CN113512027A - Indenoquinoxaline derivative and preparation method and application thereof - Google Patents

Indenoquinoxaline derivative and preparation method and application thereof Download PDF

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CN113512027A
CN113512027A CN202110819733.8A CN202110819733A CN113512027A CN 113512027 A CN113512027 A CN 113512027A CN 202110819733 A CN202110819733 A CN 202110819733A CN 113512027 A CN113512027 A CN 113512027A
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indenoquinoxaline
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苏仕健
谢文韬
刘坤坤
李梦珂
彭晓媚
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South China University of Technology SCUT
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Abstract

The invention discloses an indenone quinoxaline derivative, a preparation method and application thereof. The indenone quinoxaline derivative disclosed by the invention takes an indenone quinoxaline group as an electron acceptor and an aromatic amine group as an electron donor, and the small organic molecule has the advantages of single structure, simplicity in purification and stable yield; the organic micromolecule derivative has the property of thermal activation delayed fluorescence, can form an organic film through vacuum evaporation or spin coating, and is applied to organic photoelectric devices such as organic light-emitting diodes; the invention has important significance for developing novel organic photoelectric materials with low cost and good performance.

Description

Indenoquinoxaline derivative and preparation method and application thereof
Technical Field
The invention belongs to the field of organic chemistry, and particularly relates to an indenone quinoxaline derivative, and a preparation method and application thereof.
Background
Organic electroluminescent (OLED) devices have received much attention due to their applications in solid state lighting and flexible displays. The common luminescent materials of the OLED can be divided into two main material systems of organic micromolecules and organic polymer luminescent materials, and compared with the polymer luminescent materials, the organic micromolecules have the advantages of simple synthesis and preparation, clear and stable structure and high material purity, so that higher device performance and better stability can be obtained. At present, red, green and blue display devices prepared based on organic small molecule luminescent materials have been commercialized successfully, but due to high material preparation cost and poor device performance, development of novel luminescent materials with high efficiency and low cost becomes an important subject in the field of organic electroluminescence.
In recent years, the luminescent material based on the thermal activation delayed fluorescence mechanism is widely applied to OLED devices, and the material can effectively get rid of the problem of low exciton utilization rate of the traditional fluorescent material due to the existence of a small single triplet state energy level difference, and meanwhile, the singlet state excitons with the probability of being generated under the condition of electro-excitation being 25% and the triplet state excitons with the probability of being 75% are utilized, so that the luminous efficiency of the OLED can be greatly improved. At present, the luminous efficiency based on the thermal activation delayed fluorescence blue light and green light is close to the commercial level, but the efficiency of the red light material is far from reaching the height of the commercial second generation precious metal complex luminous material. Therefore, the development of pure organic light emitting materials with high efficiency and high stability is of great significance to reduce the cost of OLEDs.
Disclosure of Invention
In order to overcome the problems of the prior art, the invention aims to provide an indenoquinoxaline derivative; the second purpose of the invention is to provide a preparation method of the indenone quinoxaline aromatic amine derivative; the third purpose of the invention is to provide a preparation method of the indenone quinoxaline derivative; the fourth purpose of the invention is to provide the application of the indenone quinoxaline aromatic amine derivative in luminescent materials; the fifth object of the present invention is to provide an exciplex; the sixth purpose of the present invention is to provide a photoelectric device.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides an indanone quinoxaline derivative, the structure of which is shown as formula (I), formula (II) or formula (III):
Figure BDA0003171448820000021
in the formula (I), R1And R2R in the formula (II)3And R4R in the formula (III)5And R6Each independently selected from the group consisting of (a) - (k) aromatic amine units or halogen as shown:
Figure BDA0003171448820000022
preferably, the indenoquinoxaline derivative has a structure shown in formula (1) to formula (21):
Figure BDA0003171448820000031
Figure BDA0003171448820000041
Figure BDA0003171448820000051
Figure BDA0003171448820000061
the second aspect of the present invention provides a method for preparing an indenone-quinoxaline aromatic amine derivative, comprising the steps of:
mixing a compound with a structure shown as a formula (IV), a formula (V) or a formula (VI) with an aromatic amine pinacol borate derivative, and reacting to obtain the indanone quinoxaline aromatic amine derivative;
the structural formula of the formula (IV), the formula (V) or the formula (VI) is as follows:
Figure BDA0003171448820000062
x in the formula (IV)1And X2X in the formula (V)3And X4X in the formula (VI)5And X6Each independently selected from chlorine, bromine or iodine;
the structure of the indeno-quinoxaline aromatic amine derivative is shown as a formula (I), a formula (II) or a formula (III):
Figure BDA0003171448820000063
in the formula (I), R1And R2R in the formula (II)3And R4R in the formula (III)5And R6Each independently selected from the group consisting of the aromatic amine units shown in (a) - (k):
Figure BDA0003171448820000071
preferably, in the preparation method of the indenoquinoxaline aromatic amine derivative, X in the formula (IV)1And X2X in the formula (V)3And X4X in the formula (VI)5And X6Is a bromine atom.
Preferably, in the preparation method of the indeno-quinoxaline aromatic amine derivative, the molar ratio of the compound shown in the formula (IV), the formula (V) or the formula (VI) to the aromatic amine pinacol borate derivative is 1 (1.5-3.5); further preferably, the molar ratio of the compound shown in the formula (IV), the formula (V) or the formula (VI) to the aromatic amine pinacol borate derivative is 1 (1.8-3.2); still more preferably, the molar ratio of the compound shown in the formula (IV), the formula (V) or the formula (VI) to the aromatic amine pinacol borate derivative is 1 (2.2-2.8).
Preferably, in the preparation method of the indenoquinoxaline aromatic amine derivative, the reaction also comprises adding a catalyst to participate in the reaction; further preferably, the catalyst comprises a palladium-based catalyst; still more preferably, the catalyst is tetrakis (triphenylphosphine) palladium.
Preferably, in the preparation method of the indenone quinoxaline aromatic amine derivative, the reaction temperature is 75-95 ℃; further preferably, the reaction temperature is 80-90 ℃.
Preferably, in the preparation method of the indeno-quinoxaline aromatic amine derivative, the reaction time is 9h to 15 h; more preferably, the reaction time is 11h-13 h.
Preferably, in the preparation method of the indenoquinoxaline aromatic amine derivative, the reaction solvent is toluene, ethanol and K2CO3A mixed solvent composed of aqueous solution; further preferably, the reaction solvent is toluene, ethanol and K2CO3The water solution is a mixed solvent composed of (2-4): (0.8-1.4):1 by volume ratio.
The third aspect of the present invention provides a method for preparing an indenoquinoxaline derivative, comprising the steps of:
mixing a compound with a structure shown as a formula (VII), (VIII) or (IX) with a compound with a structure shown as a formula (X), and reacting to obtain the indenone quinoxaline derivative;
the structural formulas of the formula (VII), the formula (VIII), the formula (IX) and the formula (X) are as follows:
Figure BDA0003171448820000081
x in the formula (VII)1And X2X in the formula (VIII)3And X4X in the formula (IX)5And X6Each independently selected from chlorine, bromine or iodine;
the indenoquinoxaline derivative has a structural formula shown as a formula (IV), a formula (V) and a formula (VI):
Figure BDA0003171448820000082
x in the formula (IV)1And X2X in the formula (V)3And X4X in the formula (VI)5And X6Respectively correspond to X in the formula (VII)1And X2X in the formula (VIII)3And X4X in the formula (IX)5And X6。
Preferably, in the preparation method of the indenoquinoxaline derivative, the molar ratio of the compound shown in the formula (VII), (VIII) or (IX) to the compound shown in the formula (X) is 1 (0.6-1.4); further preferably, the molar ratio of the compound represented by the formula (VII), (VIII) or (IX) to the compound represented by the formula (X) is 1 (0.8-1.2).
Preferably, in the preparation method of the indenoquinoxaline derivative, the reaction time is 6-10 h; further preferably, the reaction time is 7h-9 h.
Preferably, in the preparation method of the indenoquinoxaline derivative, the reaction temperature is 70-90 ℃; further preferably, the reaction temperature is 75-85 ℃.
Preferably, in the preparation method of the indenoquinoxaline derivative, the reaction solvent is an organic acid solvent; further preferably, the reaction solvent is acetic acid.
The fourth aspect of the invention provides the use of the indenoquinoxaline derivative in a luminescent material.
In a fifth aspect, the invention provides an exciplex comprising the indenoquinoxaline derivative.
A sixth aspect of the present invention provides an optoelectronic device comprising said indenoquinoxaline derivative.
Preferably, the photoelectric device comprises a transparent substrate, a transparent anode layer on the substrate, a plurality of organic functional layer units and a cathode layer.
Preferably, the organic light emitting layer unit in the photovoltaic device includes a hole injection layer, a hole transport layer, one or more light emitting layers and an electron transport layer.
Preferably, the method for manufacturing the photoelectric device comprises at least one of thermal evaporation, spin coating, brush coating, spray coating, dip coating, roll coating, printing or ink jet printing.
The invention has the beneficial effects that:
the indenone quinoxaline derivative disclosed by the invention takes an indenone quinoxaline group as an electron acceptor and an aromatic amine group as an electron donor, and the small organic molecule has the advantages of single structure, simplicity in purification and stable yield; the organic micromolecule derivative has the property of thermal activation delayed fluorescence, can form an organic film through vacuum evaporation or spin coating, and is applied to organic photoelectric devices such as organic light-emitting diodes; the invention has important significance for developing novel organic photoelectric materials with low cost and good performance.
Specifically, the invention has the following advantages:
1. the organic small molecular material prepared by the invention with the indenone quinoxaline as the receptor core unit has the advantages of simple structure, determined molecular weight, good electrochemical stability and easy research on the structure-activity relationship. Meanwhile, the invention can further adjust the light-emitting property of the light-emitting material and deeply research the light-emitting mechanism of the material to optimize the material performance by adjusting different conjugation lengths of the small organic molecules.
2. The invention discloses a preparation method of indenone quinoxaline derivative, which is characterized in that 1H-indene-1, 2, 3-triketone hydrate and o-phenylenediamine are used as initial reaction raw materials, and then a target compound is obtained through a series of reactions. The indenoquinoxaline derivative disclosed by the invention has very high decomposition temperature and proper sublimation temperature, and is easy to sublimate and purify. The preparation method disclosed by the invention has the advantages of easiness in purification, stable yield, mild reaction conditions and simplicity in operation.
3. The organic small molecular material taking the indenoquinoxaline as the acceptor core unit has larger molecular horizontal orientation, high fluorescence quantum yield, and can realize lower efficiency roll-off while presenting the heat activation delayed fluorescence property. Meanwhile, the organic micromolecules can also effectively adjust the material characteristics such as molecular weight, charge transfer degree, light-emitting wavelength and the like of the material by changing the conjugation length of the receptor unit and the type and size of the connecting unit, and meet the requirements of organic photoelectric devices. The bipolar photoelectric material connected by the electron donor and the electron acceptor can form a large torsion angle between the donor and the electron acceptor, so that the non-planarity of the structure is improved, the accumulation degree of the material is reduced, the aggregation quenching of the material is effectively inhibited, and the problem of unbalanced current carriers of the unipolar organic photoelectric material is solved; meanwhile, the conjugation length of molecules can be effectively controlled, and the horizontal molecular orientation is improved, so that the simplification of the device structure and the improvement of the device performance are realized. The material disclosed by the invention has the advantages of adjustable light color, high efficiency, high stability and the like when being used as a light-emitting layer of an organic electroluminescent device, and has important significance for developing a novel organic photoelectric material with low cost and good performance.
Drawings
FIG. 1 is a graph showing absorption spectrum-emission spectrum of Compound 2 in a toluene solution.
FIG. 2 is a graph showing absorption spectrum-emission spectrum of Compound 10 in a toluene solution.
Fig. 3 is a graph showing the relationship of current efficiency-luminance-external quantum efficiency of an organic electroluminescent device fabricated using compound 2.
Fig. 4 is a graph showing the relationship between current density and voltage and luminance of an organic electroluminescent device fabricated using compound 2.
FIG. 5 is a graph showing an electroluminescence spectrum using Compound 2.
Fig. 6 is a graph showing the relationship of current efficiency-luminance-external quantum efficiency of an organic electroluminescent device fabricated using compound 10.
Fig. 7 is a graph showing the relationship between current density and voltage and luminance of an organic electroluminescent device fabricated using compound 10.
FIG. 8 is a graph showing an electroluminescence spectrum using Compound 10.
Detailed Description
The following description of the embodiments of the present invention is provided in connection with the accompanying drawings and examples, but the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available through commercial purchase.
The preparation process of the indenone-quinoxaline aromatic amine derivative disclosed by the invention relates to three intermediates, namely brominated indenone-quinoxaline derivatives, which are named as M1, M2 and M3 respectively, and the preparation process of the three brominated indenone-quinoxaline derivatives disclosed by the invention is further explained by combining specific experimental steps.
The preparation chemistry and experimental procedure of intermediate M1 are as follows:
Figure BDA0003171448820000101
1.43g of 1H-indene-1, 2, 3-trione hydrate (8mmol) and 2.13g of 4, 5-dibromobenzene-1, 2-diamine (8mmol) are dissolved in 80mL of acetic acid under an argon atmosphere and then heated to 80 ℃ for 8 hours under reflux. After the reaction was completed, it was cooled to room temperature, and the resulting mixture was filtered to remove the solvent, and then the crude product was purified by silica gel column chromatography and dried under vacuum to finally obtain the product intermediate M1 in 54.8% yield. The molecular formula of the product is as follows: c15H6Br2N2O; 389.88 molecular weight m/z. And (3) carrying out an element analysis test on the obtained product, wherein the element analysis result is as follows: c, 46.19; h, 1.55; br, 40.97; n, 7.18; and O,4.10, and the element analysis result conforms to the theoretical value of the product. Identified to obtainThe product was M1.
The preparation chemistry and experimental procedure of intermediate M2 are as follows:
Figure BDA0003171448820000111
1.43g of 1H-indene-1, 2, 3-trione hydrate (8mmol) and 2.93g of 3, 6-dibromophenanthrene-9, 10-diamine (8mmol) are dissolved in 80mL of acetic acid under an argon atmosphere and then heated to 80 ℃ for 8 hours under reflux. After the reaction was completed, it was cooled to room temperature, the resulting mixture was filtered to remove the solvent, and then the crude product was purified by silica gel column chromatography and dried under vacuum to finally obtain the product intermediate M2 in 65% yield. The molecular formula of the product is as follows: c23H10Br2N2O; 489.91 molecular weight m/z. And (3) carrying out an element analysis test on the obtained product, wherein the element analysis result is as follows: c, 56.36; h, 2.06; br, 32.60; n, 5.72; and O,3.26, and the element analysis result conforms to the theoretical value of the product. The product was identified as M2.
The preparation chemistry and experimental procedure of intermediate M3 are as follows:
Figure BDA0003171448820000112
1.43g of 1H-indene-1, 2, 3-trione hydrate (8mmol) and 3.33g of 7, 10-dibromotriphenylene-2, 3-diamine (8mmol) were dissolved in 80mL of acetic acid under an argon atmosphere, and then heated to 80 ℃ for 8 hours under reflux. After the reaction was completed, it was cooled to room temperature, the resulting mixture was filtered to remove the solvent, and then the crude product was purified by silica gel column chromatography and dried under vacuum to finally obtain the product intermediate M3 in 73% yield. The molecular formula of the product is as follows: c27H12Br2N2O; 539.93 molecular weight m/z. And (3) carrying out an element analysis test on the obtained product, wherein the element analysis result is as follows: c, 60.03; h, 2.24; br, 29.58; n, 5.19; and O,2.96, and the element analysis result conforms to the theoretical value of the product. The product was identified as M3.
The preparation process of the indenone-quinoxaline aromatic amine derivative disclosed by the invention is further described by combining specific experimental steps, wherein the specific experimental steps are as follows:
example 1
The chemical reaction formula for preparing compound 1 in this example is shown below, and the specific experimental procedure is as follows:
Figure BDA0003171448820000121
intermediate M1(1.14mmol, 445mg) and pinacol 4- (carbazol-9-yl) phenylboronate (2.85mmol, 1052mg) were dissolved in a solution containing 60mL of toluene, 25mL of ethanol and 20mL of 2mol/L K2CO3250mL round bottom flask of aqueous solution. After a further 15 minutes of aeration with argon, the catalyst Pd (PPh) is added rapidly3)4(0.057mmol, 66mg) and then purged with argon for 10 minutes. The reaction was then heated to 85 ℃ and stirred vigorously for 12 hours. After cooling the reaction to room temperature, the solvent was removed by rotary evaporator in vacuo and the mixture was extracted 3 times with Dichloromethane (DCM). The collected organic phase was further washed with deionized water 3 times, and finally the organic phase was washed with anhydrous magnesium sulfate (MgSO)4) And (5) drying. The next purification was performed by silica gel column chromatography to finally obtain the product compound 1 in 63% yield. The molecular formula of the product is as follows: c51H30N4O; 714.24 molecular weight m/z. And (3) carrying out an element analysis test on the obtained product, wherein the element analysis result is as follows: c, 85.69; h, 4.23; n, 7.84; and O,2.24, and the element analysis result conforms to the theoretical value of the product. The product obtained was identified as compound 1.
Example 2
The chemical reaction formula for preparing compound 2 in this example is shown below, and the specific experimental procedure is as follows:
Figure BDA0003171448820000122
compared with example 1, except that the 4- (carbazol-9-yl) phenylboronic acid pinacol esterAfter replacing the equivalent amount of triphenylamine-4-boronic acid pinacol ester and carrying out the same procedures as in example 1, compound 2 was finally obtained in a yield of 76%. The molecular formula of the product is as follows: c51H34N4O; 718.27 molecular weight m/z. And (3) carrying out an element analysis test on the obtained product, wherein the element analysis result is as follows: c, 85.21; h, 4.77; n, 7.79; and O,2.23, and the element analysis result conforms to the theoretical value of the product. The product obtained was identified as compound 2.
Example 3
The chemical reaction formula for preparing compound 3 in this example is shown below, and the specific experimental procedure is as follows:
Figure BDA0003171448820000131
compared with example 1, except that pinacol 4- (carbazol-9-yl) phenylboronate was replaced with equivalent amount of 9, 9-dimethyl-10- (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -9, 10-dihydroacridine, and other raw materials and procedures were the same as in example 1, compound 3 was finally obtained in 66% yield. The molecular formula of the product is as follows: c57H42N4O; 798.34 molecular weight m/z. And (3) carrying out an element analysis test on the obtained product, wherein the element analysis result is as follows: c, 85.69; h, 5.30; n, 7.01; and O,2.00, and the element analysis result conforms to the theoretical value of the product. The product obtained was identified as compound 3.
Example 4
The chemical reaction formula for preparing compound 4 in this example is shown below, and the specific experimental procedure is as follows:
Figure BDA0003171448820000132
compared with example 1, except that the pinacol ester of 4- (carbazol-9-yl) phenylboronic acid was replaced with an equivalent amount of 10- (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -10H-phenoxazine, the other raw materials and procedures were the same as in example 1, and compound 4 was finally obtained in 71% yield. Product ofThe molecular formula is as follows: c51H30N4O3(ii) a 746.23 molecular weight m/z. And (3) carrying out an element analysis test on the obtained product, wherein the element analysis result is as follows: c, 82.02; h, 4.05; n, 7.50; and O,6.43, and the element analysis result conforms to the theoretical value of the product. The product obtained was identified as compound 4.
Example 5
The chemical reaction formula for preparing compound 5 in this example is shown below, and the specific experimental procedure is as follows:
Figure BDA0003171448820000141
compared with example 1, except that the 4- (carbazol-9-yl) phenylboronic acid pinacol ester was replaced by an equivalent amount of 10- (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -10H-phenothiazine, the other raw materials and procedures were the same as in example 1, and compound 5 was finally obtained in 68% yield. The molecular formula of the product is as follows: c51H30N4OS2(ii) a 778.19 molecular weight m/z. And (3) carrying out an element analysis test on the obtained product, wherein the element analysis result is as follows: c, 78.64; h, 3.88; n, 7.19; o, 2.05; and S,8.23, wherein the element analysis result accords with the theoretical value of the product. The product obtained was identified as compound 5.
Example 6
The chemical reaction for preparing compound 6 in this example is shown below, and the specific experimental procedure is as follows:
Figure BDA0003171448820000142
compared with example 1, except that the 4- (carbazol-9-yl) phenylboronic acid pinacol ester is replaced by equivalent amount of (10- (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -10H-phenoselenazine, and other raw materials and steps are the same as those of example 1, the product compound 6 is finally obtained with a yield of 73%, the product molecular formula is C51H30N4OSe2(ii) a 874.08 molecular weight m/z. Subjecting the obtained product to elemental analysisTest, the elemental analysis result is: c, 70.19; h, 3.46; n, 6.42; o, 1.83; se,18.10, and the element analysis result conforms to the theoretical value of the product. The product obtained was identified as compound 6.
Example 7
The chemical reaction scheme for preparing compound 7 in this example is shown below, and the specific experimental procedure is as follows:
Figure BDA0003171448820000151
the difference compared to example 1 was that intermediate M1 was replaced with an equivalent amount of intermediate M2 and the other starting materials and procedures were the same as in example 1 to give the product compound 7 in 73% yield. The molecular formula of the product is as follows: c59H34N4O; 814.27 molecular weight m/z. And (3) carrying out an element analysis test on the obtained product, wherein the element analysis result is as follows: c, 86.96; h, 4.21; n, 6.88; and O,1.96, and the element analysis result conforms to the theoretical value of the product. The product obtained was identified as compound 7.
Example 8
The chemical reaction scheme for preparing compound 8 in this example is shown below, and the specific experimental procedure is as follows:
Figure BDA0003171448820000152
the difference compared to example 2 was that intermediate M1 was replaced with an equivalent amount of intermediate M2 and the other starting materials and procedures were the same as in example 2 to give the product compound 8 in 63% yield. The molecular formula of the product is as follows: c59H38N4O; 818.30 molecular weight m/z. And (3) carrying out an element analysis test on the obtained product, wherein the element analysis result is as follows: c, 86.53; h, 4.68; n, 6.84; and O,1.95, and the element analysis result conforms to the theoretical value of the product. The product obtained was identified as compound 8.
Example 9
The chemical reaction scheme for preparing compound 9 in this example is shown below, and the specific experimental procedure is as follows:
Figure BDA0003171448820000161
the difference compared to example 3 was that intermediate M1 was replaced with an equivalent amount of intermediate M2 and the other starting materials and procedures were the same as in example 3 to give the product compound 9 in 71% yield. The molecular formula of the product is as follows: c65H46N4O; 898.37 molecular weight m/z. And (3) carrying out an element analysis test on the obtained product, wherein the element analysis result is as follows: c, 86.83; h, 5.16; n, 6.23; and O,1.78, and the element analysis result conforms to the theoretical value of the product. The product obtained was identified as compound 9.
Example 10
The chemical reaction for preparing compound 10 in this example is shown below, and the specific experimental procedure is as follows:
Figure BDA0003171448820000162
the difference compared to example 4 was that intermediate M1 was replaced with an equivalent amount of intermediate M2 and the other starting materials and procedures were the same as in example 4 to give the product compound 10 in 77% yield. The molecular formula of the product is as follows: c59H34N4O3(ii) a 846.26 molecular weight m/z. And (3) carrying out an element analysis test on the obtained product, wherein the element analysis result is as follows: c, 83.67; h, 4.05; n, 6.62; and O,5.67, and the element analysis result conforms to the theoretical value of the product. The product obtained was identified as compound 10.
Example 11
The chemical reaction scheme for preparing compound 11 in this example is shown below, and the specific experimental procedure is as follows:
Figure BDA0003171448820000171
compared with example 5, the difference is that intermediate M1 is replaced by intermediate M2 with equivalent weight, other raw materials andthe procedure was as in example 5 to give the final product compound 11 in 68% yield. The molecular formula of the product is as follows: c59H34N4OS2(ii) a 878.22 molecular weight m/z. And (3) carrying out an element analysis test on the obtained product, wherein the element analysis result is as follows: c, 80.61; h, 3.90; n, 6.37; o, 1.82; s,7.29, and the element analysis result accords with the theoretical value of the product. The product obtained was identified as compound 11.
Example 12
The chemical reaction scheme for preparing compound 12 in this example is shown below, and the specific experimental procedure is as follows:
Figure BDA0003171448820000172
the difference compared to example 6 was that intermediate M1 was replaced with an equivalent amount of intermediate M2 and the other starting materials and procedures were the same as in example 6 to give the product compound 12 in 73% yield. The molecular formula of the product is as follows: c59H34N4OSe2(ii) a 974.11 molecular weight m/z. And (3) carrying out an element analysis test on the obtained product, wherein the element analysis result is as follows: c, 72.84; h, 3.52; n, 5.76; o, 1.64; se,16.23, and the element analysis result conforms to the theoretical value of the product. The product obtained was identified as compound 12.
Example 13
The chemical reaction scheme for preparing compound 13 in this example is shown below, and the specific experimental procedure is as follows:
Figure BDA0003171448820000181
the difference compared to example 1 was that intermediate M1 was replaced with an equivalent amount of intermediate M3 and the other starting materials and procedures were the same as in example 1 to give the product compound 13 in 76% yield. The molecular formula of the product is as follows: c63H36N4O; 864.29 molecular weight m/z. And (3) carrying out an element analysis test on the obtained product, wherein the element analysis result is as follows: c, 87.48; h, 4.20; n, 6.48; o,1.85, the elemental analysis result is in accordance withTheoretical value of the product. The product obtained was identified as compound 13.
Example 14
The chemical reaction scheme for preparing compound 14 in this example is shown below, and the specific experimental procedure is as follows:
Figure BDA0003171448820000182
the difference compared to example 2 was that intermediate M1 was replaced with an equivalent amount of intermediate M3 and the other starting materials and procedures were the same as in example 2, to give the product compound 14 in 77% yield. The molecular formula of the product is as follows: c63H40N4O; 868.32 molecular weight m/z. And (3) carrying out an element analysis test on the obtained product, wherein the element analysis result is as follows: c, 87.07; h, 4.64; n, 6.45; o,1.84, and the element analysis result conforms to the theoretical value of the product. The product obtained was identified as compound 14.
Example 15
The chemical reaction scheme for preparing compound 15 in this example is shown below, and the specific experimental procedure is as follows:
Figure BDA0003171448820000191
the difference compared to example 3 was that intermediate M1 was replaced with an equivalent amount of intermediate M3 and the other starting materials and procedures were the same as in example 3 to give the product compound 15 in 64% yield. The molecular formula of the product is as follows: c69H48N4O; 948.38 molecular weight m/z. And (3) carrying out an element analysis test on the obtained product, wherein the element analysis result is as follows: c, 87.31; h, 5.10; n, 5.90; o,1.69, and the element analysis result conforms to the theoretical value of the product. The product obtained was identified as compound 15.
Example 16
The chemical reaction scheme for preparing compound 16 in this example is shown below, and the specific experimental procedure is as follows:
Figure BDA0003171448820000192
the difference compared to example 4 was that intermediate M1 was replaced with an equivalent amount of intermediate M3 and the other starting materials and procedures were the same as in example 4 to give the product compound 16 in 79% yield. The molecular formula of the product is as follows: c63H36N4O3(ii) a 896.28 molecular weight m/z. And (3) carrying out an element analysis test on the obtained product, wherein the element analysis result is as follows: c, 84.36; h, 4.05; n, 6.25; and O,5.35, and the element analysis result conforms to the theoretical value of the product. The product obtained was identified as compound 16.
Example 17
The chemical reaction scheme for preparing compound 17 in this example is shown below, and the specific experimental procedure is as follows:
Figure BDA0003171448820000201
the difference compared to example 5 was that intermediate M1 was replaced with an equivalent amount of intermediate M3 and the other starting materials and procedures were the same as in example 5 to give the product compound 17 in 65% yield. The molecular formula of the product is as follows: c63H36N4OS2(ii) a 928.23 molecular weight m/z. And (3) carrying out an element analysis test on the obtained product, wherein the element analysis result is as follows: c, 81.44; h, 3.91; n, 6.03; o, 1.72; s,6.90, and the element analysis result accords with the theoretical value of the product. The product obtained was identified as compound 17.
Example 18
The chemical reaction scheme for preparing compound 18 in this example is shown below, and the specific experimental procedure is as follows:
Figure BDA0003171448820000202
the difference from example 6 was that intermediate M1 was replaced with equivalent intermediate M3 and the other starting materials and procedures were the same as in example 6 to give the product compound 18 in high yieldThe content was 73%. The molecular formula of the product is as follows: c63H36N4OSe2(ii) a 1024.12 molecular weight m/z. And (3) carrying out an element analysis test on the obtained product, wherein the element analysis result is as follows: c, 73.97; h, 3.55; n, 5.48; o, 1.56; se,15.44, and the element analysis result conforms to the theoretical value of the product. The product obtained was identified as compound 18.
Compound 2 and compound 10 were analyzed for absorbance and emission spectra, respectively, as follows:
compound 2 and compound 10 were formulated separately at 5 x 10 concentration-8And (3) carrying out ultraviolet-visible light absorption spectrum and photoluminescence emission spectrum tests on the solution of toluene in mol/L. The ultraviolet-visible light absorption spectrum is measured by a UV-3600 instrument model of Shimadzu corporation, and the photoluminescence emission spectrum is measured by a FluoroMax-4 spectrometer instrument model of Shichwan corporation.
Fig. 1 is an absorption spectrum-emission spectrum of compound 2 in a toluene solution, and fig. 2 is an absorption spectrum-emission spectrum of compound 10 in a toluene solution. As can be seen from fig. 1 and 2, compound 2 and compound 10 have similar absorption spectra, and the peak of the emission spectrum of compound 10 is larger than the wavelength of compound 2.
Application example
The compounds 1 to 18 prepared above are applied to an Organic Light Emitting Diode (OLED) device, and specific application embodiments are as follows:
the specific laminated materials and thicknesses of the universal organic electroluminescent device of the application example are as follows:
glass substrate/ITO (95nm)/TAPC (30nm)/mCP (10nm)/5 wt% of compound X (compound 1-18) +95 wt% CBP (20nm)/TmPyPB (50nm)/LiF (1nm)/Al (100 nm). ITO is used as an anode, TAPC is used as a hole injection layer, mCP is an electron blocking layer, CBP is a luminescent material doping main body, TmPyPB is used as an electron transport layer, LiF is used as an electron injection layer, and Al is used as a cathode.
The molecular structural formulas of TAPC, mCP, CBP and TmPyPB described in the above application examples are respectively as follows:
Figure BDA0003171448820000211
the manufacturing steps of the light-emitting device are as follows:
and ultrasonically cleaning the ITO transparent conductive glass for 15 minutes by using acetone, a micron-sized special semiconductor detergent, deionized water and isopropanol in sequence to remove dirt on the surface of the substrate. And then putting the mixture into a thermostat to be dried at 80 ℃ for later use. The dried ITO substrate was treated with an oxygen plasma cleaning device for 3 minutes to further remove organic deposits on the surface. The glass with the anode ITO is placed in a vacuum chamber under the vacuum condition of-4 multiplied by 10-4At Pa, in
Figure BDA0003171448820000212
The deposition rate of the organic material layer is evaporated on the anode film, wherein in the evaporation of the luminescent layer, the CBP and the luminescent material are respectively placed on two evaporation sources, and the mixing ratio of the CBP and the luminescent material is controlled by a certain deposition rate. Then is followed by
Figure BDA0003171448820000213
Evaporating LiF at a deposition rate of
Figure BDA0003171448820000214
The Al electrode was evaporated at the deposition rate of (3) to obtain the organic light emitting diode device of the present example.
The manufactured light emitting device was subjected to a performance test, and the test results are shown in table 1.
Table 1: performance test results for OLED devices fabricated with Compounds 1-18
Figure BDA0003171448820000221
The compound 2 and the compound 10 are subjected to an electroluminescence spectrum test, which comprises the following steps:
the prepared device was directly tested at room temperature without encapsulation, an Electroluminescence (EL) spectrum was measured by an optical analyzer Photo Research PR745, and current density and luminance versus driving voltage characteristics were measured by Keithley 2420 of giemli and a konica minolta colorimeter CS-200. Here, the area of the prepared light emitting region was 3mm by 3mm, and the External Quantum Efficiency (EQE) was calculated from the luminance, current density, and EL spectrum, provided that the light distribution was assumed to be lambertian.
The fabricated devices No. 2 and No. 7 were subjected to more detailed photoelectric performance test analysis, and the results are shown in fig. 3 to 8. Fig. 3 is a graph showing a relationship between current efficiency and luminance and external quantum efficiency of an organic electroluminescent device fabricated using compound 2, fig. 4 is a graph showing a relationship between current density and voltage and luminance of an organic electroluminescent device fabricated using compound 2, and fig. 5 is an electroluminescence spectrum of compound 2. Fig. 6 is a graph showing a relationship between current efficiency and luminance and external quantum efficiency of an organic electroluminescent device fabricated using compound 10, fig. 7 is a graph showing a relationship between current density and voltage and luminance of an organic electroluminescent device fabricated using compound 10, and fig. 8 is an electroluminescence spectrum of compound 10.
As can be seen from Table 1 and FIGS. 3 to 8, the organic electroluminescent device produced from Compound 2 had CIE color coordinate values of (0.55, 0.44) and a maximum luminance of 5391cd/m2External quantum efficiency of 15.0% and current efficiency of 38.9 cd/A; the organic electroluminescent element prepared from compound 10 had CIE color coordinate values of (0.63, 0.36) and maximum luminance of 1380cd/m2The external quantum efficiency was 15.3% and the current efficiency was 18.0 cd/A. The lighting voltage of the devices manufactured in all application examples is less than 4.5V, which shows that the charge injection and exciton recombination conditions of the manufactured devices are good, and the maximum external quantum efficiency of all the manufactured devices exceeds 5 percent of the maximum external quantum efficiency of the traditional fluorescent material, and proves that the organic small molecular material based on the indenoquinoxaline as the acceptor has great application potential in the fields of luminescent materials, exciplexes and organic electroluminescence.
The above examples are preferred embodiments of the present invention, but the present invention is not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and they are included in the scope of the present invention.

Claims (10)

1. An indenoquinoxaline derivative characterized in that: the indenoquinoxaline derivative has a structure shown as a formula (I), a formula (II) or a formula (III):
Figure FDA0003171448810000011
in the formula (I), R1And R2R in the formula (II)3And R4R in the formula (III)5And R6Each independently selected from the group consisting of (a) - (k) aromatic amine units or halogen as shown:
Figure FDA0003171448810000012
2. the indenoquinoxaline derivative according to claim 1, wherein: the indenoquinoxaline derivative has a structure shown in formula (1) to formula (21):
Figure FDA0003171448810000021
Figure FDA0003171448810000031
Figure FDA0003171448810000041
Figure FDA0003171448810000051
3. a preparation method of indenone quinoxaline aromatic amine derivatives is characterized in that: the method comprises the following steps:
mixing a compound with a structure shown as a formula (IV), a formula (V) or a formula (VI) with an aromatic amine pinacol borate derivative, and reacting to obtain the indanone quinoxaline aromatic amine derivative;
the structural formula of the formula (IV), the formula (V) or the formula (VI) is as follows:
Figure FDA0003171448810000052
x in the formula (IV)1And X2X in the formula (V)3And X4X in the formula (VI)5And X6Each independently selected from chlorine, bromine or iodine;
the structure of the indeno-quinoxaline aromatic amine derivative is shown as a formula (I), a formula (II) or a formula (III):
Figure FDA0003171448810000053
in the formula (I), R1And R2R in the formula (II)3And R4R in the formula (III)5And R6Each independently selected from the group consisting of the aromatic amine units shown in (a) - (k):
Figure FDA0003171448810000061
4. the process for producing an indenone-quinoxaline aromatic amine derivative according to claim 3, wherein: the molar ratio of the compound shown in the formula (IV), the formula (V) or the formula (VI) to the aromatic amine pinacol borate derivative is 1 (1.5-3.5).
5. The process for producing an indenone-quinoxaline aromatic amine derivative according to claim 3, wherein: the reaction also comprises adding a catalyst to participate in the reaction.
6. A method for preparing indenoquinoxaline derivatives is characterized in that: the method comprises the following steps:
mixing a compound with a structure shown as a formula (VII), (VIII) or (IX) with a compound with a structure shown as a formula (X), and reacting to obtain the indenone quinoxaline derivative;
the structural formulas of the formula (VII), the formula (VIII), the formula (IX) and the formula (X) are as follows:
Figure FDA0003171448810000071
x in the formula (VII)1And X2X in the formula (VIII)3And X4X in the formula (IX)5And X6Each independently selected from chlorine, bromine or iodine;
the indenoquinoxaline derivative has a structural formula shown as a formula (IV), a formula (V) and a formula (VI):
Figure FDA0003171448810000072
x in the formula (IV)1And X2X in the formula (V)3And X4X in the formula (VI)5And X6Respectively correspond to X in the formula (VII)1And X2X in the formula (VIII)3And X4X in the formula (IX)5And X6。
7. The process for producing an indenoquinoxaline derivative according to claim 6, wherein: the molar ratio of the compound shown in the formula (VII), (VIII) or (IX) to the compound shown in the formula (X) is 1 (0.6-1.4).
8. Use of the indenoquinoxaline derivative according to claim 1 or 2 in a light-emitting material.
9. An exciplex, comprising: the exciplex comprises the indenoquinoxaline derivative according to any one of claims 1 or 2.
10. An optoelectronic device, characterized by: an optoelectronic device comprising the indenoquinoxaline derivative of any of claims 1 or 2.
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