CN114573583A - Organic small molecule based on quinoline [3,2,1-de ] acridine-5, 9-diketone and application thereof in photoluminescence - Google Patents

Organic small molecule based on quinoline [3,2,1-de ] acridine-5, 9-diketone and application thereof in photoluminescence Download PDF

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CN114573583A
CN114573583A CN202210250459.1A CN202210250459A CN114573583A CN 114573583 A CN114573583 A CN 114573583A CN 202210250459 A CN202210250459 A CN 202210250459A CN 114573583 A CN114573583 A CN 114573583A
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路萍
靳海旭
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Jilin University
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Abstract

Based on quinoline [3,2,1-de]Organic micromolecules of acridine-5, 9-diketone and application thereof in photoluminescence belong to the technical field of organic photoelectric materials. The invention relates to a quinoline [3,2,1-de ]]Acridine-5, 9-diketone molecule as core, on one hand, proper donor group is introduced at the periphery of the molecule, and the molecule is inhibited from being excited to S state1Transition back to ground state S0So that the molecules are in an excited state S1Transition back to ground state S0Recombination energy required for recombination is reduced, and the half-peak width of the molecule is narrowed; on the other hand, the molecules are effectively inhibited in the transition process by increasing the rigid structure of the moleculesThe vibration relaxes, the peripheral tert-butyl can effectively inhibit the interaction between molecules to weaken the surface vibration of the molecules, so that the structural configuration of the molecules in an excited state is reduced, the recombination energy of the molecules is reduced, and the luminescent molecules with narrow-spectrum (the half-peak width is less than 20nm) emission properties are obtained.

Description

Organic small molecule based on quinoline [3,2,1-de ] acridine-5, 9-diketone and application thereof in photoluminescence
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a small organic molecule based on quinoline [3,2,1-de ] acridine-5, 9-diketone (QAO) and application thereof in photoluminescence.
Background
Organic electroluminescent diode (OLED) technology has advanced significantly in recent decades, becoming the most promising full-color display and lighting technology. There are more and more deep applications ranging from commercial display screens to bio-imaging, medical, military, etc. The Organic Light Emitting Diode (OLED) does not depend on a backlight source to emit light actively, so that the OLED has the characteristics of high response speed, wide viewing angle, lightness, thinness, low energy consumption, easiness in flexibility and the like, and gradually replaces an LCD (liquid crystal display) to become a next generation of star display technology.
An Organic Light Emitting Diode (OLED) based on a Thermally-Activated Delayed Fluorescence (TADF) mechanism adopts a pure organic fluorescent material which does not contain precious metals such as iridium and platinum, and can realize 100% of exciton utilization rate by utilizing an inverse Intersystem Crossing (RISC) process from a triplet state to a singlet state, and the External Quantum Efficiency (EQE) of the TADF-OLED approaches or even exceeds the level of a phosphorescent device through the development of recent years. TADF materials not only have the advantage of low cost, but also can be used as luminescent materials and host materials to realize multifunctional applications, and have been considered as the next generation OLED materials and widely studied, but now face some problems to be solved. Although the introduction of TADF material as the light emitting material in the OLED device can indeed achieve high efficiency, most devices have poor color purity and are increasingly unable to meet the requirements of people for full-color display technology, so the development of OLED materials with high efficiency, high definition and high color gamut is urgent.
When charge transfer occurs in a molecule, the TADF molecule causes vibrational relaxation in the molecule, rotation between donor and acceptor molecules, vibration of the plane of the molecule itself, and the like, so that recombination energy of the molecule is increased, and a broad emission peak without a fine structure is expressed, and the full-width at half-height maximum (FWHM) of the emission peak is approximately distributed between 80 nm and 100 nm. It cannot meet the requirements of high efficiency, high definition, high color gamut. Therefore, the development of a novel high-efficiency narrow-spectrum TADF luminescent material can fundamentally solve the problem of impure light color, and is a new research hotspot in the field of OLED.
In recent years, Hatakeyama et al have proposed a completely new narrow-spectrum molecular design strategy, MR-TADF, by designing planar boron and oxygen (or nitrogen) aromatic compounds. The multiple resonance effect (MR) of boron atoms and nitrogen atoms is utilized to effectively inhibit the vibration relaxation of molecules, and the rigid structure of the molecules inhibits the vibration, rotation and other activities of the molecules, thereby reducing the excited state S of the molecules1Transition back to S0The reorganization energy of the process (. lamda.) results in a relatively narrow half-peak width (FWHM < 30 nm). However, due to the unique molecular structure of the MR-TADF molecule, the research system of the molecule is too single, the types of the molecules are few, and the research and the development of the narrow-spectrum molecule are not facilitated.
Disclosure of Invention
The invention aims to provide a small organic molecule based on quinoline [3,2,1-de ] acridine-5, 9-diketone (QAO) and application thereof in photoluminescence. The organic micromolecule material is a high blue light luminous efficiency material based on a TADF luminous mechanism, integrates narrow spectrum emission, high luminous efficiency, good thermal stability and excellent photoluminescence performance, and can be used for preparing a luminous layer of a doped organic electroluminescent device.
The invention relates to a novel organic micromolecule based on quinoline [3,2,1-de ] acridine-5, 9-diketone (QAO), which has the following structural general formula:
Figure BDA0003543065720000021
wherein R is1、R2、R3Is diphenylamine and its derivatives, carbazole and its derivatives, phenothiazine and its derivatives, phenoxazine and its derivatives.
R1、R2、R3The group structure is shown as follows:
Figure BDA0003543065720000022
the molecule (P1-P5) involved in the invention is shown as the following figure:
Figure BDA0003543065720000023
Figure BDA0003543065720000031
the principle of the invention is as follows: with quino [3,2,1-de]Acridine-5, 9-diketone molecule as core, quinoline [3,2,1-de]The No. 6 site and the No. 7 site of the acridine-5, 9-dione molecule are connected to obtain a more rigid molecular structure of a large plane, so that not only is the vibration relaxation of the molecule in the transition process further inhibited, but also the energy loss caused by the vibration and rotation of the molecular plane is greatly inhibited, the recombination energy of the molecule in the process of transition from an excited state to a ground state is further reduced, and a narrower emission spectrum is obtained. Furthermore, in the case of quino [3,2,1-de]The periphery of the acridine-5, 9-diketone molecule is introduced with proper substituent groups, and although the rotation vibration between molecules is increased, the electron-donating groups added on the periphery not only inhibit the molecules from being in an excited state S1Transition back to ground state S0So that the molecules are in an excited state S1Transition back to ground state S0Recombination energy required for recombination can be reduced, and large steric hindrance groups can weaken interaction between molecules and reduce recombination energy. The increase in the recombination energy due to the rotational vibration is smaller than the decrease in the recombination energy due to the suppression of the high-frequency vibration of the molecule, so that the recombination energy of the molecule as a whole is decreased, and the half-width of the molecule is narrowed.
The organic micromolecule luminescent material has the following characteristics:
1. the molecular system is novel, has high expansion space and narrow half-peak width of the spectrum.
2. The preparation method is simple, the reaction conditions are mild, and the prepared target product has excellent thermal stability and chemical stability.
3. The quantum chemical theory calculation shows that the peripheral group substituted by the single bond can inhibit the carbon-carbon stretching vibration of the high frequency of the molecule, the low-frequency vibration mainly comprising the torsional vibration is dominant, the recombination energy of the molecule is reduced, the structural configuration of the molecule in an excited state is reduced, and the half-peak width of the target molecule is further narrowed.
Drawings
FIG. 1 is an absorption and emission spectrum of compound P1 in toluene solution; the left peak is an absorption peak, and the absorption peak position is 422 nm; the right peak is an emission peak which is at 439nm, is a deep blue light molecule and has a full width at half maximum FWHM of 17nm, so that the increase of the rigidity of the molecule can weaken the vibration and rotation of the molecule and reduce the recombination energy, thereby narrowing the full width at half maximum.
FIG. 2 is an absorption and emission spectrum of compound P2 in toluene solution; the left peak is an absorption peak, and the absorption peak position is 458 nm; the right peak is an emission peak which is 481nm, is a blue light molecule and has a full width at half maximum FWHM of 30 nm; therefore, the proper electron-donating group is introduced to the periphery of the quinoline [3,2,1-de ] acridine-5, 9-diketone, so that the high-frequency vibration of molecules can be effectively inhibited, the recombination energy of the molecules is reduced, and the half-peak width of the molecules is narrowed.
FIG. 3 is an absorption and emission spectrum of compound P3 in toluene solution; the left peak is an absorption peak, and the absorption peak position is 468 nm; the right side is an emission peak, the position of the emission peak is 528nm, and the emission peak is a green light molecule.
FIG. 4 is an absorption and emission spectrum of compound P4 in toluene solution; the left peak is an absorption peak, and the absorption peak position is 460 nm; the right peak is an emission peak which is 481nm, is a light blue photon and has a full width at half maximum FWHM of 26 nm; therefore, proper electron-donating groups are introduced to the periphery of the quinoline [3,2,1-de ] acridine-5, 9-diketone, so that the high-frequency vibration of molecules can be effectively inhibited, the recombination energy of the molecules is reduced, and the half-peak width of the molecules is narrowed.
FIG. 5 is an absorption and emission spectrum of compound P5 in toluene solution; the left peak is an absorption peak, and the absorption peak position is 434 nm; the right peak is an emission peak, the emission peak position is 453nm, the emission peak position is a blue light molecule, and the full width at half maximum FWHM is 32 nm; therefore, the proper electron-donating group is introduced to the periphery of the quinoline [3,2,1-de ] acridine-5, 9-diketone, so that the high-frequency vibration of molecules can be effectively inhibited, the recombination energy of the molecules is reduced, and the half-peak width of the molecules is narrowed.
FIG. 6 is a spectrum of a doped electroluminescent device prepared by using the material P4 of the invention.
FIG. 7 is a spectrum of a doped electroluminescent device prepared by using the inventive material P5.
The electroluminescent device can be used for preparing an illuminating light source, a signal lamp, a sign or a flat panel display.
Detailed Description
Example 1: the preparation method of the P1 comprises the following steps:
synthesis of M1: dimethyl iodoisophthalate (4.8g,15mmol), 3, 6-di-tert-butylcarbazole (4.464g,16mmol), potassium carbonate (2.49g,18mmol), and activated copper (0.19g,3mmol) were mixed with 100mL of o-dichlorobenzene in a 250mL round-bottom flask, and vacuum/nitrogen evacuation was repeated 3 times. A condensing reflux device was set up and the reaction mixture was heated to 180 ℃ for 48h under nitrogen. After cooling to room temperature, the reaction was poured into 200mL of purified water, the reaction was extracted with dichloromethane, the solvent was removed under vacuum, and then the sample was purified by silica gel column chromatography using petroleum ether/dichloromethane (1/2, v/v) as eluent to obtain 5.91g (yield 84%) of a pale green oily liquid finally. Mass Spectrometry MALDT-TOF (M/z) [ M+]: the measured value was 471.3 and the theoretical value was 471.6.
Figure BDA0003543065720000041
Synthesis of M2: m1(4.71g,10mmol) and sodium hydroxide (2.0g,50mmol), ethanol/water (volume ratio 1: 1)100mL were added to a 250mL round bottom flask and returned at 78 deg.CStream 12 h. Acidification with 37% by weight of concentrated hydrochloric acid gave a pale yellow precipitate which was collected by vacuum filtration and dried in an oven (80 ℃) overnight before being used as such without further purification. Finally, 4.33g of a pale yellow solid was obtained (yield 98%). Mass Spectrometry MALDT-TOF (M/z) [ M+]: the measured value was 443.23, and the theoretical value was 443.54.
Figure BDA0003543065720000051
Synthesis of P1: m2(3.544g,8mmol) was charged into a 250mL three-necked round bottom flask, anhydrous dichloromethane (80mL) was added, two drops (0.04mL) of N, N-Dimethylformamide (DMF) were added dropwise via a dropper, a reflux apparatus with a condenser tube was set up, oxalyl chloride (1.5mL,17.6mmol) was then added, and the reaction was heated under reflux for 0.5 h. Tin tetrachloride (2.0mL,17.6mmol) was added and the reaction refluxed for an additional 3 h. After completion of the reaction, the reaction mixture was added dropwise to an aqueous solution of sodium hydroxide (1mol/L) and extracted with methylene chloride. The organic layer was dried over sodium sulfate and concentrated. The crude product was then purified by column chromatography on silica gel using dichloromethane/petroleum ether (4/1, v/v) as eluent to give finally 2.45g (77% yield) of a bright yellow solid. Mass Spectrometry MALDT-TOF (M/z) [ M+]: measured value 407.24, theoretical value 407.51 elemental analysis: for C28H25NO2: the measured values are: c83.09, H6.147, N3.34, theoretical values: c82.53, H6.18, N3.44.
Figure BDA0003543065720000052
Example 2: the preparation method of P2 comprises the following steps:
Figure BDA0003543065720000053
synthesis of M1: the compound dimethyl 1, 5-bromo-2-iodoisophthalate (5.97g,15mmol), 3,6 di-tert-butyldiphenylamine (4.50g,16mmol), potassium carbonate (2.49g,18mmol) and activated copper powder (0.19g,3mmol) were combined with 100mL of o-dichlorobenzene in a 250mL round-bottomed flask and evacuated/charged with nitrogen for 3 iterations. A condensing reflux device was set up and the reaction mixture was heated to 180 ℃ under nitrogen for 48 h. After cooling to room temperature, the reaction was poured into 200mL of purified water, the reaction was extracted with dichloromethane, the solvent was removed under vacuum, and then the sample was purified by silica gel column chromatography using petroleum ether/dichloromethane (1/1, v/v) as eluent to obtain 6.87g (yield 84.5%) of pale yellow solid finally.
Mass Spectrometry MALDT-TOF (M/z) [ M+]: the measured value was 552.34, and the theoretical value was 552.51.
Figure BDA0003543065720000061
Synthesis of M2: m1(5.52g,10mmol) and sodium hydroxide (2.0g,50mmol), 100mL ethanol/water (1: 1 by volume) were added to a 250mL round bottom flask and mixed. Stirring and refluxing at 78 deg.C for 12 h. After cooling to room temperature, a yellow solid precipitated by acidification with 37% by weight of concentrated hydrochloric acid, filtered through a buchner funnel, washed with deionized water and dried in a vacuum oven overnight. The product was used as a yellow solid, 4.98g (95% yield) without further purification. Mass Spectrometry MALDT-TOF (M/z) [ M+]: the measured value was 524.26, and the theoretical value was 524.64.
Figure BDA0003543065720000062
Synthesis of M3: m2(4.20g,8mmol) was charged into a 250mL three-necked round bottom flask, anhydrous dichloromethane (80mL) was added, two drops (0.04mL) of N, N-Dimethylformamide (DMF) were added dropwise via a dropper, a reflux apparatus with a condenser was set up, and then oxalyl chloride (1.5mL,17.6mmol) was added and the reaction heated to reflux for 0.5 h. Tin tetrachloride (2.0mL,17.6mmol) was added and the reaction was refluxed for an additional 3 h. After completion of the reaction, the reaction mixture was added dropwise to an aqueous solution of sodium hydroxide (1mol/L) and extracted with methylene chloride. The organic layer was dried over sodium sulfate and concentrated. Then using silica gel columnThe crude product was chromatographed using dichloromethane/petroleum ether (3/1, v/v) as eluent to give 3.12g (80% yield) of a bright orange-yellow solid. Mass Spectrometry MALDT-TOF (M/z) [ M+]: the measured value was 448.21, and the theoretical value was 448.43.
Figure BDA0003543065720000063
Synthesis of P2: m3(4.88g,10mmol), 4- (9H-phenothiazin-9-yl) phenylboronic acid (3.83g,12mmol), palladium tetratriphenylphosphine (0.34g,0.3mmol), potassium carbonate (2.76g,20mmol), and 100mL of ultra-dry tetrahydrofuran were charged into a 250mL round-bottomed flask, and vacuum evacuation/nitrogen filling was repeated 3 times. A condensing reflux device was set up and the reaction mixture was heated to 70 ℃ under nitrogen for 24 h. After cooling to room temperature, the reaction was poured into 200mL of purified water, extracted with dichloromethane, the solvent was removed under vacuum, and the sample was purified by silica gel column chromatography using dichloromethane/petroleum ether (9/1, v/v) as eluent to obtain 5.46g (yield 80%) of a yellow solid finally. Mass Spectrometry MALDT-TOF (M/z) [ M+]: the measured value was 682.47, and the theoretical value was 682.88. Elemental analysis: for C46H38N202S: measured values are C81.75, H5.484, N4.07, S3.635, theoretical values are: c80.91, H5.61, N4.10, S4.69.
Figure BDA0003543065720000071
Example 3: the preparation method of the P3 comprises the following steps:
synthesis of M1: the compound dimethyl 1, 5-bromo-2-iodoisophthalate (5.97g,15mmol), 3, 6-di-tert-butyldiphenylamine (4.50g,16mmol), potassium carbonate (2.49g,18mmol) and activated copper powder (0.19g,3mmol) were combined with 100mL of o-dichlorobenzene in a 250mL round-bottomed flask and evacuated/charged with nitrogen 3 times. A condensing reflux device was set up and the reaction mixture was heated to 180 ℃ under nitrogen for 48 h. After cooling to room temperature, the reaction was poured into 200mL of purified water, and the mixture was washed with waterThe reaction was extracted with dichloromethane, the solvent was removed under vacuum, and the sample was purified by silica gel column chromatography using petroleum ether/dichloromethane (1/1, v/v) as eluent to give 6.87g (yield 84.5%) of a pale yellow solid. Mass Spectrometry MALDT-TOF (M/z) [ M+]: the measured value was 552.34, and the theoretical value was 552.51.
Figure BDA0003543065720000072
Synthesis of M2: m1(5.52g,10mmol) and sodium hydroxide (2.0g,50mmol), ethanol/water (1: 1, v/v) were added to a 250mL round bottom flask. Stirring and refluxing at 78 deg.C for 12 h. After cooling to room temperature, a yellow solid precipitated by acidification with 37% by weight of concentrated hydrochloric acid, filtered through a buchner funnel, washed with deionized water and dried in a vacuum oven overnight. The product was used as a yellow solid, 4.98g (95% yield), without further purification. Mass Spectrometry MALDT-TOF (M/z) [ M+]: the measured value was 524.26, and the theoretical value was 524.64.
Figure BDA0003543065720000081
Synthesis of M3: m2(4.20g,8mmol) was charged into a 250mL three-necked round bottom flask, anhydrous dichloromethane (80mL) was added, two drops (0.04mL) of N, N-Dimethylformamide (DMF) were added dropwise via a dropper, a reflux apparatus with a condenser was set up, and then oxalyl chloride (1.5mL,17.6mmol) was added to heat the reaction to reflux for 0.5 h. Tin tetrachloride (2.0mL,17.6mmol) was added and the reaction refluxed for an additional 3 h. After completion of the reaction, the reaction mixture was added dropwise to an aqueous solution of sodium hydroxide (1mol/L) and extracted with methylene chloride. The organic layer was dried over sodium sulfate and concentrated. The crude product was then purified by column chromatography on silica gel using dichloromethane/petroleum ether (3/1, v/v) as eluent to give 3.12g (80% yield) of a bright orange-yellow solid. Mass Spectrometry MALDT-TOF (M/z) [ M+]: the measured value was 448.21, and the theoretical value was 448.43.
Figure BDA0003543065720000082
Synthesis of P3: m3(4.88g,10mmol), triphenylamine phenylboronic acid (3.47g,12mmol), tetratriphenylphosphine palladium (0.34g,0.3mmol), potassium carbonate (2.76g,20mmol), 100mL of extra dry tetrahydrofuran was added to a 250mL round bottom flask and vacuum/nitrogen evacuation was repeated 3 times. A condensing reflux device was set up and the reaction mixture was heated to 70 ℃ under nitrogen for 24 h. After cooling to room temperature, the reaction was poured into 200mL of purified water, extracted with dichloromethane, the solvent was removed under vacuum, and the sample was purified by silica gel column chromatography using dichloromethane as eluent to obtain 4.89g (yield 75%) of a yellow solid. Mass Spectrometry MALDT-TOF (M/z) [ M+]: the measured value was 652.67, and the theoretical value was 652.84. Elemental analysis for C46H40N202: the measured values are C81.69, H6.010, N4.00, and the theoretical values are C84.63, H6.18, N4.29.
Figure BDA0003543065720000083
Example 4: the preparation method of the P4 comprises the following steps:
synthesis of M1: the compound dimethyl 1, 5-bromo-2-iodoisophthalate (5.97g,15mmol), 3, 6-di-tert-butyldiphenylamine (4.50g,16mmol), potassium carbonate (2.49g,18mmol) and activated copper powder (0.19g,3mmol) were combined with 100mL of o-dichlorobenzene in a 250mL round-bottomed flask and vacuum/nitrogen purge repeated 3 times. A condensing reflux device was set up and the reaction mixture was heated to 180 ℃ under nitrogen for 48 h. After cooling to room temperature, the reaction was poured into 200mL of purified water, extracted with dichloromethane, the solvent was removed under vacuum, and then the sample was purified by silica gel column chromatography using petroleum ether/dichloromethane (1/1, v/v) as eluent to obtain 6.87g (yield 84.5%) of a pale yellow solid. Mass Spectrometry MALDT-TOF (M/z) [ M+]: the measured value was 552.34, and the theoretical value was 552.51.
Figure BDA0003543065720000091
Synthesis of M2: m1(5.52g,10mmol) and sodium hydroxide (2.0g,50mmol), ethanol/water (1: 1)100mL, were added to a 250mL round bottom flask. Stirring and refluxing at 78 deg.C for 12 h. After cooling to room temperature, a yellow solid precipitated by acidification with 37% by weight of concentrated hydrochloric acid, filtered through a buchner funnel, washed with deionized water and dried in a vacuum oven overnight. The product was used as a yellow solid, 4.98g (95% yield), without further purification. Mass Spectrometry MALDT-TOF (M/z) [ M+]: the measured value was 524.26, and the theoretical value was 524.64.
Figure BDA0003543065720000092
Synthesis of M3: m2(4.20g,8mmol) was charged into a 250mL three-necked round bottom flask, anhydrous dichloromethane (80mL) was added, two drops (0.04mL) of N, N-Dimethylformamide (DMF) were added dropwise via a dropper, a reflux apparatus with a condenser was set up, and then oxalyl chloride (1.5mL,17.6mmol) was added to heat the reaction to reflux for 0.5 h. Tin tetrachloride (2.0mL,17.6mmol) was added and the reaction was refluxed for an additional 3 hours. After completion of the reaction, the reaction mixture was added dropwise to an aqueous solution of sodium hydroxide (1mol/L) and extracted with methylene chloride. The organic layer was dried over sodium sulfate and concentrated. The crude product was then purified by column chromatography on silica gel using dichloromethane/petroleum ether (3/1, v/v) as eluent to give 3.12g (80% yield) of a bright orange-yellow solid. Mass Spectrometry MALDT-TOF (M/z) [ M+]: the measured value was 448.21, and the theoretical value was 448.43.
Figure BDA0003543065720000101
Synthesis of P4: m3(4.88g,10mmol), 4- (9H-carbazol-9-yl) phenylboronic acid (3.44g,12mmol), palladium tetratriphenylphosphine (0.34g,0.3mmol), potassium carbonate (2.76g,20mmol), 100mL of ultra dry tetrahydrofuran were added to a 250mL round bottom flask and vacuum/nitrogen evacuation was repeated 3 times.A condensing reflux device was set up and the reaction mixture was heated to 70 ℃ under nitrogen for 24 h. After cooling to room temperature, the reaction was poured into 200mL of purified water, extracted with dichloromethane, the solvent was removed under vacuum, and the sample was purified by silica gel column chromatography using dichloromethane as eluent to obtain 4.75g (yield 73%) of a yellow solid. Mass Spectrometry MALDT-TOF (M/z) [ M+]: the measured value was 650.65, and the theoretical value was 650.82. Elemental analysis for C46H38N2O2: the measured values are C85.41, H5.875, N4.25, and the theoretical values are C84.89, H5.89, N4.30.
Figure BDA0003543065720000102
Example 5: the preparation method of the P5 comprises the following steps:
synthesis of M1: the compound dimethyl 5-bromo-2-iodoisophthalate (5.97g,15mmol), diphenylamine (2.71g,16mmol), potassium carbonate (2.49g,18mmol) and activated copper powder (0.19g,3mmol) were combined with 100mL of o-dichlorobenzene in a 250mL round-bottomed flask and evacuated/purged with nitrogen 3 times. A condensing reflux device was set up and the reaction mixture was heated to 180 ℃ under nitrogen for 48 h. After cooling to room temperature, the reaction was poured into 200mL of purified water, extracted with dichloromethane, the solvent was removed under vacuum, and then the sample was purified by silica gel column chromatography using petroleum ether/dichloromethane (1/1, v/v) as eluent to obtain 5.52g (yield 83%) of a pale yellow solid. Mass Spectrometry MALDT-TOF (M/z) [ M+]: the measured value was 440.19, and the theoretical value was 440.29.
Figure BDA0003543065720000111
Synthesis of M2: m1(4.40g,10mmol) and sodium hydroxide (2.0g,50mmol), ethanol/water (1: 1)100mL were heated at 78 ℃ under reflux for 12 h. Acidifying with 37% by weight of concentrated hydrochloric acid, collecting Compound 3 by vacuum filtration and drying in an oven(80 ℃) overnight, then used directly without further purification. The final yield was 4.03g of yellow solid (97.5% yield). Mass Spectrometry MALDT-TOF (M/z) [ M+]: the measured value was 412.12, and the theoretical value was 412.24.
Figure BDA0003543065720000112
Synthesis of M3: m2(3.30g,8mmol) was charged into a 250mL three-necked round bottom flask, anhydrous dichloromethane (80mL) was added, two drops (0.04mL) of N, N-Dimethylformamide (DMF) were added dropwise via a dropper, a reflux apparatus with a condenser was set up, and oxalyl chloride (1.5mL,17.6mmol) was added. The reaction was heated to reflux for 0.5 h. Tin tetrachloride (2.0mL,17.6mmol) was added and the reaction was refluxed for an additional 3 h. After completion of the reaction, the reaction mixture was added dropwise to an aqueous solution of sodium hydroxide (1mol/L) and extracted with methylene chloride. The organic layer was dried over sodium sulfate and concentrated. The crude product was then purified by column chromatography on silica gel using dichloromethane/petroleum ether (4/1, v/v) as eluent to give 3.01g (79% yield) of a bright orange-yellow solid. Mass Spectrometry MALDT-TOF (M/z) [ M+]: the measured value was 376.16, and the theoretical value was 376.21.
Figure BDA0003543065720000113
Synthesis of P5: mixing M3(4.88g,10mmol), 3, 6-di-tert-butylcarbazole (3.35g,12mmol), and tris [ dibenzylideneacetone]Dipalladium (0.275g,0.3mmol), tri-tert-butylphosphine tetrafluoroborate (0.145g,0.5mmol), potassium tert-butoxide (2.24g,20mmol), 100mL of toluene were added to a 250mL round-bottomed flask, and vacuum evacuation/nitrogen filling were repeated 3 times. A condensing reflux device was set up and the reaction mixture was heated to 110 ℃ for 48h under nitrogen. After cooling to room temperature, the reaction was poured into 200mL of purified water, extracted with dichloromethane, the solvent was removed under vacuum, and the sample was purified by silica gel column chromatography using dichloromethane/petroleum ether (6/1, v/v) as eluent to obtain 4.02g (yield 71%) of a yellow solid. Mass Spectrometry MALDT-TOF (M/z) [ M+]: the measured value was 574.56, and the theoretical value was 574.72. Elemental analysis for C40H34N2O2: the measured values are C81.42, H4.140, N4.61, and the theoretical values are C83.59, H5.96, N4.87.
Figure BDA0003543065720000121
Example 6: light-emitting device [ ITO/HAT-CN/TAPC/TCTA/compound P44% mCBP/TmPyPB/LiF/Al ]
On a glass substrate plated with an ITO anode, a hole transport layer HAT-CN (thickness 6nm), a hole blocking layer TAPC (thickness 30nm), a light-emitting layer with mCBP as a host, a compound P4 prepared in example 4 as a guest, a guest doping concentration of 4 wt% (20nm), an electron transport layer TmPyPB (30nm), an electron injection material LiF (5), and an Al cathode (2000) were sequentially vapor-deposited. The pressure during the evaporation process was kept at 5X 10-6Pa. As shown in FIG. 6, the device turn-on voltage is 6.0V, the maximum current efficiency is 2.6cd/A, and the power efficiency is 1.0 lm/W. The device emits blue light, the peak position is 492nm, and the maximum brightness is 1860cd/m2。
Example 7: light-emitting device [ ITO/HAT-CN/TAPC/TCTA/Compound P54% mCBP/TmPyPB/LiF/Al ]
A hole transport layer HAT-CN (thickness of 6nm), a hole blocking layer TAPC (thickness of 30nm), a light-emitting layer, a compound P5 prepared in example 5, a light-emitting layer and an electron injection material LiF, wherein the light-emitting layer and the light-emitting layer are formed by vapor deposition, the light-emitting layer and the light-emitting layer are respectively formed by vapor deposition, the light-emitting layer and the light-emitting layer are formed by vapor deposition, the light-emitting layer is formed by vapor deposition, the compound P5 is formed by vapor deposition, the doping concentration of the light-emitting layer is 4 wt% (20nm), the electron transport layer TmPyPB (30nm), and the electron injection material LiF is formed by vapor deposition
Figure BDA0003543065720000122
Al cathode
Figure BDA0003543065720000123
The pressure during the evaporation process was kept at 5X 10-6Pa. As shown in FIG. 7, the device turn-on voltage is 6.0V, the maximum current efficiency is 14.2cd/A, and the power efficiency is 5.6 lm/W. The device emits blue light, with peak position 468nm and maximum brightness 2275cd/m2。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (4)

1. A small organic molecule based on quinoline [3,2,1-de ] acridine-5, 9-diketone has a structural general formula shown in one of the following formulas:
Figure FDA0003543065710000011
wherein R is1、R2、R3Is diphenylamine and derivatives thereof, carbazole and derivatives thereof, phenothiazine and derivatives thereof or phenoxazine and derivatives thereof.
2. A quino [3,2, 1-de-based composition according to claim 1]Organic small molecules of acridine-5, 9-dione, wherein R1、R2、R3The group structure is shown as one of the following:
Figure FDA0003543065710000012
3. the small organic molecule based on quinolino [3,2,1-de ] acridine-5, 9-dione as claimed in claim 2, having a structural formula as shown in one of the following:
Figure FDA0003543065710000013
4. the use of a small organic molecule based on a quino [3,2,1-de ] acridine-5, 9-dione as claimed in any one of claims 1 to 3 in electroluminescence.
CN202210250459.1A 2022-03-11 2022-03-11 Organic small molecule based on quinoline [3,2,1-de ] acridine-5, 9-diketone and application thereof in photoluminescence Pending CN114573583A (en)

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