CN104592194A - Thianthrene oxide-aromatic amine organic luminescent small molecule as well as preparation and application thereof - Google Patents

Thianthrene oxide-aromatic amine organic luminescent small molecule as well as preparation and application thereof Download PDF

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CN104592194A
CN104592194A CN201510007139.3A CN201510007139A CN104592194A CN 104592194 A CN104592194 A CN 104592194A CN 201510007139 A CN201510007139 A CN 201510007139A CN 104592194 A CN104592194 A CN 104592194A
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thianthrene
aromatic amine
light emission
organic light
oxide compound
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苏仕健
谢高瞻
李云川
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South China University of Technology SCUT
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Abstract

The invention belongs to the technical field of organic luminescent materials and discloses a thianthrene oxide-aromatic amine organic luminescent small molecule as well as preparation and an application thereof. The thianthrene oxide-aromatic amine organic luminescent small molecule has a structure formula as shown in the specification, wherein at least one of Ar1, Ar2, Ar3 and Ar4 is a group with an aromatic amine structure, and the rest is hydrogen. The preparation method comprises the following steps: (1) carrying out reaction on thianthrene and liquid bromine to obtain bromo-substituted thianthrene; (2) carrying out reaction on the bromo-substituted thianthrene and hydrogen peroxide to obtain bromo-substituted thianthrene oxide; and (3) carrying out reaction on the bromo-substituted thianthrene oxide and a compound with an aromatic amine structure to obtain the thianthrene oxide-aromatic amine organic luminescent small molecule. The thianthrene oxide-aromatic amine organic luminescent small molecule is good in luminescent property and can be used for preparing organic luminescent devices as a luminescent layer material.

Description

A kind of thianthrene oxide compound-aromatic amine organic light emission small molecules and preparation and application
Technical field
The invention belongs to technical field of organic luminescence materials, be specifically related to a kind of thianthrene oxide compound-aromatic amine organic light emission small molecules and preparation and application.
Background technology
Organic Light Emitting Diode, through the development of more than 20 years, has started to enter industrial phases in plane display, illumination.Compared to polymkeric substance, organic light emission small molecules due to preparation process few, Stability Analysis of Structures, can purifying, thus can obtain higher device efficiency to such an extent as to can obtain commercial applications.
Traditional organic molecule fluorescent material, the triplet excitons due to 75% is spin forbidden, radioluminescence can not occur, and thus only has the singlet exciton of 25% can be luminous, and luminous efficiency is low.Comparatively speaking, the organic phosphorescent material based on the metal complexes such as iridium, platinum passes through Quantum geometrical phase, can realize the internal quantum efficiency of 100%.But the metal such as iridium, platinum is due to resource-constrained, the problem that expensive and blue phosphor materials efficiency is not high can not be resolved for a long time, and the application of organic phosphorescent material is restricted.Thus, for the long-run development in organic light emission field, developing efficient, cheap luminescent material becomes the problem that is needed badly solution.
Recent years, the people such as Japanese Chihaya professor Adachi have developed a series of thermal excitation delayed fluorescence organic materials.These luminescent materials there is very little singlet and triplet energy state poor, can by thermal excitation make triplet excitons be between anti-channeling, effectively utilize triplet excitons, thus improve the luminous efficiency of material.Meanwhile, compare organic phosphorescent material, the delayed fluorescence material of full stress-strain synthesis has easy synthesis, the advantage of low cost.Logical research in a few years, thermal excitation delayed fluorescence organic materials achieves huge progress, but in order to meet the requirement of luminescent device, the blue light of efficient stable, green glow and red light material await further exploitation more.
Up to now, for the evaporation molecule of the overwhelming majority of thermal excitation delayed fluorescence organic luminescent device with unit such as sulfobenzide, thioxanthone, triazines for core, and have no precedent report with the organic light emission small molecules that thianthrene oxide compound is core.
Summary of the invention
In order to solve the shortcoming and defect part of above prior art, primary and foremost purpose of the present invention is to provide a kind of thianthrene oxide compound-aromatic amine organic light emission small molecules.
Another object of the present invention is to provide above-mentioned thianthrene oxide compound-micromolecular preparation method of aromatic amine organic light emission.
Another object of the present invention is to provide above-mentioned thianthrene oxide compound-micromolecular application of aromatic amine organic light emission.
The object of the invention is achieved through the following technical solutions:
A kind of thianthrene oxide compound-aromatic amine organic light emission small molecules, described organic light emission small molecules has following general structure:
Wherein, Ar 1, Ar 2, Ar 3and Ar 4in have at least one to be the group with aromatic amine structure, all the other are hydrogen.
The described group with aromatic amine structure preferably has the group of structure described in any one of (1) ~ (10):
Described thianthrene oxide compound-aromatic amine organic light emission small molecules preferably has the structural formula described in any one of T1 ~ T20:
Above-mentioned thianthrene oxide compound-micromolecular preparation method of aromatic amine organic light emission, comprises the following steps:
(1) thianthrene and bromine carry out being obtained by reacting the thianthrene that bromine replaces;
(2) bromine replace thianthrene and hydroperoxidation, obtain bromine replace thianthrene oxide compound;
(3) the thianthrene oxide compound of bromine replacement and the compound of aromatic amine structure react, and obtain thianthrene oxide compound-aromatic amine organic light emission small molecules.
Above-mentioned thianthrene oxide compound-aromatic amine organic light emission small molecules is as the application of emitting layer material in organic electroluminescence device.
In above-mentioned application, described organic electroluminescence device comprises substrate, and is formed in the anode layer on substrate successively, several luminescent layer unit and cathode layers; Described luminescent layer unit comprises hole injection layer, hole transmission layer, multiple luminescent layer and electron transfer layer.
Compound of the present invention and preparation method's tool have the following advantages and beneficial effect:
(1) thianthrene oxide core has comparatively strong suction electrically, after connection having electron-donating amine aromatic compound, there is obvious dipole characteristic, and the molecule highest occupied molecular orbital (HOMO) of this series compound is separated obviously with minimum vacant track (LUMO), there is minimum singlet and triplet energy state poor, triplet excitons anti-channeling under thermal excitation can be made to form singlet exciton, effectively improve the exciton utilization ratio of material, there is delayed fluorescence characteristic;
(2) material structure containing thianthrene oxide structure is simple, and synthesis step is few, and molecular weight is determined, is convenient to purify, can produces in batches;
(3) containing the small molecule material good stability of thianthrene oxide structure, and there is lower sublimation temperature, be conducive to the preparation of small molecules evaporation device;
(4) by changing the color of dipole moment in molecule that the chemical structure that connects can regulate and control this material effectively, conjugate length and luminescence, physical property and the photoelectric device performance of this material is improved further.
Accompanying drawing explanation
Fig. 1 is absorption spectrum under filminess of the T3 material of thianthrene oxide compound-aromatic amine organic light emission small molecules T1 of obtaining of embodiment 1 and embodiment 3 and emmission spectrum;
Fig. 2 is the voltage-current density-brightness relationship curve of T3 material as the organic luminescent device of luminescent layer of thianthrene oxide compound-aromatic amine organic light emission small molecules T1 of obtaining of embodiment 1 and embodiment 3;
Fig. 3 is the brightness-external quantum efficiency relation curve of T3 material as the organic luminescent device of luminescent layer of thianthrene oxide compound-aromatic amine organic light emission small molecules T1 of obtaining of embodiment 1 and embodiment 3;
Fig. 4 is the electroluminescent spectrum of T3 material as the organic luminescent device of luminescent layer of thianthrene oxide compound-aromatic amine organic light emission small molecules T1 of obtaining of embodiment 1 and embodiment 3.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
The preparation of the present embodiment thianthrene oxide compound-aromatic amine organic light emission small molecules T1, concrete synthetic route is as follows:
Concrete preparation process is as follows:
(1) preparation of intermediate 2-bromine thianthrene (S1): raw material thianthrene (6.5g, 30mmol) is dropped in three mouthfuls of reaction flasks of 250ml, and the Glacial acetic acid adding 60ml is dissolved.Under argon shield, slowly instill the bromine (5.76g of 1.2eq, 36mmol), after dropwising, be heated to 80 DEG C, after reaction 5h, add 100ml sodium sulfite solution (1.58M) cancellation reaction, after dichloromethane extraction, wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for Rotary Evaporators; By the solid of gained normal hexane recrystallization, obtain white solid 7.35g, productive rate 83.5%.1HNMR(600MHz，CDCl 3，δ，ppm)7.23-7.26(m，2H)，7.30-7.36(m，2H)，7.45-7.48(m，2H)，7.62(s，1H)；
(2) intermediate 2-bromo-9, the preparation of 9-bis-sulfone thianthrene (S2): under argon shield, by intermediate S1 (2g, 6.78mmol) drop in 250ml there-necked flask, add 25ml methylene dichloride and 60ml Glacial acetic acid is dissolved, then slowly 15ml hydrogen peroxide (30%) is instilled, stirred at ambient temperature 1h post-heating to 90 DEG C, reaction 36h; After reaction terminates, with dichloromethane extraction, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain white solid 1.24g, productive rate 51%; 1HNMR (600MHz, CDCl 3, δ, ppm) and 8.37-8.38 (d, 1H), 8.25-8.27 (m, 2H), 8.10-8.11 (d, 1H), 7.94-7.96 (dd, 1H), 7.84-7.86 (m, 2H);
(3) product 2-pentanoic-9, the preparation of 9-bis-sulfone thianthrene (T1): under the protection of argon gas, by intermediate S2 (1.08g, 3mmol) with pentanoic (0.54g, 3.15mmol) drop in three mouthfuls of reaction flasks of 250ml, add 100ml toluene they are dissolved, after dissolving, add tertiary butyl sodium alkoxide (0.86g successively, 9mmol), three tertiary butyl phosphine (0.65ml, 1M) with palladium (146mg, 0.65mmol), system is blackish green, after feeding intake, be heated to 110 DEG C, backflow, reaction 24h; After reaction terminates, be extracted with ethyl acetate, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain faint yellow solid 0.46g, productive rate 34%; 1HNMR (600MHz, CDCl 3, δ, ppm) and 8.18-8.23 (m, 2H), 7.92-7.94 (d, 1H), 7.77-7.80 (m, 2H), 7.65 (d, 1H), 7.36-7.41 (m, 4H), 7.24-7.27 (m, 2H), 7.16-7.18 (dd, 4H), 7.09-7.10 (dd, 1H), APCI+-MS (m/z): 448.2.
Embodiment 2:
The preparation of the present embodiment thianthrene oxide compound-aromatic amine organic light emission small molecules T2, concrete synthetic route is as follows:
Concrete preparation process is as follows:
(1) intermediate 2,3,6, the preparation of 7-tetrabromo thianthrene (S3): by raw material thianthrene (4.32g, 20mmol) drop in three mouthfuls of reaction flasks of 250ml, and the Glacial acetic acid adding 50ml is dissolved, under argon shield, slowly instill the bromine (25.6g of 8eq, 160mmol), after dropwising, be heated to 80 DEG C, after reaction 5h, add 150ml sodium sulfite solution (2M) cancellation reaction; After dichloromethane extraction, wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for Rotary Evaporators; By the solid of gained normal hexane recrystallization, obtain white solid 10g, productive rate 84%.1HNMR(600MHz，CDCl 3，δ，ppm)7.63(s，4H)；
(2) intermediate 2,3, the preparation of bromo-9, the 10-bis-sulfone thianthrenes (S4) of 6,7-tetra-: under argon shield, by intermediate S3 (2g, 3.36mmol) drop in 250ml there-necked flask, add 30ml methylene dichloride and 70ml Glacial acetic acid is dissolved, then slowly instill 15ml hydrogen peroxide (30%), stirred at ambient temperature 1h post-heating to 90 DEG C, reaction 36h; After reaction terminates, with dichloromethane extraction, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain white solid 1.72g, productive rate 77.8%.1HNMR(600MHz，CDCl 3，δ，ppm)8.4(d，4H)；
(3) product 2,3,6,7-tetra-(pentanoic)-9, the preparation of 10-bis-sulfone thianthrene (T2): under the protection of argon gas, by intermediate S2 (1.98g, 3mmol) and pentanoic (2.16g, 12.6mmol) drop in three mouthfuls of reaction flasks of 250ml, add 120ml toluene and they are dissolved; After dissolving, add tertiary butyl sodium alkoxide (0.86g, 9mmol), three tertiary butyl phosphines (0.65ml, 1M) and palladium (146mg, 0.65mmol) successively, system is blackish green; After feeding intake, be heated to 110 DEG C, backflow, reaction 24h; After reaction terminates, be extracted with ethyl acetate, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain faint yellow solid 1.40g, productive rate 49.1%; C 60h 44n 4o 4s 2m/S=949.15 theoretical value: 948.28 (100.0%), 949.28 (68.1%), 950.29 (21.1%); C, 75.93; H, 4.67; N, 5.90; O, 6.74; S, 6.76.
Embodiment 3
The preparation of the present embodiment thianthrene oxide compound-aromatic amine organic light emission small molecules T3, concrete synthetic route is as follows:
Concrete preparation process is as follows:
(1) intermediate 2-bromine thianthrene (S1) is prepared according to the step (1) in embodiment 1;
(2) preparation of intermediate 2-carbazole thianthrene (S5): under argon shield, by intermediate S1 (2g, 6.78mmol), carbazole (1.2g, 7.14mmol), Anhydrous potassium carbonate (3.3g, 23.8mmol) with cuprous iodide (3.3g, 17mmol) drop in 100ml there-necked flask, add 25ml1, they dissolve by 3-DMPU (DMPU), then add phase catalyst 18 and be preced with 6 (300mg), stirred at ambient temperature 20min post-heating to 180 DEG C, reaction 24h; After reaction terminates, suction filtration removes inorganic salt, then uses dichloromethane extraction, then washes 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain white solid 1.34g, productive rate 52%; 1HNMR (600MHz, CDCl 3, δ, ppm) and 8.47-8.52 (m, 2H), 8.31-8.34 (m, 2H), 8.13-8.15 (d, 2H), 8.05-8.07 (m, 1H), 7.87-7.89 (m, 2H), 7.47-7.50 (m, 4H), 7.36-7.39 (m, 2H).
(3) product 2-carbazole-9, the preparation of 10-bis-sulfone thianthrene (T3): under the protection of argon gas, by intermediate S5 (3.62g, 9.5mmol) drop in 250ml there-necked flask, add 35ml methylene dichloride and 95ml Glacial acetic acid is dissolved, then slowly 19ml hydrogen peroxide (30%) is instilled, stirred at ambient temperature 1h post-heating to 90 DEG C, reaction 36h; After reaction terminates, with dichloromethane extraction, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain white solid 2.05g, productive rate 47.4%; 1HNMR (600MHz, CDCl 3, δ, ppm) and 8.13-8.14 (d, 2H), 7.69-7.71 (d, 2H), 7.52-7.56 (m, 2H), 7.45-7.47 (m, 1H), 7.37-7.42 (m, 4H), 7.29-7.31 (m, 4H) APCI+-MS (m/z): 446.1.
Embodiment 4
The preparation of the present embodiment thianthrene oxide compound-aromatic amine organic light emission small molecules T4, concrete synthetic route is as follows:
Concrete preparation process is as follows:
(1) intermediate 2,3,6,7-tetrabromo thianthrene (S3) is prepared according to the step (1) in embodiment 2;
(2) product 2,3,6,7-tetra-carbazole-9, the preparation of 10-bis-sulfone thianthrene (S6): under argon shield, by intermediate S3 (2g, 3.36mmol), carbazole (4.8g, 28.56mmol), Anhydrous potassium carbonate (13.2g, 95.2mmol) and cuprous iodide (13.2g, 68mmol) drop in 250ml there-necked flask, add 50ml1, they dissolve by 3-DMPU (DMPU), then add phase catalyst 18-and are preced with-6 (800mg), stirred at ambient temperature 20min post-heating to 180 DEG C, reaction 24h; After reaction terminates, suction filtration removes inorganic salt, then uses dichloromethane extraction, then washes 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain white solid 1.2g, productive rate 68.5%; C 60h 36n 4s 2m/S=877.08 theoretical value: 876.24 (100.0%), 877.24 (68.4%), 878.24 (22.7%); C, 82.16; H, 4.14; N, 6.39; S, 7.31;
(3) product 2,3, the preparation of 6,7-tetra-carbazole-9,10-bis-sulfone thianthrene (T4): under the protection of argon gas, by intermediate S6 (1.75g, 2mmol) drop in 250ml there-necked flask, add 15ml methylene dichloride and 50ml Glacial acetic acid is dissolved, then slowly instill 6ml hydrogen peroxide (30%), stirred at ambient temperature 1h post-heating to 90 DEG C, reaction 36h; After reaction terminates, with dichloromethane extraction, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for.The solid of gained is carried out post and be separated to obtain white solid 0.82g, productive rate 43%; C 60h 36n 4o 4s 2m/S=941.08 theoretical value: 940.22 (100.0%), 941.22 (67.1%), 942.22 (23.5%); C, 76.58; H, 3.86; N, 5.95; O, 6.80; S, 6.81.
Embodiment 5
The preparation of the present embodiment thianthrene oxide compound-aromatic amine organic light emission small molecules T5, concrete synthetic route is as follows:
Concrete preparation process is as follows:
(1) bromo-9, the 10-bis-sulfone thianthrenes (S2) of intermediate 2-are prepared according to step (1) (2) in embodiment 1;
(2) product 2-(3,6-di-t-butyl carbazole)-9, the preparation of 10-bis-sulfone thianthrene (T5): under the protection of argon gas, by intermediate S2 (1.15g, 3.6mmol) with tert-butyl carbazole (1.06g, 3.78mmol) drop in three mouthfuls of reaction flasks of 250ml, add 120ml toluene and they are dissolved; After dissolving, add tertiary butyl sodium alkoxide (1.04g, 10.8mmol), three tertiary butyl phosphines (0.8ml, 1M) and palladium (146mg, 0.65mmol) successively, system is blackish green; After feeding intake, be heated to 110 DEG C, backflow, reaction 24h; After reaction terminates, be extracted with ethyl acetate, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain faint yellow solid 1.40g, productive rate 49.1%; C 32h 31nO 4s 2m/S=949.15 theoretical value: 948.28 (100.0%), 949.28 (68.1%), 950.29 (21.1%); C, 75.93; H, 4.67; N, 5.90; O, 6.74; S, 6.76.
Embodiment 6
The preparation of the present embodiment thianthrene oxide compound-aromatic amine organic light emission small molecules T6, concrete synthetic route is as follows:
Concrete preparation process is as follows:
(1) bromo-9, the 10-bis-sulfone thianthrenes (S4) of intermediate 2,3,6,7-tetra-are prepared according to step (1) (2) in embodiment 2;
(2) product 2,3,6, the preparation of 7-tetra-(3,6-di-t-butyl carbazole)-9,10-bis-sulfone thianthrene (T6): under the protection of argon gas, by intermediate S4 (1.19g, 2mmol) drop in three mouthfuls of reaction flasks of 250ml with tert-butyl carbazole (2.46g, 8.8mmol), add 120ml toluene and they are dissolved; After dissolving, add tertiary butyl sodium alkoxide (3.84g, 40mmol), three tertiary butyl phosphines (3.2ml, 1M) and palladium (584mg, 2.6mmol) successively, system is blackish green; After feeding intake, be heated to 110 DEG C, backflow, reaction 24h; After reaction terminates, be extracted with ethyl acetate, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain faint yellow solid 1.52g, productive rate 54.7%; C 92h 100n 4o 4s 2m/S=1389.93 theoretical value: 1389.72 (100.0%), 1388.72 (96.3%); C, 79.50; H, 7.25; N, 4.03; O, 4.60; S, 4.61.
Embodiment 7
The preparation of the present embodiment thianthrene oxide compound-aromatic amine organic light emission small molecules T7, concrete synthetic route is as follows:
Concrete preparation process is as follows:
(1) bromo-9, the 10-bis-sulfone thianthrenes (S2) of intermediate 2-are prepared according to step (1) (2) in embodiment 1;
(2) product 2-(9,9-dimethyl acridinium)-9, the preparation of 10-bis-sulfone thianthrene (T7): under the protection of argon gas, by intermediate S2 (0.718g, 2mmol) with tert-butyl carbazole (0.46g, 2.2mmol) drop in three mouthfuls of reaction flasks of 250ml, add 100ml toluene and they are dissolved; After dissolving, add tertiary butyl sodium alkoxide (0.58g, 6mmol), three tertiary butyl phosphines (0.45ml, 1M) and palladium (81mg, 0.36mmol) successively, system is blackish green; After feeding intake, be heated to 110 DEG C, backflow, reaction 24h; After reaction terminates, be extracted with ethyl acetate, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain faint yellow solid 0.68g, productive rate 66.6%; C 27h 21nO 4s 2m/S=508.7 theoretical value: 508.20 (100.0%), 509.21 (29.6%), 510.2 (9.2%); C, 63.75; H, 8.31; N, 2.75; O, 12.58; S, 12.61.
Embodiment 8
The preparation of the present embodiment thianthrene oxide compound-aromatic amine organic light emission small molecules T8, concrete synthetic route is as follows:
Concrete preparation process is as follows:
(1) bromo-9, the 10-bis-sulfone thianthrenes (S4) of intermediate 2,3,6,7-tetra-are prepared according to step (1) (2) in embodiment 2;
(2) product 2,3,6,7-tetra-(9,9-dimethyl acridinium)-9, the preparation of 10-bis-sulfone thianthrene (T8): under the protection of argon gas, by intermediate S4 (1.19g, 2mmol) and 9,9-dimethyl acridinium (1.84g, 8.8mmol) drop in three mouthfuls of reaction flasks of 250ml, add 120ml toluene and they are dissolved; After dissolving, add tertiary butyl sodium alkoxide (3.84g, 40mmol), three tertiary butyl phosphines (3.2ml, 1M) and palladium (584mg, 2.6mmol) successively, system is blackish green; After feeding intake, be heated to 110 DEG C, backflow, reaction 24h; After reaction terminates, be extracted with ethyl acetate, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain faint yellow solid 1.2g, productive rate 48.7%; C 72h 60n 4o 4s 2m/S=1109.40 theoretical value: 1108.41 (100.0%), 1109.41 (78.7%); C, 77.95; H, 5.45; N, 5.05; O, 5.77; S, 5.78.
Embodiment 9
The preparation of the present embodiment thianthrene oxide compound-aromatic amine organic light emission small molecules T9, concrete synthetic route is as follows:
Concrete preparation process is as follows:
(1) bromo-9, the 10-bis-sulfone thianthrenes (S2) of intermediate 2-are prepared according to step (1) (2) in embodiment 1;
(2) product 2-thiodiphenylamine-9; the preparation of 10-bis-sulfone thianthrene (T9): under the protection of argon gas; by intermediate S2 (0.718g; 2mmol) with thiodiphenylamine (0.40g; 2.2mmol) drop in three mouthfuls of reaction flasks of 250ml, add 100ml toluene and they are dissolved.After dissolving, add tertiary butyl sodium alkoxide (0.58g, 6mmol), three tertiary butyl phosphines (0.45ml, 1M) and palladium (81mg, 0.36mmol) successively, system is blackish green; After feeding intake, be heated to 110 DEG C, backflow, reaction 24h; After reaction terminates, be extracted with ethyl acetate, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain yellow solid 0.42g, productive rate 44%; C 24h 15nO 4s 3m/S=477.58 theoretical value: 477.02 (100.0%), 478.02 (28.7%), 479.01 (13.6%); C, 60.36; H, 3.17; N, 2.93; O, 13.4; S, 20.14.
Embodiment 10
The preparation of the present embodiment thianthrene oxide compound-aromatic amine organic light emission small molecules T10, concrete synthetic route is as follows:
Concrete preparation process is as follows:
(1) bromo-9, the 10-bis-sulfone thianthrenes (S4) of intermediate 2,3,6,7-tetra-are prepared according to step (1) (2) in embodiment 2;
(2) product 2,3,6,7-tetra-thiodiphenylamine-9, the preparation of 10-bis-sulfone thianthrene (T10): under the protection of argon gas, by intermediate S4 (1.19g, 2mmol) and thiodiphenylamine (1.75g, 8.8mmol) drop in three mouthfuls of reaction flasks of 250ml, add 120ml toluene and they are dissolved; After dissolving, add tertiary butyl sodium alkoxide (3.84g, 40mmol), three tertiary butyl phosphines (3.2ml, 1M) and palladium (584mg, 2.6mmol) successively, system is blackish green; After feeding intake, be heated to 110 DEG C, backflow, reaction 24h; After reaction terminates, be extracted with ethyl acetate, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain faint yellow solid 1.36g, productive rate 63.6%; C 72h 60n 4o 4s 6m/S=1069.34 theoretical value: 1068.11 (100.0%), 1069.11 (70.3%); C, 67.39; H, 3.39; N, 5.24; O, 5.98; S, 17.99.
Embodiment 11
The preparation of the present embodiment thianthrene oxide compound-aromatic amine organic light emission small molecules T11, concrete synthetic route is as follows:
Concrete preparation process is as follows:
(1) bromo-9, the 10-bis-sulfone thianthrenes (S2) of intermediate 2-are prepared according to step (1) (2) in embodiment 1;
(2) product 2-triphenylamine-9, the preparation of 10-bis-sulfone thianthrene (T11): under the protection of argon gas, by intermediate S2 (0.718g, 2mmol) with triphenylamine boric acid ester (0.816g, 2.2mmol) drop in three mouthfuls of reaction flasks of 100ml, add 24ml toluene and they dissolve by 8ml dehydrated alcohol, then add 6.5ml wet chemical (2M); After stirring 20min, add 70mg tetrakis triphenylphosphine palladium, be heated to 90 DEG C, reaction 24h; After reaction terminates, be extracted with ethyl acetate, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain yellow solid 0.83g, productive rate 79%; C 30h 21nO 4s 2m/S=523.62 theoretical value: 523.09 (100.0%), 524.09 (34.4%), 525.09 (9.7%); C, 68.81; H, 4.04; N, 2.67; O, 12.22; S, 12.25.
Embodiment 12
The preparation of the present embodiment thianthrene oxide compound-aromatic amine organic light emission small molecules T12, concrete synthetic route is as follows:
Concrete preparation process is as follows:
(1) bromo-9, the 10-bis-sulfone thianthrenes (S4) of intermediate 2,3,6,7-tetra-are prepared according to step (1) (2) in embodiment 2;
(2) product 2,3,6, the preparation of 7-tetra-triphenylamine-9,10-bis-sulfone thianthrene (T12): under the protection of argon gas, by intermediate S4 (1.19g, 2mmol) with triphenylamine boric acid ester (3.26g, 8.8mmol) drop in three mouthfuls of reaction flasks of 100ml, add 36ml toluene and they dissolve by 12ml dehydrated alcohol, then add 8ml wet chemical (2M); After stirring 20min, add 138mg tetrakis triphenylphosphine palladium, be heated to 90 DEG C, reaction 24h; After reaction terminates, be extracted with ethyl acetate, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain yellow solid 2.4g, productive rate 92.3%; C 84h 60n 4o 4s 2m/S=1289.72 theoretical value: 1288.60 (100.0%), 1289.60 (70.3%); C, 78.23; H, 7.5; N, 4.34; O, 4.96; S, 4.97.
Embodiment 13
The preparation of the present embodiment thianthrene oxide compound-aromatic amine organic light emission small molecules T13, concrete synthetic route is as follows:
Concrete preparation process is as follows:
(1) bromo-9, the 10-bis-sulfone thianthrenes (S2) of intermediate 2-are prepared according to step (1) (2) in embodiment 1;
(2) product 2-(4-(3; 6-di-t-butyl carbazole)) benzene-9; the preparation of 10-bis-sulfone thianthrene (T13): under the protection of argon gas; by intermediate S2 (0.718g; 2mmol) with 4-(3; 6-di-t-butyl carbazole) borate ester (0.962g; 2.2mmol) drop in three mouthfuls of reaction flasks of 100ml; add 24ml toluene and they dissolve by 8ml dehydrated alcohol, then add 6.5ml wet chemical (2M).After stirring 20min, add 70mg tetrakis triphenylphosphine palladium, be heated to 90 DEG C, reaction 24h; After reaction terminates, be extracted with ethyl acetate, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain yellow solid 0.88g, productive rate 65.6%; C 38h 35nO 4s 2m/S=673.03 theoretical value: 672.41 (100.0%), 673.41 (43.2%), 674.41 (10.7%); C, 67.81; H, 11.07; N, 2.08; O, 9.51; S, 9.53.
Embodiment 14
The preparation of the present embodiment thianthrene oxide compound-aromatic amine organic light emission small molecules T14, concrete synthetic route is as follows:
Concrete preparation process is as follows:
(1) bromo-9, the 10-bis-sulfone thianthrenes (S4) of intermediate 2,3,6,7-tetra-are prepared according to step (1) (2) in embodiment 2;
(2) product 2,3,6,7-tetra-(4-(3,6-di-t-butyl carbazole) benzene)-9, the preparation of 10-bis-sulfone thianthrene (T14): under the protection of argon gas, intermediate S4 (1.19g, 2mmol) and triphenylamine boric acid ester (4.24g, 8.8mmol) are dropped in three mouthfuls of reaction flasks of 100ml, add 36ml toluene and they dissolve by 12ml dehydrated alcohol, then add 8ml wet chemical (2M); After stirring 20min, add 138mg tetrakis triphenylphosphine palladium, be heated to 90 DEG C, reaction 24h; After reaction terminates, be extracted with ethyl acetate, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain yellow solid 3g, productive rate 88.2%; C 84h 60n 4o 4s 2m/S=1706.47 theoretical value: 1706.2 (100.0%), 1705.02 (79.1%); C, 80.24; H, 8.95; N, 3.28; O, 3.75; S, 3.76.
Embodiment 15
The preparation of the present embodiment thianthrene oxide compound-aromatic amine organic light emission small molecules T15, concrete synthetic route is as follows:
Concrete preparation process is as follows:
(1) bromo-9, the 10-bis-sulfone thianthrenes (S2) of intermediate 2-are prepared according to step (1) (2) in embodiment 1;
(2) product 2-(3-boric acid ester-9-phenyl carbazole)-9, the preparation of 10-bis-sulfone thianthrene (T15): under the protection of argon gas, by intermediate S2 (0.718g, 2mmol) with 3-boric acid ester-9-phenyl carbazole (0.811g, 2.2mmol) drop in three mouthfuls of reaction flasks of 100ml, add 24ml toluene and they dissolve by 8ml dehydrated alcohol, then add 6.5ml wet chemical (2M); After stirring 20min, add 70mg tetrakis triphenylphosphine palladium, be heated to 90 DEG C, reaction 24h; After reaction terminates, be extracted with ethyl acetate, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain yellow solid 1.02g, productive rate 76.7%; C 30h 19nO 4s 2m/S=566.85 theoretical value: 566.32 (100.0%), 567.32 (34.4%), 568.31 (9%); C, 63.57; H, 11.36; N, 2.47; O, 11.29; S, 11.31.
Embodiment 16
The preparation of the present embodiment thianthrene oxide compound-aromatic amine organic light emission small molecules T16, concrete synthetic route is as follows:
Concrete preparation process is as follows:
(1) bromo-9, the 10-bis-sulfone thianthrenes (S4) of intermediate 2,3,6,7-tetra-are prepared according to step (1) (2) in embodiment 2;
(2) product 2,3,6, the preparation of 7-tetra-(9-phenyl carbazole)-9,10-bis-sulfone thianthrene (T16): under the protection of argon gas, by intermediate S4 (1.19g, 2mmol) with 3-boric acid ester-9-phenyl carbazole (3.24g, 8.8mmol) drop in three mouthfuls of reaction flasks of 100ml, add 36ml toluene and they dissolve by 12ml dehydrated alcohol, then add 8ml wet chemical (2M); After stirring 20min, add 138mg tetrakis triphenylphosphine palladium, be heated to 90 DEG C, reaction 24h; After reaction terminates, be extracted with ethyl acetate, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain yellow solid 2.1g, productive rate 81.4%; C 84h 52n 4o 4s 2m/S=1293.72 theoretical value: 1292.60 (100.0%), 1293.60 (94.1%); C, 77.98; H, 7.78; N, 4.33; O, 4.95; S, 4.96.
Embodiment 17
The preparation of the present embodiment thianthrene oxide compound-aromatic amine organic light emission small molecules T17, concrete synthetic route is as follows:
Concrete preparation process is as follows:
(1) bromo-9, the 10-bis-sulfone thianthrenes (S2) of intermediate 2-are prepared according to step (1) (2) in embodiment 1;
(2) product 2-(4-(9,9-dimethyl acridinium) benzene)-9, the preparation of 10-bis-sulfone thianthrene (T17): under the protection of argon gas, by intermediate S2 (0.718g, 2mmol) with 4-(9,9-dimethyl acridinium) borate ester (0.904g, 2.2mmol) drop in three mouthfuls of reaction flasks of 100ml, add 24ml toluene and they dissolve by 8ml dehydrated alcohol, then add 6.5ml wet chemical (2M); After stirring 20min, add 70mg tetrakis triphenylphosphine palladium, be heated to 90 DEG C, reaction 24h; After reaction terminates, be extracted with ethyl acetate, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain yellow solid 0.98g, productive rate 79.6%; C 33h 25nO 4s 2m/S=614.96 theoretical value: 614.40 (100.0%), 615.40 (36.1%), 616.39 (9.1%); C, 64.45; H, 12.44; N, 2.28; O, 10.41; S, 10.43.
Embodiment 18
The preparation of the present embodiment thianthrene oxide compound-aromatic amine organic light emission small molecules T18, concrete synthetic route is as follows:
Concrete preparation process is as follows:
(1) bromo-9, the 10-bis-sulfone thianthrenes (S4) of intermediate 2,3,6,7-tetra-are prepared according to step (1) (2) in embodiment 2;
(2) product 2,3,6,7-tetra-(4-(9,9-dimethyl acridinium) benzene)-9, the preparation of 10-bis-sulfone thianthrene (T18): under the protection of argon gas, by intermediate S4 (1.19g, 2mmol) with 4-(9,9-dimethyl acridinium) borate ester (3.62g, 8.8mmol) drop in three mouthfuls of reaction flasks of 100ml, add 36ml toluene and they dissolve by 12ml dehydrated alcohol, then add 8ml wet chemical (2M); After stirring 20min, add 138mg tetrakis triphenylphosphine palladium, be heated to 90 DEG C, reaction 24h; After reaction terminates, be extracted with ethyl acetate, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain yellow solid 2.62g, productive rate 89.1%; C 96h 76n 4o 4s 2m/S=1468.07 theoretical value: 1467.82 (100.0%), 1466.82 (93.4%); C, 78.54; H, 8.92; N, 3.82; O, 4.36; S, 4.37.
Embodiment 19
The preparation of the present embodiment thianthrene oxide compound-aromatic amine organic light emission small molecules T19, concrete synthetic route is as follows:
Concrete preparation process is as follows:
(1) bromo-9, the 10-bis-sulfone thianthrenes (S2) of intermediate 2-are prepared according to step (1) (2) in embodiment 1
(2) product 2-(4-thiodiphenylamine benzene)-9, the preparation of 10-bis-sulfone thianthrene (T19): under the protection of argon gas, by intermediate S2 (0.718g, 2mmol) with 4-thiodiphenylamine borate ester (0.882g, 2.2mmol) drop in three mouthfuls of reaction flasks of 100ml, add 24ml toluene and they dissolve by 8ml dehydrated alcohol, then add 6.5ml wet chemical (2M); After stirring 20min, add 70mg tetrakis triphenylphosphine palladium, be heated to 90 DEG C, reaction 24h; After reaction terminates, be extracted with ethyl acetate, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain yellow solid 0.74g, productive rate 61.7%; C 30h 19nO 4s 3m/S=610.98 theoretical value: 610.35 (100.0%), 611.36 (32.8%), 612.35 (13.7%); C, 58.97; H, 12.51; N, 2.29; O, 10.47; S, 15.74.
Embodiment 20
The preparation of the present embodiment thianthrene oxide compound-aromatic amine organic light emission small molecules T20, concrete synthetic route is as follows:
Concrete preparation process is as follows:
(1) bromo-9, the 10-bis-sulfone thianthrenes (S4) of intermediate 2,3,6,7-tetra-are prepared according to step (1) (2) in embodiment 2;
(2) product 2,3,6, the preparation of 7-tetra-(4-thiodiphenylamine benzene)-9,10-bis-sulfone thianthrene (T20): under the protection of argon gas, by intermediate S4 (1.19g, 2mmol) with 4-thiodiphenylamine borate ester (3.53g, 8.8mmol) drop in three mouthfuls of reaction flasks of 100ml, add 36ml toluene and they dissolve by 12ml dehydrated alcohol, then add 8ml wet chemical (2M); After stirring 20min, add 138mg tetrakis triphenylphosphine palladium, be heated to 90 DEG C, reaction 24h; After reaction terminates, be extracted with ethyl acetate, then wash 3 times with saturated nacl aqueous solution, add anhydrous magnesium sulfate drying, be spin-dried for; The solid of gained is carried out post and be separated to obtain yellow solid 2.4g, productive rate 83.8%; C 84h 52n 4o 4s 6m/S=1434.05 theoretical value: 1432.55 (100.0%), 1433.56 (91.6%); C, 70.35; H, 7.86; N, 3.91; O, 4.46; S, 13.42.
The T3 that the thianthrene oxide compound that embodiment 1 obtains-aromatic amine organic light emission small molecules T1 and embodiment 3 obtain carries out heat/photophysical property test, and result is as shown in table 1:
Heat/the photophysical property of table 1 T1, T3 material
In table, subscript is expressed as follows: a heat decomposition temperature; B second-order transition temperature; Absorption under c filminess and transmitting; D cyclic voltammetry is tested, and is calculated by formula HOMO=-(Eox+4.4) eV; E calculates according to the cut-off wave long value of film absorption spectrum and HOMO energy level.
Can find out that T1 and T3 two materials have higher heat decomposition temperature by upper table result, but due to molecular weight, their second-order transition temperature is all lower; Electro-chemical test shows that it has suitable HOMO energy level, is conducive to hole and injects from anode, and reduce the driving voltage of organic luminescent device.
The absorption emmission spectrum of T1 and T3 under film as shown in Figure 1; The absorption peak peak value of T1 and T3 under filminess is close as can be seen from Figure, wherein maximum wavelength is that the absorption peak peak shape of 335nm is comparatively sharp-pointed, π-π the * belonging to molecule excites, and the absorption peak peak shape at the 376nm place of the 377nm place of T1 and T3 is comparatively flat, is that the CT state of molecule excites.In addition, although T1 with T3 two molecular structures are similar, be electrically better than carbazole due to pentanoic, make the emission wavelength of T1 compared with T3, red shift 22nm.
The T3 that the thianthrene oxide compound that embodiment 1 obtains-aromatic amine organic light emission small molecules T1 and embodiment 3 obtain is as the application of luminescent layer in organic electroluminescence device:
The device architecture implemented is as follows:
ITO(95nm)/HATCN(5nm)/TAPC(30nm)/CzSi(5nm)/EML(25nm)/TmPyPB(40nm)/LiF(1nm)/Al(80nm)
EML:Device A/T1(10％wt):mCP；Device B/T3(10％wt):mCP
The structural formula of material therefor is as follows:
Voltage-current density-brightness relationship the curve of gained luminescent device as shown in Figure 2; Its brightness-external quantum efficiency relation curve as shown in Figure 3; It is 10mA/cm in current density 2time electroluminescent spectrum as shown in Figure 4.As can be seen from Figure 4, T1 and T3 material is all blue green light, and the electroluminescence emission peak value of T1 material is 502nm, and the emission peak of T3 material is 488nm.
Above-mentioned luminescent device luminescent properties test data is summed up as shown in table 2.
Table 2 T1 and T3 sums up as the device data of luminescent layer
Subscript a represents that brightness is 1cd/m 2time voltage.
As can be seen from Table 2, T1 is 5.2V as the bright voltage that opens of the device of luminescent layer, and maximum current efficiency is 17.3cd/A, and maximum external quantum efficiency is 6.28%; T3 is better as the efficiency of the device of luminescent layer, and opening bright voltage is 4.3V, and maximum current efficiency is 23.2cd/A, and maximum external quantum efficiency is 8.83%, far above traditional fluorescent material.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (6)

1. thianthrene oxide compound-aromatic amine organic light emission small molecules, is characterized in that: described organic light emission small molecules has following general structure:
Wherein, Ar 1, Ar 2, Ar 3and Ar 4in have at least one to be the group with aromatic amine structure, all the other are hydrogen.
2. a kind of thianthrene oxide compound-aromatic amine organic light emission small molecules according to claim 1, is characterized in that: described in there is aromatic amine structure group comprise the group of structure described in any one of following (1) ~ (10):
3. a kind of thianthrene oxide compound-aromatic amine organic light emission small molecules according to claim 1, is characterized in that: described organic light emission small molecules has the structural formula described in any one of T1 ~ T20:
4. the thianthrene oxide compound described in any one of claims 1 to 3-micromolecular preparation method of aromatic amine organic light emission, is characterized in that comprising the following steps:
(1) thianthrene and bromine carry out being obtained by reacting the thianthrene that bromine replaces;
(2) bromine replace thianthrene and hydroperoxidation, obtain bromine replace thianthrene oxide compound;
(3) the thianthrene oxide compound of bromine replacement and the compound of aromatic amine structure react, and obtain thianthrene oxide compound-aromatic amine organic light emission small molecules.
5. the thianthrene oxide compound described in any one of claims 1 to 3-aromatic amine organic light emission small molecules is as the application of emitting layer material in organic electroluminescence device.
6. application according to claim 5, is characterized in that: described organic electroluminescence device comprises substrate, and is formed in the anode layer on substrate successively, several luminescent layer unit and cathode layers; Described luminescent layer unit comprises hole injection layer, hole transmission layer, multiple luminescent layer and electron transfer layer.
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US11926772B2 (en) 2020-01-03 2024-03-12 Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. High-performance sky blue thermally activated delayed fluorescent material, manufacturing method thereof, and application thereof
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