＝7.5,1.6Hz,1H),6.69(dd,J＝7.0,1.5Hz,1H),4.95(t,J＝3.6Hz,1H),3.42(m,2H),2.34(m,1H),2.18(m,1H).ESI-MS(m/z):286(M+1).
Synthesis of compound (1 f):
Weighing (1d)(5.0g,17.5mmol)、(1e)(3.7g,19.3mmol)、Pd2(dba)3(0.5g,0.5mmol)、xphos(0.5g,1.0mmol)、t-BuONa(6.7g,0.07mmol) and magnetons in a 500mL single-port reaction bottle, pouring 200mL of dry toluene, adding a reflux condenser, stirring, pumping nitrogen three times, and heating to 100 ℃ for reaction for 24 hours. The reaction solution was directly spin-dried, dissolved in dichloromethane and stirred with silica gel, and passed through a column using a mixed solvent of petroleum ether and dichloromethane as an eluent. The product after passing through the column had a small amount of impurities, which was slurried with n-hexane and filtered to give 5.8g of a white powder in 84% yield. The hydrogen spectrum data is as follows ：1H NMR(400MHz,CDCl3)δ7.34(m,10H),7.26–7.21(m,1H),7.19(m,1H),7.11–7.05(m,4H),6.98–6.90(m,2H),3.92(m 2H),2.24(m,1H),2.16(m,1H).ESI-MS(m/z):395(M+1).
Synthesis of Compound (1 g):
Similar to the synthesis of the compound (1 f), the difference is that the raw material (1 d) is replaced with (1 b), and the raw material (1 e) is replaced with (1 f). A white powder was obtained in 72% yield. The hydrogen spectrum data is as follows ：1H NMR(400MHz,Chloroform-d)δ7.34(m,10H),7.24(dd,J＝7.9,7.2Hz,1H),7.24–7.14(m,3H),7.11–7.01(m,5H),6.97–6.92(m,1H),6.88(m,1H),6.83(m,2H),6.44(m,1H),3.92(m,2H),2.24(m,1H),2.16(m,1H).ESI-MS(m/z):453(M+1),475(M+Na).
Synthesis of compound (1 i):
The preparation method comprises the steps of weighing (1g)(5.0g,11.0mmol)、(1h)(4.7g,16.6mmol)、Pd(OAc)2(0.08g,0.3mmol)、P(t-Bu)3(0.13g,0.6mmol)、t-BuONa(4.2g,0.04mmol) and magnetons in a 500mL single-port reaction bottle, pouring 200mL of dry toluene, adding a reflux condenser, stirring, pumping nitrogen three times, and heating to 115 ℃ for reaction for 16h. The reaction solution was directly dried by spin-drying, dissolved in dichloromethane and column separated using PE: dcm=20:1 to give 4.4g of white powder with 65% yield. The hydrogen spectrum data is as follows ：1H NMR(400MHz,Chloroform-d)δ7.53(dd,J＝8.3,1.3Hz,1H),7.42–7.38(m,1H),7.34(m,10H),7.31–7.21(m,3H),7.21–7.17(m,2H),7.14–7.02(m,6H),6.99(ddd,J＝7.1,2.2,1.1Hz,1H),6.97–6.93(m,1H),6.85(m,1H),6.47(t,J＝2.3Hz,1H),3.92(m,2H),2.20(m,2H).
Synthesis of Compound (1):
1000mL three-necked bottle, dropping funnel and condenser tube are assembled and then the bottle is baked twice; cooling to room temperature, adding (1 i) (13.5 g) into a reaction flask, pouring 250mL of tert-butylbenzene, and pumping air three times; t-BuLi (60 mL, 1.3M) was added to the dropping funnel using a syringe; placing the system at-40 ℃, stirring for 0.5h, dropwise adding t-BuLi, naturally heating to room temperature after the dropwise adding, and then carrying out oil bath for 90 ℃ for 2h; the system was cooled to room temperature, cooled to-30℃again, BBr 3 (9 mL) was added dropwise with a syringe, warmed to room temperature after the addition, and stirred overnight. The system was cooled to 0℃again, DIEPA (26 mL) was added by syringe, dropwise added, and the mixture was warmed to room temperature after the dropwise addition, and then warmed to 120℃again, and reacted for 24 hours. The reaction was cooled to room temperature, column separation was directly performed, the obtained sample was dissolved with DCM, methanol was added, and the mixture was allowed to stand to precipitate yellow powder, which was filtered and the cake was baked at 100 ℃ for 5h. Yield 4.3g 36％.1H NMR(400MHz,Chloroform-d)1H NMR(400MHz,Chloroform-d)δ7.49(m,2H),7.38–7.31(m,12H),7.27(m,2H),7.21–7.15(m,1H),7.15–7.12(m,2H),7.09–7.02(m,4H),6.81(m,2H),3.89(m,2H),2.31(dd,J＝6.7,3.9Hz,1H),2.19(dd,J＝6.7,3.9Hz,1H).ESI-MS(m/z):537(M+1).
Example 2:
synthesis of Compound Structure 4
Similar to the synthesis of the compound structure 1, the difference is that the raw materials (1 a) are replaced by (4 a), (1 b) are replaced by (4 b), (1 e) are replaced by (4 d), and the fourth step (1 b) is replaced by (4 f), (1 h) are replaced by (4h).1H NMR(400MHz,Chloroform-d)δ7.49(t,J＝2.1Hz,1H),7.40(d,J＝2.2Hz,1H),7.36(dd,J＝7.0,2.1Hz,2H),7.33(d,J＝2.2Hz,2H),7.31–7.25(m,5H),7.24–7.20(m,2H),7.07–7.03(m,4H),7.01–6.97(m,2H),6.88–6.82(m,2H),4.03(m,2H),2.28(m,2H),1.49–1.12(m,72H).ESI-MS(m/z):1061(M+1).
Example 3:
Synthesis of Compound Structure 9
The synthesis of compound (9 b) is similar to that of compound (1 f), except that starting material (1 d) is replaced with (3 c) and (1 e) with (9 a).
The synthesis of compound (9 d) is similar to that of compound (1 f), except that raw material (1 d) is replaced with (9 b), (1 e) and (9 c).
The synthesis of compound structure 9 is similar to that of compound structure 1, except that raw material (1 i) is replaced with (9d).1H NMR(400MHz,Chloroform-d)δ8.74(d,J＝2.3Hz,1H),8.32(d,J＝2.1Hz,1H),7.90(d,J＝2.0Hz,1H),7.50(t,J＝2.2Hz,1H),7.41(dd,J＝18.7,2.2Hz,3H),7.32–7.27(m,5H),7.19(d,J＝2.2Hz,1H),7.08–6.96(m,6H),4.03(m,2H),2.28(m,2H),1.55–1.06(m,72H).ESI-MS(m/z):1060(M+1).
Example 4:
Synthesis of Compound Structure 16
Similar to the synthesis of compound structure 9, except that starting material (9 c) was replaced with (16a).1H NMR(400MHz,Chloroform-d)δ7.82(d,J＝1.8Hz,1H),7.73(d,J＝7.5Hz,1H),7.36(dd,J＝7.6,1.9Hz,1H),7.32(d,J＝2.2Hz,1H),7.30–7.25(m,6H),7.08–7.01(m,6H),6.98(d,J＝2.2Hz,1H),6.88–6.83(m,2H),4.03(m,2H),2.28(m,2H),1.49–1.21(m,54H).
Example 5:
Synthesis of Compound Structure 26
Similar to the synthesis of compound structure 9, except that starting material (9 c) was replaced with (26a).1H NMR(400MHz,Chloroform-d)δ7.70(d,J＝7.0Hz,1H),7.42(d,J＝2.2Hz,1H),7.34–7.25(m,7H),7.22(dd,J＝6.8,1.8Hz,1H),7.08–7.03(m,6H),6.97(dd,J＝13.2,2.2Hz,2H),6.86(d,J＝2.2Hz,1H),4.03(m,2H),2.28(m,2H),1.36(s,9H),1.35–1.31(m,45H).ESI-MS(m/z):978(M+1).
Example 6:
Synthesis of Compound Structure 36
Similar to the synthesis of compound structure 9, except that starting material (9 c) was replaced with (26a).1H NMR(400MHz,Chloroform-d)δ7.69(d,J＝2.0Hz,1H),7.54(d,J＝2.2Hz,1H),7.37(d,J＝8.0Hz,1H),7.31–7.24(m,7H),7.08–7.00(m,6H),6.98(d,J＝2.2Hz,1H),6.89–6.83(m,2H),4.03(m,2H),2.28(m,2H),1.48–1.22(m,54H).
Example 7:
Synthesis of Compound Structure 61
Similar to the synthesis of compound structure 9, except that raw material (4 c) was replaced with (61 a) and raw material (9 c) was replaced with (61c).1H NMR(400MHz,Chloroform-d)δ7.52(d,J＝2.0Hz,2H),7.47(d,J＝7.9Hz,2H),7.37(dd,J＝21.1,2.2Hz,2H),7.31–7.25(m,4H),7.22(dd,J＝6.3,2.3Hz,1H),7.08(d,J＝2.2Hz,1H),7.06–7.03(m,2H),7.00(d,J＝6.4Hz,1H),6.88–6.84(m,2H),4.23(m,2H),2.27(m,2H),1.46–1.22(m,54H).ESI-MS(m/z):872(M+1).
Example 8:
Synthesis of Compound Structure 78
Similar to the synthesis of compound structure 61, except that starting material (61 c) was replaced with (78a).1H NMR(400MHz,Chloroform-d)δ7.82(d,J＝1.8Hz,1H),7.73(d,J＝7.5Hz,1H),7.52(d,J＝2.0Hz,2H),7.50–7.45(m,3H),7.38–7.35(m,2H),7.34–7.31(m,3H),7.31–7.26(m,3H),7.20(d,J＝6.7Hz,1H),7.08(d,J＝2.2Hz,1H),6.87(dd,J＝19.0,2.1Hz,2H),4.23(m,2H),2.27(m,2H),1.46–1.21(m,72H).ESI-MS(m/z):1116(M+1).
Example 9:
Synthesis of Compound Structure 136
Similar to the synthesis of compound structure 61, except that raw material (61 a) was replaced with (136 a) and raw material (61 c) was replaced with (136 c) (78a).1H NMR(500MHz,Chloroform-d)δ7.82(d,J＝1.7Hz,1H),7.73(d,J＝7.5Hz,1H),7.49(t,J＝2.1Hz,1H),7.39–7.35(m,2H),7.34–7.31(m,3H),7.29(dd,J＝6.6,1.8Hz,1H),7.27–7.23(m,2H),7.20(d,J＝6.7Hz,1H),7.17(dd,J＝7.5,2.0Hz,2H),7.13–7.07(m,3H),6.87(dd,J＝19.0,2.1Hz,2H),4.24(m,2H),2.31(m,2H),1.63(s,6H),1.44–1.27(m,72H).ESI-MS(m/z):1158(M+1).
Example 10:
The organic electroluminescent material is used for preparing an organic electroluminescent low-emission device, and the structure of the device is shown in figure 1.
First, the transparent conductive ITO glass substrate 10 (with the anode 20 thereon) was washed sequentially with deionized water, ethanol, acetone, deionized water, dried at 80 °, and then treated with oxygen plasma for 30 minutes. Then, evaporating 10nm thick HATCN as the hole injection layer 30 under vacuum <4 x10 -4 pa of an evaporator; evaporating a compound HTL to form a 40nm thick hole transport layer 40; an EBL (electron blocking layer) 50 of 10nm thickness is vapor deposited on the hole transport layer; then, an EML (host: 3% guest material, light-emitting layer) 60 of 20nm thickness is evaporated, the light-emitting layer is formed by doping the electroluminescent material (compound structure 1, 3%) of the present application with a host material; an ETL (electron transport layer) 70 of 40nm thickness, which is composed of two materials, ETL1 and LiQ, was evaporated on the light emitting layer. A 1nm ytterbium metal was evaporated as an electron injection layer 80 and 100nm Ag as a device cathode 90.
Example 11-example 18 and comparative example 1, comparative example 2:
Example 11-example 18 and comparative example 1, comparative example 2 organic electroluminescent devices were fabricated as in example 10, except that the guest materials in the light emitting layer were respectively structure 4, structure 9, structure 16, structure 26, structure 36, structure 61, structure 78, structure 136 and comparative example 1, comparative example 2 in the present application. The chemical structure of the comparative example material is shown in the figure:
the electrical and optical properties of the organic electroluminescent devices of examples 10 to 18 and comparative examples 1 and 2 were measured at 0.4mA as shown in table 1.
TABLE 1
As can be seen from the data of table 1, under the same conditions, examples 10, 11, 13, 14, 16, 17, etc. all have maximum emission wavelengths blue shifted, and deep blue light emission can be obtained, as compared with comparative example 1; compared with comparative example 2, the electroluminescent materials of the present application have smaller half-peak width, which is advantageous for obtaining excellent color purity and higher efficiency of the emitting device in the electroluminescent device, so as to achieve more excellent display effect.

Claims (11)

1. An organic electroluminescent material containing a B-N structure, the structural general formula of which is shown as formula (A1):
Wherein: ar 1-Ar3 and Cy1 are independently selected from substituted or unsubstituted aryl groups having 6-30 carbon atoms, substituted or unsubstituted heteroaryl groups having 5-30 carbon atoms; or Ar 2 and Ar 3 or Ar 1 and Cy 1 independently have O, S, se, te atoms or a single bond 、-C(R4)2-C(R5)2-、-C R4＝C R5-、-C R4＝N-、-C R4＝P-、-C≡C-、 Any one of which is bonded to form a ring;
R 1-R5 is independently selected from the group consisting of hydrogen, deuterium, cyano, nitro, halo, hydroxy, alkylthio of 1 to 4 carbon atoms, alkyl of 1 to 30 carbon atoms, cycloalkyl of 1 to 20 carbon atoms, aryloxy of 6 to 30 carbon atoms, alkoxy of 1 to 30 carbon atoms, alkylamino of 1 to 30 carbon atoms, arylamino of 6 to 30 carbon atoms, aralkylamino of 6 to 30 carbon atoms, heteroarylamino of 2 to 24 carbon atoms, alkylsilane of 1 to 30 carbon atoms, alkoxysilane of 1 to 30 carbon atoms, arylsilane of 6 to 30 carbon atoms, alkenyl of 2 to 30 carbon atoms, alkynyl of 2 to 24 carbon atoms, aralkyl of 7 to 30 carbon atoms, aryl of 6 to 30 carbon atoms, heteroaryl of 5 to 60 carbon atoms, and heteroarylalkyl of 6 to 30 carbon atoms,
The substitution is substituted by deuterium, cyano, nitro, halogen, C1-C8 alkyl, C6-C20 aryl, C5-C20 heteroaryl,
The hetero atoms in the heteroaryl and the heteroaralkylamino are one or more of O, S, N, se, te.
2. The organic electroluminescent material according to claim 1, wherein the aryl group is selected from one or more of phenyl, naphthyl, anthracenyl, binaphthyl, phenanthrenyl, dihydrophenanthrenyl, pyrenyl, perylenyl, naphthacene, pentacene, benzoperylene, benzocyclopentadienyl, spirofluorenyl and fluorenyl;
the heteroaryl is selected from the group consisting of pyrrolyl, imidazolyl, thienyl, furyl, 1, 2-thiazolyl, 1, 3-thiazolyl, 1, 2-selenazolyl, 1, 3-selenazolyl, 1, 2-tellurium oxazolyl, 1, 3-tellurium oxazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, thiadiazolyl, selenadiazolyl, tellurium diazolyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, pyridyl, pyrazinyl, pyrimidinyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, indole, isoindole, indole (3, 2, 1-JK) carbazole, benzimidazole, naphthoimidazole, phenanthroimidazole, benzotriazole, purine, benzoxazole, naphthooxazole, phenanthreneoxazoles, benzothiadiazoles, benzoselenadiazoles, benzotelluridiazoles, benzotriazoles, quinolines, isoquinolines, benzopyrazines, benzothiophenes, benzoselenophenes, benzotellurophenones, benzofurans, benzopyrroles, carbazoles, acridines, dibenzothiophenes, dibenzofurans, dibenzoselenophenes, dibenzotellurophenones, dibenzothiophenes-5, 5-dioxys, naphtolthiodiazoles, naphtolselenadiazoles, and 10, 15-dihydro-5H-diindoles [3,2-a:3',2' -c ] carbazolyl.
3. The organic electroluminescent material according to claim 1, wherein: ar 1-Ar3, cy1 are independently selected from substituted or unsubstituted aryl groups having 6-30 carbon atoms, substituted or unsubstituted heteroaryl groups having 5-30 carbon atoms; either Ar 2 and Ar 3 or Ar 1 and Cy 1 independently have O, S, se atoms or single bonds,Any one of which is bonded to form a ring;
R 1-R5 is independently selected from the group consisting of hydrogen, deuterium, cyano, nitro, halo, hydroxy, alkylthio of 1 to 4 carbon atoms, alkyl of 1 to 20 carbon atoms, cycloalkyl of 1 to 10 carbon atoms, aryloxy of 6 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, alkylamino of 1 to 20 carbon atoms, arylamino of 6 to 20 carbon atoms, aralkylamino of 6 to 20 carbon atoms, heteroarylamino of 2 to 20 carbon atoms, alkylsilane of 1 to 20 carbon atoms, arylsilane of 6 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, heteroaryl of 5 to 20 carbon atoms, and heteroarylalkyl of 6 to 20 carbon atoms,
The substitution is substituted by deuterium, cyano, nitro, halogen, C1-C8 alkyl, C6-C20 aryl, C5-C20 heteroaryl,
The hetero atoms in the heteroaryl and the heteroaralkylamino are one or more of O, S, N, se, te.
4. The organic electroluminescent material as claimed in claim 3, having a structural formula represented by one of the structures of formulae (B1) to (B5):
Wherein X 1 is selected from O, S, se, Any one of them;
Ar 1 and Cy1 are selected from substituted or unsubstituted aryl with 6-20 carbon atoms, substituted or unsubstituted heteroaryl with 5-20 carbon atoms, or Ar 1 and Cy 1 can independently have O, S, se atoms or a single bond, Any one of which is bonded to form a ring;
R 1-R5 is independently selected from the group consisting of hydrogen, deuterium, cyano, nitro, halo, hydroxy, alkylthio of 1 to 4 carbon atoms, alkyl of 1 to 10 carbon atoms, cycloalkyl of 1 to 6 carbon atoms, aryloxy of 6 to 20 carbon atoms, alkoxy of 1 to 10 carbon atoms, alkylamino of 1 to 10 carbon atoms, arylamino of 6 to 10 carbon atoms, aralkylamino of 6 to 20 carbon atoms, heteroarylamino of 2 to 20 carbon atoms, alkylsilane of 1 to 10 carbon atoms, arylsilane of 6 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, heteroaryl of 5 to 20 carbon atoms, and heteroarylalkyl of 6 to 20 carbon atoms,
The substitution is substitution by deuterium, cyano, nitro, halogen, C1-C8 alkyl, C6-C20 aryl, C5-C20 heteroaryl,
The hetero atom in the heteroaryl and the heteroaralkylamino is one or more of O, S, N, se, te,
R 6-R7、R9 is independently selected from hydrogen, deuterium, cyano, nitro, halo, C1-C8 alkyl, C6-C20 aryl, C5-C20 heteroaryl.
5. The organic electroluminescent material as claimed in claim 4, wherein the structural formula is represented by one of the structures (C1) to (C36),
Wherein X 1 is selected from O, S, se,Any one of them;
R 1-R5 is independently selected from hydrogen, deuterium, cyano, nitro, halo, alkyl of 1 to 10 carbon atoms, cycloalkyl of 1 to 6 carbon atoms, aralkyl of 7 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, heteroaryl of 5 to 20 carbon atoms, or heteroarylalkyl of 6 to 20 carbon atoms,
The substitution is substituted by deuterium, cyano, nitro, halogen, C1-C8 alkyl, C6-C20 aryl, C5-C20 heteroaryl,
The hetero atoms in the heteroaryl group are one or more of O, S, N, se,
R 6-R10 is independently selected from hydrogen, deuterium, cyano, nitro, halogen, C1-C8 alkyl, C6-C20 aryl, C5-C20 heteroaryl,
Ar 1 is independently selected from substituted or unsubstituted aryl groups having from 6 to 20 carbon atoms, or Ar 1 and R8 substituted aryl or heteroaryl groups can be independently substituted with O, S, se atoms or a single bond,Any of which are bonded to form a ring.
6. The organic electroluminescent material according to claim 5, wherein Ar1 is selected from the structures D1-D17,
7. The organic electroluminescent material as claimed in claim 6, wherein R 1–R10 is independently selected from hydrogen, deuterium, linear or branched C1-C4 alkyl, phenyl, naphthyl, carbazole, carbazolocarbazole, indole (3, 2, 1-JK) carbazole.
8. The organic electroluminescent material as claimed in claim 7, having a structure represented by one of the following formulas,
9. An electroluminescent device comprising at least one functional layer comprising an organic electroluminescent material as claimed in any one of claims 1 to 8.
10. An electroluminescent device as claimed in claim 9, wherein the organic electroluminescent material as claimed in any one of claims 1 to 8 is used as the material of the luminescent layer.
11. An OLED display element, characterized in that: an electroluminescent device comprising any of claims 9-10.
CN202311379349.6A 2022-11-14 2023-10-24 Organic electroluminescent material containing B-N structure and electroluminescent device Pending CN118027076A (en)

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