Selenophene-containing compound and use thereof in organic light-emitting device

Abstract

The present invention relates to the technical field of preparation of organic photoelectric materials, and in particular to a selenophene-containing compound and a use thereof in an organic light-emitting device. The selenophene-containing compound involved in the present invention has very low efficiency roll-off, and by introducing a rigid conjugated fused ring selenophene unit, the efficiency roll-off of a device can be reduced by means of a heavy atom effect. Additionally, a rigid conjugated group can improve the carrier transport ability and promote the direct energy transmission between a host material and a guest material. In addition, a triphenylsilicon large steric hindrance group can effectively inhibit the interaction among light-emitting molecules, and the device efficiency is further improved. Specifically, according to an organic electroluminescent device made of the selenophene-containing compound of the present invention which is used as a functional layer, and in particular as a light-emitting layer, the current efficiency is improved, the turn-on voltage is reduced, and the service life of the device is greatly prolonged, which means that when most electrons and holes are recombined, energy is effectively transferred to the selenophene-containing compound for emitting light instead of generating heat.

Description

Selenophene-containing compounds and their applications in organic light-emitting devices Technical Field

[0001] The present invention relates to the technical field of preparation of organic photoelectric materials, and in particular to selenium-containing phenanthene compounds and applications thereof in organic light-emitting devices. Background Art

[0002] With the development of multimedia technology and the increasing demand for informatization, the requirements for panel display performance are becoming increasingly higher. Among them, OLED has a series of advantages such as autonomous luminescence, low-voltage DC drive, full curing, wide viewing angle, and rich colors. It has attracted widespread attention due to its potential application in the next generation of display and lighting technologies, and its application prospects are very broad. Organic electroluminescent devices are spontaneous light-emitting devices. The mechanism of OLED light emission is that under the action of an external electric field, electrons and holes are injected from the positive and negative poles respectively, and then migrate, recombine and decay in the organic material to produce light. The typical structure of OLED includes one or more functional layers of cathode layer, anode layer, electron injection layer, electron transport layer, hole blocking layer, hole transport layer, hole injection layer and light-emitting layer. Although the research on organic electroluminescence has been progressing very rapidly, there are still many problems that need to be solved. For example, the development of high-efficiency and long-life blue light materials has always been a problem that technicians in this field need to solve.

[0003] Summary of the Invention

[0004] The purpose of the present invention is to address the deficiencies of the existing technology and provide a selenium-containing phenanthrene compound and its application in an organic light-emitting device. By introducing a selenium-containing phenanthrene group, the rigid conjugated structure of the present invention has good carrier transport capabilities, effectively suppressing interactions between luminescent molecules. The prepared selenium-containing phenanthrene compound has a low efficiency roll-off and good carrier transport capabilities, which can improve the energy transfer performance between the host and the guest, reduce the concentration of high-energy excitons in the light-emitting layer, and thus realize a high-efficiency, long-life blue light-emitting material. Therefore, this type of selenium-containing phenanthrene compound has important applications in organic light-emitting devices.

[0005] In order to achieve the purpose of the present invention, the technical solution of the present invention is as follows:

[0006] According to one or more embodiments, the present invention provides a selenium-containing phenanthrene compound having a structure shown in the following formula I:

[0007] In Formula I, Ring A and Ring B are each independently selected from a five-membered ring, a five-membered heterocyclic ring, a six-membered ring or a condensed ring;

[0008] X1, X2, X3, X4, X5, X6, X7, X8, X9, X 10Each of them is independently selected from N or CR, X1, X2, X3, X4, X5 are not selected from N at the same time, X6, X7, X8, X9, X 10 Not selected from N at the same time;

[0009] The R, R1, R2, and R3 are each independently a single substituent to the maximum possible number of substituents or no substituent, and any adjacent substituents are optionally joined or fused to form a ring;

[0010] R, R1, R2, and R3 are each independently selected from H, deuterium, a C1-C24 alkyl group, a C1-C24 deuterated alkyl group, a substituted or unsubstituted C3-C24 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C12-C30 arylamine group, a substituted or unsubstituted C12-C30 arylsilane group, a substituted or unsubstituted C12-C30 alkoxy group, a substituted or unsubstituted C12-C30 aryloxy group, a substituted or unsubstituted C2-C24 fused ring hydrocarbon group, a substituted or unsubstituted C6-C30 fused ring aromatic hydrocarbon group, and the group consisting of.

[0011] In some embodiments of the compound, Ring A in Formula I is selected from a five-membered ring or a benzene ring.

[0012] In some embodiments of the compound, Ring B in Formula I is selected from a benzene ring, a five-membered heterocyclic ring containing S or Se.

[0013] In some embodiments of the compounds, R in Formula I is selected from hydrogen, deuterium, C1-C16 alkyl, C3-C16 cycloalkyl, C6-C18 aryl, C6-C18 heteroaryl, C6-C18 arylsilane, and the group consisting of.

[0014] In some embodiments of the compounds, R2 is selected from tert-butyl, phenyl, biphenyl, triaryl, triarylsilane, or diarylamine.

[0015] In some embodiments of the compounds, R, R1, and R3 are each independently selected from the group consisting of hydrogen, deuterium, methyl, ethyl, pentyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantane, phenyl, biphenyl, fluorenyl, aryloxy, diarylamine, triarylsilane, and the like.

[0016] In some embodiments of the compound, at least one substituent among R, R1, R2, and R3 is independently selected from the group consisting of: The structure shown.

[0017] According to one or more embodiments, the selenium-containing phene compound is selected from any one of the chemical structures shown below, wherein "D" represents deuterium:

[0018] On the one hand, the present invention also provides the use of selenium-containing phenene compounds with the general structure shown in formula (I) above in electronic devices.

[0019] Furthermore, the electronic devices include organic electroluminescent devices (OLEDs), organic integrated circuits (O-ICs), organic field effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic light emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQDs), light emitting electrochemical cells (LECs) and organic laser diodes (O-lasers).

[0020] In another aspect, the present invention further provides an organic electroluminescent device, which comprises a selenium-containing phenene compound having the general structure shown in formula (I) above.

[0021] Furthermore, the organic electroluminescent device comprises a cathode, an anode, and an organic functional layer therebetween; the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises a selenium-containing phenanthrene compound having the general structure shown in formula (I) above. The mass percentage of the selenium-containing phenanthrene compound is 0.1% to 50%.

[0022] In another aspect, the present invention further provides an organic optoelectronic device comprising a first electrode; a second electrode facing the first electrode; and a light-emitting material layer disposed between the first electrode and the second electrode, wherein the light-emitting material layer comprises a selenium-containing phenanthene compound having the general structure shown in formula (I) above. For example, the selenium-containing phenanthene compound can be included in the light-emitting material layer as a dopant.

[0023] The present invention also provides a composition comprising a selenium-containing phenene compound having the general structure shown in the above formula (I).

[0024] The present invention also provides a preparation comprising a selenium-containing phenene compound having the general structure shown in formula (I) above or the composition as described above and at least one solvent. The solvent is not particularly limited and can be any solvent known to those skilled in the art, such as unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, hexyl chloride, bromohexane, chlorocyclohexane, bromocyclohexane, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, ether solvents such as tetrahydrofuran and tetrahydropyran, and ester solvents such as alkyl benzoate.

[0025] The present invention also provides a display or lighting device, which comprises one or more of the organic electroluminescent devices described above.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] The selenium-containing phenene compounds involved in the present invention all have very low efficiency roll-off. By introducing a rigidly conjugated fused-ring selenium phenene unit, the efficiency roll-off of the device can be reduced by the heavy atom effect; at the same time, the rigid conjugated group can enhance the carrier transmission capability and promote direct energy transmission between the host material and the guest material. In addition, the large steric hindrance group of triphenylsilicon can effectively inhibit the interaction between the luminescent molecules and further improve the efficiency of the device. Specifically, the organic electroluminescent device made by using the selenium-containing phenene compound of the present invention as a functional layer, especially as a light-emitting layer, has an improved current efficiency and a reduced lighting voltage. At the same time, the life of the device is greatly improved, indicating that after most of the electrons and holes recombine, the energy is effectively transferred to the selenium-containing phenene compound for luminescence, rather than heat generation. DETAILED DESCRIPTION

[0028] The content of the present invention is described in detail below. The description of the constituent elements recorded below is sometimes based on representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples. By referring to the following specific embodiments and the examples contained therein, the present disclosure can be more easily understood. Before disclosing and describing the compounds, devices and / or methods of the present invention, it should be understood that, unless otherwise stated, they are not limited to specific synthetic methods or specific reagents, as this can be varied. It should also be understood that the terms used in the present invention are only used to describe specific aspects and are not intended to be limiting. Although any methods and materials similar or equivalent to those described in the present invention can be used in this practice or test, example methods and materials are now described.

[0029] As used herein, "C1-C24 alkyl" refers to a monovalent alkyl group having 1 to 24 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Examples of this term include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, and the like.

[0030] The "C3-C24 cycloalkyl" of the present invention refers to a cyclic alkyl group having 3 to 14 carbon atoms and having a monocyclic or polycyclic condensed ring, which may be arbitrarily substituted with 1 to 3 alkyl groups. Such cycloalkyl groups include, for example, monocyclic structures such as cyclopropyl, cyclobutyl, cyclopentyl, cyclooctyl, 1-methylcyclopropyl, 2-methylcyclopentyl, 2-methylcyclooctyl, etc., or polycyclic structures such as adamantyl, etc.

[0031] The "C6-C30 aryl" herein refers to an unsaturated aromatic carbocyclic ring having 6-30 carbon atoms and having a monocyclic ring (e.g., phenyl) or a polycyclic condensed ring (e.g., naphthyl or anthracenyl). Preferred aryl groups include phenyl, naphthyl, and the like. Unless otherwise defined for an individual substituent, such an aryl group may be optionally substituted with 1-3 of the following substituents: hydroxyl, acyl, acyloxy, alkyl, alkoxy, alkenyl, alkynyl, amino, aminoacyl, aryl, aryloxy, carboxyl, carboxyl ester, aminocarboxyl ester, cyano, halogen, nitro, heteroaryl, heterocycle, thioalkoxy, trihalomethyl, and the like. Preferred substituents include, but are not limited to, alkyl, alkoxy, halogen, cyano, nitro, trihalomethyl, and thioalkoxy.

[0032] As used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a component" includes a mixture of two or more components.

[0033] Unless otherwise stated, all commercial reagents involved in the following experiments were used directly after purchase.

[0034] In a preferred embodiment of the present invention, the OLED device of the present invention comprises a hole transport layer. The hole transport material may be preferably selected from known or unknown materials, and is particularly preferably selected from the following structures, but this does not mean that the present invention is limited to the following structures (Ph is phenyl):

[0035] In a preferred embodiment of the present invention, the hole injection layer contained in the OLED device of the present invention has the following structure, but it does not mean that the present invention is limited to the following structure:

[0036] In a preferred embodiment of the present invention, the electron transport layer may be selected from at least one of the following compounds, but this does not mean that the present invention is limited to the following structures:

[0037] The preparation method of the selenium-containing phenene compound, i.e., the guest compound, and the luminescence performance of the device are explained in detail with reference to the following examples.

[0038] The OLED device of the present invention contains a host material, which can be selected from known or unknown materials, and is particularly preferably selected from the following structures, but this does not mean that the present invention is limited to the following structures:

[0039] Example 1: Synthesis of Compound 4

[0040] Synthesis of Compound 4-2: BuLi (0.5 mL, 1 mmol, 2 M hexane solution) was slowly added to a solution of Compound 4-1 (396 mg, 1 mmol) in tetrahydrofuran (50 mL) at -78°C. After 3 hours of reaction, triphenylsilyl chloride (294 mg, 1 mmol) was slowly added. The reaction mixture was slowly warmed to room temperature and allowed to react overnight, then raised to 80°C for 6 hours. After cooling to room temperature, 1 mL of ice water was added. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3 × 100 mL). The organic phase was washed with water and dried over sodium sulfate. The solvent was removed by distillation under reduced pressure, and the resulting crude product was purified by silica gel chromatography using a 1:9 ratio of dichloromethane to petroleum ether as eluent to afford 4-2 (246 mg, 47% yield). Mass spectrum: m / z: theoretical: 525.92; found: M+H: 526.94.

[0041] Synthesis of compound 4-4: Compound 4-2 (529 mg, 1 mmol) and compound 4-3 (281 mg, 1 mmol) were dissolved in 50 mL of toluene. Under a nitrogen atmosphere, sodium tert-butoxide (192 mg, 2 mmol), palladium acetate (12 mg, 0.05 mmol), and tri-tert-butylphosphine tetrafluoroborate (145 mg, 0.5 mmol) were added. The reaction system was refluxed for 72 hours and then cooled to room temperature. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3 × 100 mL). The organic phase was washed with water and dried over sodium sulfate. The solvent was removed by distillation under reduced pressure, and the resulting crude product was purified by silica gel chromatography using a 1:6 ratio of dichloromethane to petroleum ether as eluent to afford product 4-4 (222 mg, 30% yield). Mass spectrum: m / z: theoretical: 727.20; found: M+H: 728.26.

[0042] Synthesis of Compound 4-5: Compound a (316 mg, 1 mmol) and compound b (300 mg, 2 mmol) were dissolved in 50 mL of toluene. Under a nitrogen atmosphere, sodium tert-butoxide (192 mg, 2 mmol), palladium acetate (12 mg, 0.05 mmol), and tri-tert-butylphosphine tetrafluoroborate (145 mg, 0.5 mmol) were added. The reaction system was refluxed for 72 hours and then cooled to room temperature. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3 × 100 mL). The organic phase was washed with water and dried over sodium sulfate. The solvent was removed by distillation under reduced pressure, and the resulting crude product was purified by silica gel chromatography using a 1:3 ratio of dichloromethane to petroleum ether as eluent to afford product 4-5 (190 mg, 49% yield). Mass spectrum: m / z: theoretical: 385.13; found: M+H: 386.15.

[0043] Synthesis of Compound 4-6: Compound 4-4 (729 mg, 1 mmol) and Compound 4-5 (385 mg, 1 mmol) were dissolved in 50 mL of toluene. Under a nitrogen atmosphere, sodium tert-butoxide (192 mg, 2 mmol), palladium acetate (12 mg, 0.05 mmol), and tri-tert-butylphosphine tetrafluoroborate (145 mg, 0.5 mmol) were added. The reaction system was refluxed for 72 hours and then cooled to room temperature. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3 × 100 mL). The organic phase was washed with water and dried over sodium sulfate. The solvent was removed by distillation under reduced pressure, and the resulting crude product was purified by silica gel chromatography using a 1:7 ratio of dichloromethane to petroleum ether as eluent to afford product 4-6 (310 mg, 30% yield). Mass spectrum: m / z: theoretical: 1032.41; found: M+H: 1033.43.

[0044] Synthesis of Compound 4: Under a nitrogen atmosphere at zero degrees Celsius, tert-butyllithium (1.25 mL, 1.6 M pentane solution, 2 mmol) was slowly added dropwise to a solution of compound 4-6 (1032 mg, 1 mmol) in tert-butylbenzene (100 mL). The system was reacted at 60°C for 4 hours, then cooled to -50°C, and BBr3 (494 mg, 2 mmol) was added. After reacting at room temperature for 1 hour, N,N-diisopropylethylamine (259 mg, 2 mmol) was added. The temperature was then raised to 120°C and reacted for 12 hours. After cooling to room temperature, 5 mL of 1 M aqueous sodium acetate solution was added. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3 × 100 mL). The organic phase was washed with water and dried over sodium sulfate. The solvent was removed by distillation under reduced pressure, and the resulting crude product was separated and purified by silica gel chromatography using a 1:9 ratio of dichloromethane to petroleum ether as eluent to afford product 4 (271 mg, 27% yield). Mass spectrum m / z: theoretical value 1006.43; found M+H value: 1007.46.

[0045] Example 2: Synthesis of Compound 3

[0046] Compound 3

[0047] Compound 3 was synthesized by referring to the synthetic route of compound 4. The yield of the final product was 21%. Mass spectrum m / z: theoretical value 1106.46; found value M+H: 1107.48.

[0048] Example 3: Synthesis of Compound 5

[0049] Compound 5

[0050] Compound 5 was synthesized by referring to the synthetic route of compound 4. The yield of the final product was 21%. Mass spectrum m / z: theoretical value 1062.50; found value M+H: 1063.52.

[0051] Example 4: Synthesis of Compound 6

[0052] Compound 6

[0053] Compound 6 was synthesized by referring to the synthetic route of compound 4. The yield of the final product was 23%. Mass spectrum m / z, theoretical value: 1082.46; found value M+H: 1083.49.

[0054] Example 5: Synthesis of Compound 8

[0055] Compound 8

[0056] Compound 8 was synthesized by referring to the synthetic route of compound 4. The yield of the final product was 24%. Mass spectrum m / z: theoretical value 1138.53; found value M+H: 1139.55.

[0057] Example 6: Synthesis of Compound 12

[0058] Compound 12

[0059] Compound 12 was synthesized using the synthetic route of compound 4. The yield of the final product was 26%. Mass spectrum m / z: theoretical value 1138.43; found value M+H: 1139.45.

[0060] Example 7: Synthesis of Compound 14

[0061] Compound 14

[0062] Compound 14 was synthesized by referring to the synthetic route of compound 4. The yield of the final product was 22%. Mass spectrum m / z: theoretical value 1229.57; found value M+H: 1230.59.

[0063] Example 8: Synthesis of Compound 33

[0064] Compound 33

[0065] Compound 33 was synthesized using the synthetic route of compound 4. The yield of the final product was 20%. Mass spectrum m / z: theoretical value 1178.46; found value M+H: 1179.49.

[0066] Example 9: Synthesis of Compound 44

[0067] Compound 44

[0068] Compound 44 was synthesized by referring to the synthetic route of compound 4. The yield of the final product was 23%. Mass spectrum m / z: theoretical value 1214.46; found value M+H: 1215.48.

[0069] Example 10: Synthesis of Compound 48

[0070] Compound 48

[0071] Compound 48 was synthesized by referring to the synthetic route of compound 4. The yield of the final product was 28%. Mass spectrum m / z: theoretical value 1290.59; found value M+H: 1290.62.

[0072] Example 11: Synthesis of Compound 49

[0073] Compound 49

[0074] Compound 49 was synthesized using the synthetic route of compound 4. The yield of the final product was 26%. Mass spectrum m / z: theoretical value 1249.54; found value M+H: 1250.56.

[0075] Example 12: Synthesis of Compound 51

[0076] Compound 51

[0077] Compound 51 was synthesized using the synthetic route of compound 4. The yield of the final product was 23%. Mass spectrum m / z: theoretical value 1194.59; found value M+H: 1195.62.

[0078] Example 13: Synthesis of Compound 57

[0079] Compound 57

[0080] Compound 57 was synthesized by referring to the synthetic route of compound 4. The yield of the final product was 21%. Mass spectrum m / z: theoretical value 1138.53; found value M+H: 1139.55.

[0081] Example 14: Synthesis of Compound 66

[0082] Compound 66

[0083] Compound 66 was synthesized by referring to the synthetic route of compound 4. The yield of the final product was 21%. Mass spectrum m / z: theoretical value 1154.52; found value M+H: 1155.55.

[0084] Example 15: Synthesis of Compound 79

[0085] Compound 79

[0086] Compound 79 was synthesized using the synthetic route of compound 4. The yield of the final product was 25%. Mass spectrum m / z, theoretical value 1374.35; found M+H 1375.37.

[0087] Example 16: Synthesis of Compound 80

[0088] Compound 80

[0089] Compound 80 was synthesized by referring to the synthetic route of compound 4. The yield of the final product was 28%. Mass spectrum m / z: theoretical value 1138.34; found value M+H: 1139.36.

[0090] Example 17: Synthesis of Compound 84

[0091] Compound 84

[0092] Compound 84 was synthesized by referring to the synthetic route of compound 4. The yield of the final product was 24%. Mass spectrum m / z: theoretical value 1190.49; found value M+H: 1191.51.

[0093] Example 18: Synthesis of Compound 92

[0094] Compound 92 was synthesized using the synthetic route of compound 4. The yield of the final product was 28%. Mass spectrum m / z: theoretical value 1020.40; found value M+H: 1021.42.

[0095] Example 19: Synthesis of Compound 108

[0096] Compound 108

[0097] Compound 108 was synthesized by referring to the synthetic route of compound 4. The yield of the final product was 26%. Mass spectrum m / z: theoretical value 1260.60; found value M+H: 1261.62.

[0098] Example 20: Synthesis of Compound 111

[0099] Compound 111

[0100] Compound 111 was synthesized using the synthetic route of compound 4. The yield of the final product was 24%. Mass spectrum m / z: theoretical value 1300.57; found value M+H: 1301.59.

[0101] Example 21: Synthesis of Compound 114

[0102] Compound 114

[0103] Compound 114 was synthesized using the synthetic route of compound 4. The yield of the final product was 26%. Mass spectrum m / z: theoretical value 1067.43; found value M+H: 1068.45.

[0104] Example 22: Synthesis of Compound 120

[0105] Compound 120

[0106] Compound 120 was synthesized by referring to the synthetic route of compound 4. The yield of the final product was 22%. Mass spectrum m / z: theoretical value 1246.53; found value M+H: 1247.55.

[0107] Example 23: Synthesis of Compound 124

[0108] Compound 124

[0109] Compound 124 was synthesized using the synthetic route of compound 4. The yield of the final product was 25%. Mass spectrum m / z: theoretical value 1123.49; found value M+H: 1124.51.

[0110] Example 24: Synthesis of Compound 138

[0111] Compound 138

[0112] Compound 138 was synthesized using the synthetic route of compound 4. The yield of the final product was 28%. Mass spectrum m / z: theoretical value 1182.50; found value M+H: 1183.52.

[0113] Example 25: Synthesis of Compound 151

[0114] Compound 151

[0115] Compound 151 was synthesized using the synthetic route of compound 4. The yield of the final product was 26%. Mass spectrum m / z: theoretical value 1205.57; found value M+H: 1206.59.

[0116] Example 26: Synthesis of Compound 157

[0117] Compound 157

[0118] Compound 157 was synthesized using the synthetic route of compound 4. The yield of the final product was 25%. Mass spectrum m / z: theoretical value 1149.51; found value M+H: 1150.53.

[0119] Example 27: Synthesis of Compound 161

[0120] Compound 161

[0121] Compound 161 was synthesized using the synthetic route of compound 4. The yield of the final product was 22%. Mass spectrum m / z: theoretical value 1250.53; found value M+H: 1251.55.

[0122] Example 28: Synthesis of Compound 168

[0123] Compound 168

[0124] Compound 168 was synthesized using the synthetic route of compound 4. The yield of the final product was 23%. Mass spectrum m / z: theoretical value 1084.46; found value M+H: 1085.48.

[0125] Example 29: Synthesis of Compound 173

[0126] Compound 173

[0127] Compound 173 was synthesized using the synthetic route of compound 4. The yield of the final product was 26%. Mass spectrum m / z: theoretical value 1126.43; found value M+H: 1127.45.

[0128] Example 30: Synthesis of Compound 176

[0129] Compound 176

[0130] Compound 176 was synthesized using the synthetic route of compound 4. The yield of the final product was 21%. Mass spectrum m / z: theoretical value 1254.57; found value M+H: 1255.59.

[0131] Example 31: Synthesis of Compound 180

[0132] Compound 180

[0133] Compound 180 was synthesized using the synthetic route of compound 4. The yield of the final product was 24%. Mass spectrum m / z: theoretical value 1232.58; found value M+H: 1233.61.

[0134] Fabrication of OLED devices:

[0135] As a reference preparation method for a device embodiment, the present invention evaporates a p-doped material on the surface of an ITO glass with a light-emitting area of ​​2mm×2mm or on the anode, or co-evaporates the p-doped material with a hole transport material at a concentration of 1% to 50% to form a 5-100nm hole injection layer (HIL), forms a 5-200nm hole transport layer (HTL) on the hole injection layer, then co-evaporates a host material and a selenium-containing phenene compound (guest material) prepared by the present invention on the hole transport layer in a volume ratio of 3:97 to form a 10-100nm light-emitting layer (EML), and finally co-evaporates to form a 35nm electron transport layer (ETL), and then evaporates 70nm of cathode Al to manufacture an organic electroluminescent diode.

[0136] In a preferred embodiment, the structure of the bottom-emitting OLED device provided by the present invention is: glass containing ITO is used as the anode, and the HIL is sequentially evaporated to be HT-1:P-3 (95:5, v / v%) with a thickness of 10 nanometers; the HTL is HT-1 with a thickness of 90 nanometers; the EBL is HT-8 with a thickness of 10 nanometers, the EML is the main material (H-1): the selenium-containing phenene compound 4 provided by the present invention (97:3, v / v%) with a thickness of 35 nanometers, the ETL is ET-3:LiQ (50:50, v / v%) with a thickness of 35 nanometers, and then the cathode Al is evaporated to be 70 nanometers to prepare an organic electroluminescent diode, which is recorded as Application Example 1.

[0137] Referring to the method provided in Application Example 1, the prepared selenium-containing phenene compound 3, compound 5, compound 6, compound 8, compound 12, compound 14, compound 33, compound 44, compound 48, compound 49, compound 51, compound 57, compound 66, compound 79, compound 80, compound 84, compound 92, compound 108, compound 111, compound 114, compound 120, compound 124, compound 138, compound 151, compound 157, compound 161, compound 168, compound 173, compound 176, and compound 180 were selected as implementation objects to replace compound 4, and they were co-evaporated with the host material compound in a volume ratio of 3:97 to form a light-emitting layer to prepare organic electroluminescent diodes, which are recorded as Application Examples 2 to Application Examples 31.

[0138] Preparation of Comparative Examples 1 to 2

[0139] Comparative Examples 1 and 2 were prepared according to the method provided in Application Example 1, except that BN-1 and BN-2 were used as the guest materials in the light-emitting layer in Comparative Examples 1 and 2, respectively, instead of the selenium-containing phenene compound of the present invention. The chemical structures of the compounds BN-1 and BN-2 in the comparative examples are as follows:

[0140] The current efficiency, voltage, lifespan and other characteristics of the device examples and comparative examples prepared above were tested by standard methods, and the device luminescence characteristic data are shown in Table 1.

[0141] Table 1. Device luminescence characteristics data table

[0142] As can be seen from Table 1, compared with Comparative Examples 1 and 2, Application Examples 1 to 31 all demonstrate good device performance in terms of current efficiency and lifespan. The improved performance of each device application example is based on the improved carrier transport capability of the selenium-containing phenanthrene compound material of the present invention. Furthermore, when used as the main material for the light-emitting layer to prepare electronic devices, the selenium-containing phenanthrene compound exhibits higher current efficiency and lifespan while reducing the driving voltage. This indicates that the selenium-containing phenanthrene compound provided by the present invention has certain commercial application value.

[0143] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A selenophene-containing compound, characterized in that: The selenium-containing phene compound has a structure shown in the following formula I: In Formula I, Ring A and Ring B are each independently selected from a five-membered ring, a five-membered heterocyclic ring, a six-membered ring or a condensed ring; X1, X2, X3, X4, X5, X6, X7, X8, X9, X 10 Each of them is independently selected from N or CR, the X1, X2, X3, X4, and X5 are not selected from N at the same time, and the X6, X7, X8, X9, X 10 Not selected from N at the same time; The R, R1, R2, and R3 are each independently a single substituent to the maximum possible number of substituents or no substituent, and any adjacent substituents are optionally joined or fused to form a ring; R, R1, R2, and R3 are each independently selected from H, deuterium, C1-C24 alkyl, C1-C24 deuterated alkyl, substituted or unsubstituted C3-C24 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C12-C30 aromatic amine, substituted or unsubstituted C12-C30 aromatic silane, substituted or unsubstituted C12-C30 alkoxy, substituted or unsubstituted C12-C30 aromatic oxy, substituted or unsubstituted C2-C24 condensed ring hydrocarbon group, substituted or unsubstituted C6-C30 condensed ring aromatic hydrocarbon group, and the group consisting of.

2. The selenium-containing phene compound according to claim 1, characterized in that Ring A in formula I is selected from a five-membered ring or a benzene ring.

3. The selenium-containing phenene compound according to claim 1, characterized in that Ring B in Formula I is selected from a benzene ring, a five-membered heterocyclic ring containing S or Se.

4. The selenium-containing phenene compound according to claim 1, characterized in that R in Formula I is selected from hydrogen, deuterium, C1-C16 alkyl, C3-C16 cycloalkyl, C6-C18 aryl, C6-C18 heteroaryl, C6-C18 arylsilane, and the group consisting thereof.

5. The selenium-containing phene compound according to claim 1, characterized in that R2 is selected from tert-butyl, phenyl, biphenyl, triaryl, triarylsilane or diarylamine.

6. The selenium-containing phene compound according to claim 1, characterized in that: R, R1, and R3 are each independently selected from the group consisting of hydrogen, deuterium, methyl, ethyl, pentyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantane, phenyl, biphenyl, fluorenyl, aryloxy, diarylamine, triarylsilane, and the like.

7. The selenium-containing phenene compound according to claim 1, characterized in that At least one substituent group among R, R1, R2 and R3 is independently selected from the group consisting of: The structure shown.

8. The selenium-containing phene compound according to claim 1, characterized in that The selenium-containing phenene compound is selected from any one of the following chemical structures, wherein "D" represents deuterium:

9. Use of the selenium-containing phenene compound according to any one of claims 1 to 8 in electronic devices.

10. The use according to claim 9, characterized in that: The electronic device is an organic electroluminescent device, an organic integrated circuit, an organic field effect transistor, an organic thin film transistor, an organic light emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field quenching device, a light emitting electrochemical cell and / or an organic laser diode.

11. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises the selenium-containing phenene compound as claimed in any one of claims 1 to 8.

12. The organic electroluminescent device according to claim 11, comprising a cathode, an anode and an organic functional layer therebetween; characterized in that: The organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises the selenium-containing phenene compound according to any one of claims 1 to 8.

13. An organic photoelectric device, comprising a first electrode, a second electrode facing the first electrode, and a light-emitting material layer disposed between the first electrode and the second electrode; characterized in that: The luminescent material layer contains the selenium-containing phenene compound as described in any one of claims 1 to 8.

14. A composition, characterized in that The composition comprises the selenophene-containing compound as described in any one of claims 1 to 8.

15. A preparation, characterized in that The preparation comprises the selenophene compound according to any one of claims 1 to 8 and at least one solvent.

16. A display or lighting device, characterized in that: The device comprises one or more of the organic electroluminescent devices according to claim 11.

Images