An OLED light-emitting composition and an electroluminescent device comprising the same

Abstract

The present application relates to the technical field of electroluminescent device preparation, in particular to an OLED light-emitting composition and an electroluminescent device comprising the composition. The OLED light-emitting composition comprises an electron transport material and a light-emitting material, the electron transport material combines o-phenanthroline and a xanthene group, and has high electron mobility and a low energy level. A boron-nitrogen compound skeleton structure with multiple benzene rings is introduced into the light-emitting material, the skeleton structure is twisted in a planar configuration, the alkyl substituents contained in the large steric group are adjusted, the π-π mutual attraction caused by the introduction of benzene rings is weakened, the intermolecular force is further weakened, and the adverse effects of concentration quenching on efficiency are weakened. The OLED device prepared by using the composition of the present application has low starting voltage, high light-emitting efficiency and better service life, can meet the requirements of current panel manufacturing enterprises for high-performance materials, and has great commercial value.

Description

Technical Field

[0001] This invention relates to the field of electroluminescent device fabrication technology, and more specifically to an OLED luminescent composition and an electroluminescent device comprising the composition. Background Technology

[0002] In recent years, optoelectronic devices based on organic materials have become increasingly popular. Examples of such organic optoelectronic devices include organic light-emitting diodes (OLEDs), organic field-effect transistors, organic photovoltaic cells, and organic sensors. Among them, OLEDs have developed particularly rapidly and have already achieved commercial success in the field of information display. OLEDs can provide highly saturated red, green, and blue colors, and full-color displays made with them do not require an additional backlight, offering advantages such as vibrant colors, short response time, wide color gamut, and high contrast.

[0003] The core of OLED devices is a thin-film structure containing various organic functional materials. Common functionalized organic materials include: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, as well as luminescent host materials and luminescent guest materials (dyes). When an electric current is applied, electrons and holes are injected and transported to the luminescent region, where they recombine to generate excitons and emit light. The core organic luminescent material in OLED display technology achieves full color gamut by mixing red, green, and blue light materials. The development of novel luminescent materials is the driving force behind the continuous progress of electroluminescence technology and a research hotspot in the organic electroluminescence industry. The development of novel blue organic electroluminescent materials enables devices to achieve high luminous efficiency and better lifespan. Meanwhile, blue luminescent materials with narrow half-width and high color purity are the focus of blue luminescent material development. Generally, the hole mobility in organic compounds is an order of magnitude higher than the electron mobility; therefore, the selection of electron transport region materials and luminescent materials in OLED devices has a significant impact on the performance of OLED devices. Summary of the Invention

[0004] To address the aforementioned problems in the prior art, the present invention provides an OLED light-emitting composition and an electroluminescent device comprising the composition. Based on the combination method of the composition described in this invention, the overall performance of organic electroluminescent devices can be effectively improved.

[0005] To achieve the objectives of this invention, the technical solution is as follows:

[0006] This invention provides an OLED luminescent composition, the composition comprising at least an electron transport material and a luminescent material, the electron transport material comprising a compound having the structural features shown in Formula 1, and the luminescent material comprising a compound having the structural features shown in Formula 2.

[0007]

[0008] In Formula 1, L1, L2, R1, and R2 are each independently selected from non-existent, hydrogen, deuterium, C6-C30 aryl, and C5-C30 heteroaryl.

[0009] Ar1, Ar2 and Ar3 are each independently selected from benzo[h]quinoline or 1,10-o-phenanthroline;

[0010] In Formula 2, R3 is selected from hydrogen-based, C1-C... 12 Alkyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted diphenylamino, triarylsilane or silyl; when containing a substituent, the substituent is selected from C1-C1. 12 alkyl;

[0011] R4-R6 are each independently selected from hydrogen groups, C1-C6 groups. 12 Alkyl or C1-C 12 Alkyl-substituted phenyl;

[0012] X1 is either S or O.

[0013] Furthermore, L1, L2, R1, and R2 are each independently selected from non-existent, phenyl, or pyridyl groups.

[0014] Preferably, L1 and L2 are each independently selected from the absence of 1,3-phenylene, 2,6-pyridylene, or 3,5-pyridylene.

[0015] Furthermore, each of R4-R6 is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, or tert-butylphenyl.

[0016] More preferably, the electron transport material in the OLED luminescent composition is selected from any of the following compounds:

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035] The luminescent material in the OLED luminescent composition is selected from any of the following compounds:

[0036]

[0037]

[0038] Furthermore, the present invention also provides the application of OLED compositions having the structural features of Formula 1 and Formula 2 as described above in electronic devices.

[0039] Furthermore, the electronic devices include organic electroluminescent devices, organic integrated circuits (O-IC), organic field-effect transistors (O-FET), organic thin-film transistors (O-TFT), organic light-emitting transistors (O-LET), organic solar cells (O-SC), organic optical detectors, organic photosensors, organic field quenching devices (O-FQD), light-emitting electrochemical cells (LEC), and organic laser diodes (O-laser).

[0040] In another aspect, the present invention also provides an organic electroluminescent device, the organic electroluminescent device comprising a cathode, an anode and an organic functional layer therebetween; the organic functional layer comprising an electron transport layer and a light-emitting layer, the electron transport layer comprising a compound having the structure shown in Formula 1, and the light-emitting layer comprising a compound having the structure shown in Formula 2;

[0041]

[0042] In Formula 1, L1, L2, R1, and R2 are each independently selected from non-existent, hydrogen, deuterium, C6-C30 aryl, and C5-C30 heteroaryl.

[0043] Ar1, Ar2 and Ar3 are each independently selected from benzo[h]quinoline or 1,10-o-phenanthroline;

[0044]

[0045] In Formula 2, R3 is selected from hydrogen-based, C1-C... 12 Alkyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted diphenylamino, triarylsilane or silyl; when containing a substituent, the substituent is selected from C1-C1. 12 alkyl;

[0046] R4-R6 are each independently selected from hydrogen groups, C1-C6 groups. 12 Alkyl or C1-C 12 Alkyl-substituted phenyl;

[0047] X1 is either S or O.

[0048] Furthermore, L1, L2, R1, and R2 are each independently selected from non-existent, phenyl, or pyridyl groups.

[0049] Preferably, L1 and L2 are each independently selected from the absence of 1,3-phenylene, 2,6-pyridylene, or 3,5-pyridylene.

[0050] Furthermore, each of R4-R6 is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, or tert-butylphenyl.

[0051] The present invention also provides an organic optoelectronic device comprising: a substrate layer; a first electrode on the substrate; an organic light-emitting functional layer on the first electrode; and a second electrode on the organic light-emitting functional layer; wherein the organic light-emitting functional layer comprises an OLED composition having the compound structures of Formula 1 and Formula 2 as described above.

[0052] The present invention also provides a formulation comprising an OLED composition having the structures of Formula 1 and Formula 2 as described above and at least one solvent. The solvent is not particularly limited and may be any solvent well known to those skilled in the art, such as unsaturated hydrocarbon solvents like toluene, xylene, mesitylene, tetrahydronaphthalene, decahydronaphthalene, dicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, etc.; halogenated saturated hydrocarbon solvents like carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, etc.; halogenated unsaturated hydrocarbon solvents like chlorobenzene, dichlorobenzene, trichlorobenzene, etc.; ether solvents like tetrahydrofuran, tetrahydropyran, etc.; and ester solvents like alkyl benzoates.

[0053] The present invention also provides a display or lighting device comprising one or more of the organic optoelectronic devices described above.

[0054] Compared with the prior art, the beneficial effects of the present invention are:

[0055] This invention provides an OLED composition with specific electron transport and luminescent materials. The electron transport material combines o-phenanthroline and azine groups, exhibiting high electron mobility and low energy levels. A boron-nitrogen compound framework structure with multiple linked benzene rings containing alkyl substituents is introduced into the luminescent material, distorting its planar configuration. By adjusting the alkyl substituents on the sterically hindered groups, the π-π interactions caused by the introduction of benzene rings are weakened, further reducing intermolecular forces and thus mitigating the adverse effects of concentration quenching on efficiency. OLED devices prepared using the composition of this invention exhibit low start-up voltage, high luminous efficiency, and superior lifespan, meeting the current requirements of panel manufacturers for high-performance materials and possessing significant commercial value. Detailed Implementation

[0056] The present invention will now be described in detail. The descriptions of the constituent elements described below are 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.

[0057] The term "substituted" as used in this invention is intended to encompass all permissible substituents of organic compounds. In a broad sense, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and non-aromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. For a suitable organic compound, permissible substituents may be one or more, the same or different. For the purposes of this invention, heteroatoms (e.g., nitrogen) may have hydrogen substituents and / or any permissible substituent of the organic compound described herein, satisfying the valence bond of that heteroatom. This invention is not intended to limit in any way to permissible substituents of organic compounds. Similarly, the terms "substituted" or "substituted with" implicitly include the condition that such substitution conforms to the permissible valence bond of the substituted atom and the substituent, and that the substitution results in a stable compound (e.g., a compound that does not spontaneously undergo transformations (e.g., by rearrangement, cyclization, elimination, etc.)). It is also expected that, in some respects, unless explicitly stated otherwise, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted).

[0058] The compounds disclosed herein can exhibit desired properties and have emission and / or absorption spectra that can be tuned by selecting suitable ligands. On the other hand, the invention excludes any one or more compounds, structures, or portions thereof specifically described herein. The compounds of the invention can be prepared using a variety of methods, including but not limited to those described in the examples provided herein. It should be noted that the general description above and the detailed description below are exemplary and illustrative only, and not limiting. This application can be more readily understood by referring to the following detailed description and the examples contained therein.

[0059] Before disclosing and describing the compounds, devices, and / or methods of the present invention, it should be understood that they are not limited to specific synthetic methods (otherwise indicated) or specific reagents (otherwise indicated), as these are, of course, subject to variation. It should also be understood that the terminology used in this invention is for descriptive purposes only and is not intended to be limiting. While any methods and materials similar to or equivalent to those described in this invention may be used in this practice or experiment, exemplary methods and materials are described below. All raw materials and solvents used in the synthetic examples are commercially available unless otherwise specified, and the solvents were used directly without further processing.

[0060] The substrate described in this invention can be any substrate typically used in organic optoelectronic devices. It can be a glass or transparent plastic substrate, or an opaque material such as silicon or stainless steel, or a flexible PI film. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and water resistance, and their applications vary depending on their properties. As a material for hole injection layers, hole transport layers, electron injection layers, etc., any material can be selected from known materials used in OLED devices; this invention does not impose specific limitations.

[0061] Synthesis Examples

[0062] The examples of compound synthesis, composition, devices, or methods below are intended to provide a general approach to the industry and are not intended to limit the scope of this patent. While we strive for accuracy in the data (quantities, temperatures, etc.) mentioned in the patent, some errors may still exist. Unless otherwise specified, weighings are performed separately, temperatures are in °C or room temperature, and pressures are close to atmospheric pressure.

[0063] The examples below provide methods for preparing novel compounds, but the preparation of such compounds is not limited to these methods. In this field of expertise, since the compounds protected in this invention are easily modified and prepared, their preparation can be carried out using the methods listed below or other methods. The examples below are merely illustrative and are not intended to limit the scope of this patent. Temperature, catalyst, concentration, reactants, and reaction process can all be varied to select different conditions for preparing the compounds with different reactants.

[0064] Example 1: Synthesis of Compound 1-01

[0065]

[0066] (1) After dissolving compound 2,9-dibromo-1,10-phenanthroline (5.41 g, 16 mmol) in 1,4-dioxane (130 mL), 1,3-phenylenediboronic acid (5.47 g, 33 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol) were added, and the mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 1-01-1 (4.71 g, 70% yield). LC-MS: M / Z 420.15 (M+).

[0067] (2) After dissolving compound 1-01-1 (6.72 g, 16 mmol) in 1,4-dioxane (130 mL), 2-bromo-1,10-phenanthroline (58.55 g, 33 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol) were added, and the mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 1-01 (9.81 g, 89% yield). LC-MS: M / Z 688.24 (M+).

[0068] Example 2: Synthesis of compounds 1-71

[0069]

[0070] (1) After dissolving pyridine-3,5-dimethyldiboronic acid (5.50 g, 33 mmol) in 1,4-dioxane (130 mL), 2-bromo-9-pyridyl-1,10-phenanthroline (10.76 g, 32 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol) were added, and the mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 1-71-1 (9.44 g, 78% yield). LC-MS: M / Z 378 (M+).

[0071] (2) After dissolving pyridine-3,5-dimethyldiboronic acid (5.50 g, 33 mmol) in 1,4-dioxane (130 mL), 2-bromo-9-phenyl-1,10-phenanthroline (10.72 g, 32 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol) were added, and the mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 1-71-2 (9.78 g, 81% yield). LC-MS: M / Z 377 (M+).

[0072] (3) After dissolving compound 1-71-1 (12.10 g, 32 mmol) in 1,4-dioxane (130 mL), 4,7-dibromo-1,10-phenanthroline (10.82 g, 32 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol) were added, and the mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 1-71-3 (14.20 g, 75% yield). LC-MS: M / Z 590 (M+).

[0073] (4) After dissolving compound 1-71-2 (12.07 g, 32 mmol) in 1,4-dioxane (130 mL), 1-71-3 (18.93 g, 32 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol) were added, and the mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 1-71 (23.17 g, 86% yield). LC-MS: M / Z 841 (M+).

[0074] Example 3: Synthesis of compounds 1-99

[0075]

[0076] (1) After dissolving 2-bromo-9-phenyl-1,10-phenanthroline (10.73 g, 32 mmol) in 1,4-dioxane (130 mL), 1,3-phenyldiboronic acid (5.47 g, 33 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol) were added, and the mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 1-99-1 (7.34 g, 61% yield). LC-MS: M / Z 376 (M+).

[0077] (2) After dissolving compound 1-99-1 (12.04 g, 32 mmol) in 1,4-dioxane (130 mL), 5,6-dibromo-1,10-phenanthroline (10.82 g, 32 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol) were added, and the mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 1-99-2 (13.70 g, 56% yield). LC-MS: M / Z 588 (M+).

[0078] (3) After dissolving compound 1-01-2 (9.60 g, 32 mmol) in 1,4-dioxane (130 mL), 1-99-2 (19.45 g, 33 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol) were added, and the mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 1-99 (18.34 g, 75% yield). LC-MS: M / Z 764 (M+).

[0079] Example 4: Synthesis of Compound 1-139

[0080]

[0081]

[0082] (1) Under nitrogen atmosphere, 5,6-dibromo-1,10-phenanthroline (3.38 g, 10 mmol) was dissolved in DMF (100 mL), and then pinacol diboronate (6.10 g, 24 mmol), palladium acetate (0.18 g, 0.08 mmol), and potassium acetate (4.0 g, 40 mmol) were added. The mixture was reacted at 80-100 °C for 5 h. After cooling, EA was added for extraction. The organic phase was filtered through diatomaceous earth and concentrated. The crude product was washed with ethanol to obtain the target compound 1-139-1 (4.23 g, yield 98%). LC-MS: M / Z 432 (M+)

[0083] (2) After dissolving 2-bromo-9-phenyl-1,10-phenanthroline (11.06 g, 33 mmol) in 1,4-dioxane (130 mL), 1-139-1 (6.91 g, 16 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (13.83 g, 93 mmol) were added, and the mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 1-139 (5.40 g, 49% yield). LC-MS: M / Z 688 (M+).

[0084] Example 5: Synthesis of Compound 2-05

[0085]

[0086] (1) After dissolving 4-bromo-7-phenyl-1,10-phenanthroline (10.72 g, 32 mmol) in 1,4-dioxane (130 mL), pyridine-2,6-diyldiboronic acid (5.34 g, 32 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol) were added, and the mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to give the target compound 2-05-1 (5.07 g, 42% yield). LC-MS: M / Z 377 (M+).

[0087] (2) After dissolving compound 2-05-1 (11.13 g, 33 mmol) in 1,4-dioxane (130 mL), 2,9-dibromo-1,10-phenanthroline (5.41 g, 16 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol) were added, and the mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 2-05 (6.47 g, 48% yield). LC-MS: M / Z 842 (M+).

[0088] Example 6: Synthesis of Compound 2-38

[0089]

[0090] Compound 2-38-1 (7.39 g, 33 mmol) was dissolved in 1,4-dioxane (130 mL), followed by the addition of 2,9-dibromo-1,10-phenanthroline (5.41 g, 16 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol). The mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to give the target compound 2-38 (7.38 g, 86% yield). LC-MS: M / Z 536 (M+).

[0091] Example 7: Synthesis of Compounds 2-56

[0092]

[0093] (1) After dissolving pyridine-3,5-dimethyldiboronic acid (5.34 g, 32 mmol) in 1,4-dioxane (130 mL), 2-56-1 (10.73 g, 32 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol) were added, and the mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 2-56-2 (8.09 g, 67% yield). LC-MS: M / Z 377 (M+).

[0094] (2) After dissolving compound 2-56-2 (12.45 g, 33 mmol) in 1,4-dioxane (130 mL), 4,7-dibromo-1,10-phenanthroline (5.41 g, 16 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol) were added, and the mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 2-56 (7.28 g, 54% yield). LC-MS: M / Z 842 (M+).

[0095] Example 8: Synthesis of Compounds 2-92

[0096]

[0097] (1) After dissolving compound 2-92-1 (9.64 g, 32 mmol) in 1,4-dioxane (130 mL), 4,7-dibromo-1,10-phenanthroline (10.82 g, 32 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol) were added, and the mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 2-92-2 (7.28 g, 58% yield). LC-MS: M / Z 513 (M+).

[0098] (2) After dissolving compound 2-92-2 (16.97 g, 33 mmol) in 1,4-dioxane (130 mL), 2-92-3 (7.17 g, 32 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol) were added, and the mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 2-92 (15.71 g, 80% yield). LC-MS: M / Z 613 (M+).

[0099] Example 9: Synthesis of Compounds 3-16

[0100]

[0101] (1) Compound 3-16-1 (9.64 g, 32 mmol) was dissolved in 1,4-dioxane (130 mL), followed by the addition of 4,7-dibromo-1,10-phenanthroline (10.82 g, 32 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol). The mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 3-16-2 (8.89 g, 54% yield). LC-MS: M / Z 513 (M+).

[0102] (2) After dissolving compound 3-16-2 (16.97 g, 33 mmol) in 1,4-dioxane (130 mL), 3-16-3 (9.60 g, 32 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol) were added, and the mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 3-16 (17.88 g, 81% yield). LC-MS: M / Z 689 (M+).

[0103] Example 10: Synthesis of Compound 3-44

[0104]

[0105] Compound 3-44-1 (9.94 g, 33 mmol) was dissolved in 1,4-dioxane (130 mL), followed by the addition of 2,9-dibromo-1,10-phenanthroline (5.41 g, 16 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol). The mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to give the target compound 3-44 (7.07 g, 64% yield). LC-MS: M / Z 690 (M+).

[0106] Example 11: Synthesis of compound 3-138

[0107]

[0108] (1) Compound 3-138-1 (9.60 g, 32 mmol) was dissolved in 1,4-dioxane (130 mL), followed by the addition of 5,6-dibromo-1,10-phenanthroline (10.82 g, 32 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol). The mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 3-138-2 (8.71 g, 53% yield). LC-MS: M / Z 512 (M+).

[0109] (2) After dissolving compound 3-138-2 (16.94 g, 33 mmol) in 1,4-dioxane (130 mL), 3-138-3 (7.17 g, 32 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol) were added, and the mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 3-138 (10.20 g, 52% yield). LC-MS: M / Z 612 (M+).

[0110] Example 12: Synthesis of Compound 4-11

[0111]

[0112] (1) Compound 4-11-1 (12.04 g, 32 mmol) was dissolved in 1,4-dioxane (130 mL), followed by the addition of 2,9-dibromo-1,10-phenanthroline (10.82 g, 32 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol). The mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 4-11-2 (9.24 g, 49% yield). LC-MS: M / Z 588 (M+).

[0113] (2) After dissolving compound 4-11-2 (19.45 g, 33 mmol) in 1,4-dioxane (130 mL), 4-11-3 (9.60 g, 32 mmol), tetrakis(triphenylphosphine)palladium (1.8 g, 1.5 mmol), and potassium carbonate (12.8 g, 93 mmol) were added, and the mixture was stirred at 100 °C for 6 hours. After the reaction was terminated, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as the developing solvent to obtain the target compound 4-11 (13.19 g, 49% yield). LC-MS: M / Z 840 (M+).

[0114] Example 13: Synthesis of Compound 5-1

[0115]

[0116] Step 1. Add 5.80 g (12 mmol) of sodium tert-butoxide (3.56 g, 37 mmol) to a three-necked flask, add toluene (150 mL), purge twice with nitrogen, add 1-tert-butyl-3,5-dichlorobenzene (2.42 g, 12 mmol) and catalyst Pd2(dba)3 (0.43 g, 0.37 mmol), purge three times with N2, inject tri-tert-butylphosphine (0.06 mL, 2.5 mmol), heat to 70 °C, and react for 1 h. Cool the reaction solution, wash with water, remove the palladium catalyst by passing through diatomaceous earth, evaporate to dryness, recrystallize with dichloromethane / petroleum ether to obtain a solid, wash with a toluene / ethyl acetate mixture at 45 °C for 2 h, filter to obtain 5.1-2 (4.84 g, 62%). LC-MS: M / Z 649 (M+).

[0117] Step 2. Add 7.80 g (12 mmol) of sodium tert-butoxide (3.56 g, 37 mmol) to a three-necked flask, purge twice with toluene (150 mL) and nitrogen. Add 3.38 g (12 mmol) of 5-1-3 and catalyst Pd2(dba)3 (0.43 g, 0.37 mmol), purge three times with N2, and inject 0.06 mL (2.5 mmol) of tri-tert-butylphosphine. Heat to 70 °C and react for 1 h. Cool the reaction solution, wash with water, remove the palladium catalyst with diatomaceous earth, evaporate to dryness, recrystallize with dichloromethane / petroleum ether to obtain a solid, wash with a toluene / ethyl acetate mixture at 45 °C for 2 h, filter to obtain 8.27 g (77%) of 5-1-4. LC-MS: M / Z 894 (M+).

[0118] Step 3. Dissolve 5-1-4 (22.39 g, 25 mmol) in dichloromethane (300 mL) at 0 °C, purging twice with nitrogen. Slowly add N-bromosuccinimide (4.63 g, 26 mmol) and stir for 30 minutes. Stir at room temperature for 4 hours. Extract with dichloromethane and concentrate the organic layer. Recrystallize from ethyl acetate to obtain 5-1-5 (22.41 g, 92%). LC-MS: M / Z 972 (M+).

[0119] Step 4. Add 22.41 g (23 mmol) of 5-1-5 and 120 mL of tert-butylbenzene to a 300 mL reactor. Add 42.5 mL (68 mmol) of n-butyllithium dropwise at -78 °C, and stir at 60 °C for 3 hours. Then, purge with nitrogen to remove heptane. Add 11.3 g (45 mmol) of boron tribromide dropwise at -78 °C, and stir at room temperature for 1 hour. Add 5.9 g (45 mmol) of N,N-diisopropylethylamine dropwise at 0 °C, and stir at 120 °C for 2 hours. After the reaction is complete, add an aqueous solution of sodium acetate at room temperature and stir. Extract with ethyl acetate, concentrate the organic layer, and separate by column chromatography to obtain 5-1 (3.53 g, 17%). LC-MS: M / Z: 902 (M+).

[0120] Example 14: Preparation of compounds 5-8

[0121] Compound 5-8 was synthesized using the same method as compound 5-1 in Example 13, yielding compound 5-8. LC-MS: M / Z 982 (M+).

[0122] Example 15: Preparation of compounds 5-17

[0123] Compound 5-17 was synthesized using the same method as compound 5-1 in Example 13, yielding compound 5-17. LC-MS: M / Z 1054 (M+).

[0124] Example 16: Preparation of compound 5-25

[0125] Compound 5-25 was synthesized using the same method as compound 5-1 in Example 13, yielding compound 5-25. LC-MS: M / Z 1125 (M+).

[0126] Example 17: Preparation of compound 5-36

[0127] Compound 5-36 was synthesized using the same method as compound 5-1 in Example 13, yielding compound 5-36. LC-MS: M / Z 974 (M+).

[0128] Example 18: Preparation of compound 5-40

[0129] Compound 5-40 was synthesized using the same method as compound 5-1 in Example 13, yielding compound 5-40. LC-MS: M / Z 1088 (M+).

[0130] The HOMO, LUMO, triplet excited state level, and S1 level of compound 5-1 prepared in this invention and compound P-1, which has a similar structure, were evaluated. Table 1 is a comparison table of energy level evaluations.

[0131] Table 1. Comparison of HOMO, LUMO, triple excited state level and S1 level evaluations

[0132]

[0133] As shown in Table 1, compound 5-1 has a larger band gap (HOMO-LUMO) and a smaller S1-T1 value compared to compound P-1, which has a similar structure. This demonstrates that the selection of the triphenylsilane linking position in this invention can improve the electronic properties of the compound.

[0134] Device fabrication examples:

[0135] Comparative Example 1 Implementation Scheme: ITO / HI (10nm) / HT (30nm) / EBL (10nm) / Host: 3wt% doping (30nm) / / HBL (20nm)ET (30nm) / LiF (0.5nm) / Al (150nm).

[0136] A first hole injection layer (HIL) with a thickness of 10 nm was formed by evaporating HATCN on an ITO substrate. A hole transport layer (HTL) with a thickness of 30 nm was formed by evaporating HTL-1 on the first hole injection layer. An electron blocking layer (EBL) with a thickness of 10 nm was formed by evaporating CzSi on the hole transport layer. An emissive layer (EML) with a thickness of 30 nm was formed by evaporating (pBH+nBH):P-1 (3wt%) on the electron blocking layer. A hole blocking layer (HBL) with a thickness of 20 nm was formed by evaporating TSPO1. An electron transport layer (ET) with a thickness of 30 nm was formed by evaporating ET-1. An electron injection layer with a thickness of 0.5 nm was formed by evaporating LiF. An electron cathode (Al with a thickness of 150 nm) was formed by evaporating. Comparative Example 1 of an organic electroluminescent device was thus fabricated.

[0137] The device structures and fabrication methods of the first to twelfth embodiments are similar to those of Comparative Example 1, except that the electron transport layer and light-emitting layer materials of the OLED devices are the compounds listed in Table 2. The electron emission characteristics of the fabricated organic light-emitting devices are also shown in Table 2. The molecular structural formulas of the relevant materials are shown below:

[0138]

[0139] Table 2. Comparison of Electroluminescent Devices and Their Electroluminescence Performance

[0140]

[0141] As shown in Table 2, compared with Comparative Example 1, the first to eighteenth embodiments show significant improvements in luminous efficiency and lifetime under the same current density, demonstrating higher luminous efficiency and longer lifetime. The performance improvements of the electronic devices in each embodiment are achieved based on the superior electronic properties of the specific materials of this invention. The azine group structure in the electron transport material of this invention is relatively stable, resistant to acids, alkalis, and high temperatures, and has a high glass transition temperature. The combination of o-phenanthroline and azine groups, as typical strong electron-withdrawing groups, results in compounds with high electron mobility and low energy levels centered around them. Furthermore, in the selection of luminescent materials, this invention introduces a boron-nitrogen compound skeleton structure with multiple benzene rings containing alkyl substituents as a sterically hindered group, distorting its planar configuration. By adjusting the alkyl substituents on the sterically hindered group, the π-π mutual attraction caused by the introduction of benzene rings is weakened, further reducing intermolecular forces and thus mitigating the adverse effects of concentration quenching on efficiency. Simultaneously, the multi-benzene ring skeleton is beneficial for increasing the dihedral angle formed by the boron atom and the two aromatic rings on either side, which helps maintain PL spectrum stability. It is evident that OLED devices prepared using the composition of this invention have high luminous efficiency and superior lifespan, meeting the current requirements of panel manufacturers for high-performance materials and possessing significant commercial value.

[0142] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. An OLED light-emitting composition, characterized in that, The composition comprises at least an electron transport material and a luminescent material, wherein the electron transport material comprises a compound with the structural characteristics shown in Formula 1, and the luminescent material comprises a compound with the structural characteristics shown in Formula 2. In Formula 1, L1 and L2 are each independently selected from non-existent, phenylene, or pyridylene; R1 and R2 are each independently selected from non-existent, hydrogen, phenyl, or pyridylene. Ar1, Ar2 and Ar3 are each independently selected from benzo[h]quinoline or 1,10-o-phenanthroline; In Equation 2, R3 is selected from hydrogen, C1-C 12 Alkyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted diphenylamino, triarylsilane or silyl; when containing a substituent, the substituent is selected from C1-C1. 12 alkyl; R4-R6 are each independently selected from hydrogen, C1-C 12 Alkyl or C1-C 12 Alkyl-substituted phenyl; X1 is either S or O.

2. The OLED light-emitting composition according to claim 1, characterized in that, The L1 and L2 are each independently selected from the absence of, 1,3-phenylene, 2,6-pyridylene, or 3,5-pyridylene.

3. The OLED light-emitting composition according to claim 1, characterized in that, R4-R6 are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl or tert-butylphenyl.

4. The OLED light-emitting composition according to claim 1, characterized in that, The electron transport material in the OLED luminescent composition is selected from any of the following compounds:

5. The OLED light-emitting composition according to claim 1, characterized in that, The luminescent material in the OLED luminescent composition is selected from any of the following compounds:

6. The use of the OLED luminescent composition according to any one of claims 1-5 in the preparation of organic electroluminescent devices.

7. An organic electroluminescent device, characterized in that, The organic electroluminescent device comprises: a substrate layer; a first electrode on the substrate; an organic light-emitting functional layer on the first electrode; and a second electrode on the organic light-emitting functional layer; wherein the organic light-emitting functional layer comprises the OLED light-emitting composition according to any one of claims 1-5.

8. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes a cathode, an anode, and an organic functional layer between them; the organic functional layer comprises the OLED light-emitting composition according to any one of claims 1-5.

9. A formulation, characterized in that, The formulation comprises the OLED luminescent composition according to any one of claims 1-5 and at least one solvent.

10. A display or lighting device, characterized in that, The device comprises one of the organic electroluminescent devices according to claim 8.

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