Donor-acceptor type tetradentate cyclometalated platinum or palladium complex phosphorescent material based on aromatic amine donor substituted benzene, and application thereof

Abstract

The invention provides a donor-acceptor type tetradentate cyclometalated platinum or palladium complex phosphorescent material based on aromatic amine donor substituted benzene, and application thereof. The aromatic amine donor is introduced into cyclometalated tetradentate platinum-palladium phosphorescent molecules to construct a donor-acceptor skeleton, so realization of smaller HOMO and LUMO overlap is benefited, [delta]ES1 - T1 is reduced, and the intersystem crossing rate and the quantum efficiency can be improved. The chemical formula of the phosphorescent material is represented by general formula (1) shown in the specification.

Description

technical field

[0001] The present invention relates to a phosphorescent material and its application, in particular to a tetradentate ring metal platinum (II) or palladium (II) complex phosphorescent material based on an aromatic amine donor substituting benzene and its application in organic light-emitting elements . Background technique

[0002] Organic Light-Emitting Diode (OLED) has achieved rapid development in recent years, OLED has been widely used in flat panel display, solid-state lighting, military and aerospace fields, and is expected to replace Liquid Crystal Display (Liquid Crystal Display, LCD). Compared with LCD display technology, OLED has the following advantages: foldable or bendable, self-luminous, high contrast, wide operating temperature range, low material cost, high luminous efficiency, low power consumption, etc. In the early stage of OLED development, traditional fluorescent materials were mainly used, which have good device stability. But theore...

Examples

Embodiment 1

[0039] Example 1: The synthetic route of tetracyclic metal platinum (II) complex phosphorescent material Pt (bp-3-Cz) is as follows:

[0040]

[0041]

[0042] Synthesis of intermediate (1a): Add 1,3-dibromo-5-fluorobenzene (911mg, 3.59mmol, 1.20eq), carbazole (500mg, 2.99mmol, 1.00eq ) and potassium tert-butoxide (502mg, 4.47mmol, 1.50 equiv), injected into dimethylsulfoxide (7mL). Then put it into an oil bath with magnetic stirring, raise the temperature to 140° C. and react for 15 hours, and monitor by thin-layer chromatography until the reaction of the raw materials is completed. The reaction was cooled to room temperature, diluted with ethyl acetate, and the organic phase was washed with water. After liquid separation, the organic phase was dried with anhydrous sodium sulfate. After filtration, the filtrate was distilled off under reduced pressure to remove the solvent. The obtained crude product was separated by silica gel column chromatography, eluent: petroleum ...

Embodiment 2

[0046] Example 2: The synthetic route of tetracyclic metal platinum (II) complex phosphorescent material Pt (bp-3-tBuCz) is as follows:

[0047]

[0048]

[0049] Synthesis of intermediate (2a): 9H-pyrido[2,3-b]indole (1.00g, 5.95mmol, 1.0 equivalents), cuprous iodide (1.13 g, 5.95mmol, 1.0 equivalent) and potassium phosphate (3.79g, 17.85mmol, 3.0 equivalent), the nitrogen was replaced three times, and 1,3-dibromo-5-fluorobenzene (3.02g, 11.89mmol, 2.0 equivalents), trans-1,2-cyclohexanediamine (679 mg, 5.95 mmol, 1.0 equivalents) and toluene (30 mL), put the three-necked bottle into an oil bath with magnetic stirring, and heat up to 85 ° C to react for 55 Hour. The reaction was cooled to room temperature, diluted with ethyl acetate, and the organic phase was washed with water. After liquid separation, the organic phase was dried with anhydrous sodium sulfate. After filtration, the filtrate was distilled off under reduced pressure to remove the solvent. The obtained c...

Embodiment 3

[0053] Example 3: The synthesis route of tetradentate ring metal platinum (II) complex phosphorescent material Pt (bp-3-PhCz) is as follows:

[0054]

[0055]

[0056] Synthesis of intermediate (3b): Add 2a (380mg, 1.11mmol, 1.00eq), 3,6-diphenyl-9H-carbazole (462mg, 1.45mmol, 1.30eq ) and potassium carbonate (460mg, 3.33mmol, 3.00 equiv), into dimethylsulfoxide (18mL). Then put it into an oil bath with magnetic stirring, and raise the temperature to 150° C. for 64 hours. The reaction was cooled to room temperature, diluted with ethyl acetate, and the organic phase was washed with water. After liquid separation, the organic phase was dried with anhydrous sodium sulfate. After filtration, the filtrate was distilled off under reduced pressure to remove the solvent. The obtained crude product was separated by silica gel column chromatography, eluent: petroleum ether / dichloromethane=30:1, and 360 mg of white solid was obtained with a yield of 51%. 1 H NMR (500MHz, CDCl 3 ...

technical field

[0001] The present invention relates to a phosphorescent material and its application, in particular to a tetradentate ring metal platinum (II) or palladium (II) complex phosphorescent material based on an aromatic amine donor substituting benzene and its application in organic light-emitting elements . Background technique

[0002] Organic Light-Emitting Diode (OLED) has achieved rapid development in recent years, OLED has been widely used in flat panel display, solid-state lighting, military and aerospace fields, and is expected to replace Liquid Crystal Display (Liquid Crystal Display, LCD). Compared with LCD display technology, OLED has the following advantages: foldable or bendable, self-luminous, high contrast, wide operating temperature range, low material cost, high luminous efficiency, low power consumption, etc. In the early stage of OLED development, traditional fluorescent materials were mainly used, which have good device stability. But theore...

Examples

Embodiment 1

[0039] Example 1: The synthetic route of tetracyclic metal platinum (II) complex phosphorescent material Pt (bp-3-Cz) is as follows:

[0040]

[0041]

[0042] Synthesis of intermediate (1a): Add 1,3-dibromo-5-fluorobenzene (911mg, 3.59mmol, 1.20eq), carbazole (500mg, 2.99mmol, 1.00eq ) and potassium tert-butoxide (502mg, 4.47mmol, 1.50 equiv), injected into dimethylsulfoxide (7mL). Then put it into an oil bath with magnetic stirring, raise the temperature to 140° C. and react for 15 hours, and monitor by thin-layer chromatography until the reaction of the raw materials is completed. The reaction was cooled to room temperature, diluted with ethyl acetate, and the organic phase was washed with water. After liquid separation, the organic phase was dried with anhydrous sodium sulfate. After filtration, the filtrate was distilled off under reduced pressure to remove the solvent. The obtained crude product was separated by silica gel column chromatography, eluent: petroleum ...

Embodiment 2

[0046] Example 2: The synthetic route of tetracyclic metal platinum (II) complex phosphorescent material Pt (bp-3-tBuCz) is as follows:

[0047]

[0048]

[0049] Synthesis of intermediate (2a): 9H-pyrido[2,3-b]indole (1.00g, 5.95mmol, 1.0 equivalents), cuprous iodide (1.13 g, 5.95mmol, 1.0 equivalent) and potassium phosphate (3.79g, 17.85mmol, 3.0 equivalent), the nitrogen was replaced three times, and 1,3-dibromo-5-fluorobenzene (3.02g, 11.89mmol, 2.0 equivalents), trans-1,2-cyclohexanediamine (679 mg, 5.95 mmol, 1.0 equivalents) and toluene (30 mL), put the three-necked bottle into an oil bath with magnetic stirring, and heat up to 85 ° C to react for 55 Hour. The reaction was cooled to room temperature, diluted with ethyl acetate, and the organic phase was washed with water. After liquid separation, the organic phase was dried with anhydrous sodium sulfate. After filtration, the filtrate was distilled off under reduced pressure to remove the solvent. The obtained c...

Embodiment 3

[0053] Example 3: The synthesis route of tetradentate ring metal platinum (II) complex phosphorescent material Pt (bp-3-PhCz) is as follows:

[0054]

[0055]

[0056] Synthesis of intermediate (3b): Add 2a (380mg, 1.11mmol, 1.00eq), 3,6-diphenyl-9H-carbazole (462mg, 1.45mmol, 1.30eq ) and potassium carbonate (460mg, 3.33mmol, 3.00 equiv), into dimethylsulfoxide (18mL). Then put it into an oil bath with magnetic stirring, and raise the temperature to 150° C. for 64 hours. The reaction was cooled to room temperature, diluted with ethyl acetate, and the organic phase was washed with water. After liquid separation, the organic phase was dried with anhydrous sodium sulfate. After filtration, the filtrate was distilled off under reduced pressure to remove the solvent. The obtained crude product was separated by silica gel column chromatography, eluent: petroleum ether / dichloromethane=30:1, and 360 mg of white solid was obtained with a yield of 51%. 1 H NMR (500MHz, CDCl 3 ...

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