Organic phosphorus luminescent compound and preparation method and application thereof

文档序号：997921 发布日期：2020-10-23 浏览：7次中文

阅读说明：本技术 一种有机磷发光化合物及其制备方法和应用 (Organic phosphorus luminescent compound and preparation method and application thereof ) 是由赵贺陈剑锋张颖张思铭李金磊马晓宇于 2020-07-09 设计创作，主要内容包括：本发明公开了一种有机磷发光化合物,所述有机磷发光化合物的结构通式如化学式1所示：<Image he="320" wi="700" file="DDA0002577273520000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>式中R1a、R1b、R1c、R1d、R2a、R2b、R2c、R2d、R3a、R3b、R4a、R4b、R4c、R5a、R5b、R5c、R5d各自独立地选自以下基团：氢、氘、卤素、氰基、取代或非取代的C1～C8烷基、取代或非取代的C3～C30的环烷基、取代或非取代的C6～C18芳基；本发明提供的上述制备方法简单易行,产物纯度高,产物纯度可到99％以上；本发明制备化学式1所示有机磷发光化合物,能够使有机电致发光器件的驱动电压降至4.0V以下,发光效率提高至35cd/A以上,寿命T(95)达到670以上。(The invention discloses an organic phosphorus luminescent compound, which has a structural general formula shown in chemical formula 1: in the formula R 1a 、R 1b 、R 1c 、R 1d 、R 2a 、R 2b 、R 2c 、R 2d 、R 3a 、R 3b 、R 4a 、R 4b 、R 4c 、R 5a 、R 5b 、R 5c 、R 5d Each independently selected from the group consisting of: hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C8 alkyl, or a salt thereofSubstituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C18 aryl; the preparation method provided by the invention is simple and feasible, the product purity is high, and the product purity can reach more than 99%; the organic phosphorus luminescent compound shown in chemical formula 1 prepared by the invention can reduce the driving voltage of an organic electroluminescent device to be below 4.0V, improve the luminous efficiency to be above 35cd/A, and prolong the service life T (95) to be above 670.)

1. An organic phosphorus luminescent compound, wherein the structural general formula of the organic phosphorus luminescent compound is shown in chemical formula 1:

wherein R is_1a、R_1b、R_1c、R_1d、R_2a、R_2b、R_2c、R_2d、R_3a、R_3b、R_4a、R_4b、R_4c、R_5a、R_5b、R_5c、R_5dEach independently selected from: hydrogen, deuterium, halogen, cyanogenThe aryl group comprises a substituent or non-substituent C1-C8 alkyl group, a substituent or non-substituent C3-C30 cycloalkyl group and a substituent or non-substituent C6-C18 aryl group.

2. A preparation method of an organic phosphorus luminescent compound is characterized by comprising the following steps:

(1) under the protection of inert gas, mixing the compound A and iridium trichloride trihydrate, adding the mixture into a solvent I for heating reaction, wherein the solvent I is ethylene glycol ethyl ether and/or water, performing suction filtration after the reaction is finished, and sequentially washing and drying to obtain a bridging ligand B;

(2) under the protection of inert gas, mixing the bridging ligand B and silver trifluoromethanesulfonate, adding the mixture into a solvent II for heating reaction, wherein the solvent II is dichloromethane and/or methanol, and performing column chromatography separation and rotary evaporation concentration after the reaction to obtain an intermediate C;

(3) under the protection of inert gas, mixing the intermediate C with the compound D, adding the mixture into a solvent III, heating and reacting, wherein the solvent III is ethanol and/or tetrahydrofuran, and performing suction filtration, washing, drying, column chromatography and rotary evaporation concentration after the reaction is finished to obtain an organophosphorus luminescent compound shown in a chemical formula 1;

the synthetic route of the organic phosphorus luminescent compound shown in chemical formula 1 is as follows:

3. the method of claim 2, wherein the inert gas used in steps (1) to (3) is nitrogen or argon;

in the step (1):

the molar ratio of the compound A to the iridium trichloride trihydrate is (2-3) to 1;

the heating reaction temperature is 130-140 ℃, and the reaction time is 20-30 h;

the volume ratio of the ethylene glycol ethyl ether to the water in the solvent I is 3: 1;

the ratio of the compound A to the solvent I is 64.4mmol (350-400) mL;

the detergent is one or a mixture of water, absolute ethyl alcohol and petroleum ether;

the drying temperature is 70-80 ℃, and the drying time is 5 h.

4. The method for preparing an organophosphorus luminescent compound according to claim 2, wherein the molar ratio of the bridging ligand B to the silver trifluoromethanesulfonate in the step (2) is 1 (2-3);

the reaction temperature is 55-65 ℃, and the reaction time is 20-30 h;

the volume ratio of dichloromethane to methanol in the solvent II is 5: 2;

the ratio of the bridging ligand B to the solvent II is 6.4mmol: 105-140 mL.

The column chromatography separation adopts a short column for column chromatography.

5. The method for preparing an organophosphorus luminescent compound according to claim 2, wherein the molar ratio of the intermediate C to the compound D in the step (3) is 1 (2-3);

the reaction temperature is 75-80 ℃, and the reaction time is 20-30 h;

ethanol in the solvent III;

the ratio of the intermediate C to the solvent III is 11.2mmol: 90-130 mL.

The detergent is ethanol; the drying temperature is 70-80 ℃, and the drying time is 5 hours;

the column chromatography is carried out by using dichloromethane and petroleum ether according to the weight ratio of 1: mixing the raw materials in a volume ratio of 1-15 to serve as a solvent, and performing silica gel column chromatography.

6. Use of the organophosphorus light-emitting compound according to claim 1 for producing an organic electroluminescent device.

7. An organic electroluminescent device comprising an anode, a cathode and an intermediate layer disposed between the anode and the cathode;

wherein the intermediate layer comprises a light-emitting layer comprising the organic phosphorus light-emitting compound according to claim 1.

8. The organic electroluminescent device as claimed in claim 7, wherein the anode is selected from indium tin oxide, zinc oxide or indium oxide, and the thickness of the anode is 10 to 500 nm;

the cathode is selected from Al, Li, Na, K, Mg, Ca, Au, Ag or Pb, and the thickness of the cathode is 100-1000 nm.

9. The organic electroluminescent device as claimed in claim 7, wherein the organic phosphorus luminescent compound accounts for 0.5-10% of the luminescent layer;

the luminescent layer also comprises a main material, and the main material is one or a mixture of more of 4, 4'-N, N' -biphenyl dicarbazole, octahydroxyquinoline, a metal phenoxy benzothiazole compound, polyfluorene, aromatic condensed rings and a zinc complex;

the thickness of the light emitting layer is 10-500 nm.

10. The organic electroluminescent device according to claim 7, wherein the intermediate layer further comprises a functional layer;

the functional layer is one or more of a hole injection layer, a hole transport layer, a hole injection-hole transport functional layer, an Electron Blocking Layer (EBL), a hole blocking layer, an electron transport layer, an electron injection layer and an electron transport-electron injection functional layer.

Technical Field

The invention relates to the technical field of luminescent materials, in particular to an organic phosphorus luminescent compound and a preparation method and application thereof.

Background

2002- & 2005 was the growth stage of organic light emitting diodes, and people have been in wide contact with products with organic light emitting diodes, including vehicle-mounted displays, PDAs, mobile phones, DVDs, digital cameras, microdisplays for helmets, and household electrical appliances. Organic light emitting diode products are formally introduced into the market, and mainly enter the display fields of traditional LCD, VFD and the like. In this period, passive driving, single-color or multi-color display, and panels of 10 inches or less have been mainly used, but active driving, full-color, and panels of 10 inches or more have also come into use. In 2005, with the increasing maturity of the organic light emitting diode industrialization technology, the organic light emitting diode began to strike the display market and expand its application field, and the advantages of the organic light emitting diode in each technology were fully explored and exerted. The industrialization of organic light emitting diodes has begun, and it is now the stage where OLED technology is going to mature and market demand is growing at a high rate.

Although there are many new findings on high-efficiency heavy metal phosphors on the market, they all have high power, short lifetime, and low luminous efficiency;

therefore, it is an urgent technical problem to provide an organic phosphorus light-emitting compound and an organic electroluminescent device having lower power, longer lifetime and higher luminous efficiency.

Disclosure of Invention

In view of the above, the present invention provides an organic phosphorus light-emitting compound having high light-emitting efficiency, low driving voltage, and long lifetime;

in order to achieve the purpose, the invention adopts the following technical scheme: the organic phosphorus luminescent compound has a structural general formula shown in chemical formula 1:

wherein R is_1a、R_1b、R_1c、R_1d、R_2a、R_2b、R_2c、R_2d、R_3a、R_3b、R_4a、R_4b、R_4c、R_5a、R_5b、R_5c、R_5dEach independently selected from: hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, and substituted or unsubstituted C6-C18 aryl.

Further, the halogen is selected from one of fluorine, chlorine, bromine or iodine; preferably fluorine;

further, in the substituted or unsubstituted C1-C8 alkyl, any one or more C atoms may be substituted by N, O, S, Si, Se or Ge; preferably, the alkyl group is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl;

further, the substituted or unsubstituted cycloalkyl group having C3 to C30 is preferably a cycloalkyl group having C3 to C15; the cycloalkyl is monocyclic alkyl, polycyclic alkyl or spiroalkyl; more preferably, the cycloalkyl group is selected from cyclopropyl, cyclopentyl, cyclohexyl or adamantyl; the cycloalkyl is optionally substituted, and the substituent is selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C8 alkyl;

further, in the substituted or unsubstituted aryl group having C6-C18, the aryl group includes a monocyclic group or a polycyclic group. Wherein the polycyclic group includes two or more rings having two carbon atoms in two adjoining common and at least one of the rings is an aromatic ring and the other ring is a cycloalkyl, cycloalkenyl, aryl or heteroaryl group; the aryl group is more preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group or a fluorenyl group; aryl is optionally substituted, the substituents being preferably selected from deuterium, methyl, ethyl, propyl, isopropyl, phenyl.

The above-mentioned "substitution" means that a hydrogen atom bonded to a carbon atom of a compound becomes an additional substituent, and the position of substitution is not limited as long as the position is a position at which the hydrogen atom is substituted, that is, a position at which the substituent can be substituted, and when two or more substituents are substituted, the two or more substituents may be the same as or different from each other.

Preferably, the organic phosphorus luminescent compound has a structural formula of any one of the following structural formulas:

the invention also provides a preparation method of the organic phosphorus luminescent compound, which comprises the following steps:

(1) under the protection of inert gas, mixing the compound A and iridium trichloride trihydrate, adding the mixture into a solvent I for heating reaction, performing suction filtration after the reaction is finished, and sequentially washing and drying to obtain a bridging ligand B;

(2) under the protection of inert gas, mixing the bridging ligand B and silver trifluoromethanesulfonate, adding the mixture into a solvent II for heating reaction, and performing column chromatography separation and rotary evaporation concentration after the reaction to obtain an intermediate C;

(3) under the protection of inert gas, mixing the intermediate C with the compound D, adding the mixture into a solvent III for heating reaction, and performing suction filtration, washing, drying, column chromatography, rotary evaporation and concentration after the reaction is finished to obtain an organophosphorus luminescent compound shown in a chemical formula 1;

the synthetic route of the organic phosphorus luminescent compound shown in chemical formula 1 is as follows:

in the compound C shown, "-OTf" means silver trifluoromethanesulfonate ion

Further, the inert gases in the steps (1) to (3) are all nitrogen or argon;

the molar ratio of the compound A to the iridium trichloride trihydrate in the step (1) is (2-3) to 1, and preferably 2.6: 1;

the heating reaction temperature is 130-140 ℃, and the reaction time is 20-30 h;

the solvent I is ethylene glycol ethyl ether and/or water; when the solvent I is a mixed solution of ethylene glycol ethyl ether and water, the volume ratio of the ethylene glycol ethyl ether to the water is 3: 1;

the ratio of the compound A to the solvent I is 64.4mmol: 350-400 mL;

the detergent is one or a mixture of water, absolute ethyl alcohol and petroleum ether; preferably, water, absolute ethyl alcohol and petroleum ether are adopted for washing in sequence;

the drying temperature is 70-80 ℃.

Further, the molar ratio of the bridging ligand B to the silver trifluoromethanesulfonate in the step (2) is 1: 2-3, preferably 1: 3;

the reaction temperature is 55-65 ℃, and the reaction time is 20-30 h;

the solvent II is dichloromethane and/or methanol; when the solvent II is a mixed solution of dichloromethane and methanol, the volume ratio of the dichloromethane to the methanol is 5: 2;

the ratio of the bridging ligand B to the solvent II is 6.4mmol: 105-140 mL.

The column chromatography separation adopts a short column for column chromatography.

Further, the inert gas in the step (3) is nitrogen or argon;

the molar ratio of the intermediate C to the compound D is 1 (2-3); preferably 1: 3.

The reaction temperature is 75-80 ℃, and the reaction time is 20-30 h;

the solvent III is ethanol;

the ratio of the intermediate C to the solvent III is 11.2mmol: 90-130 mL.

The washing is washing with ethanol; the drying temperature is 70-80 ℃;

The invention has the beneficial effects that: the preparation method provided by the invention is simple and feasible, the product purity is high, and the product purity can reach more than 99%; the organic phosphorus luminescent compound shown in chemical formula 1 prepared by the invention can reduce the driving voltage of an organic electroluminescent device to be below 4.0V, improve the luminous efficiency to be above 35cd/A, and prolong the service life T (95) to be above 670.

The invention also provides an application of the organic phosphorus luminescent compound in preparing organic electroluminescent devices.

An organic electroluminescent device comprising an anode, a cathode and an intermediate layer disposed between the anode and cathode; wherein the intermediate layer includes a light emitting layer including the organic phosphorus light emitting compound of chemical formula 1.

Further, the anode is indium tin oxide, zinc oxide or indium oxide, and the thickness of the anode is 10-500 nm;

the cathode is Al, Li, Na, K, Mg, Ca, Au, Ag or Pb, and the thickness of the cathode is 100-1000 nm.

Further, the organic phosphorus luminescent compound accounts for 0.5-10% of the mass of the luminescent layer;

the thickness of the light emitting layer is 10-500 nm.

Further, the intermediate layer further comprises a functional layer; the functional layer is one or more of a hole injection layer, a hole transport layer, a hole injection-hole transport functional layer, an Electron Blocking Layer (EBL), a hole blocking layer, an electron transport layer, an electron injection layer and an electron transport-electron injection functional layer.

Further, the hole injection layer is one of 2-TNATA (i.e., N1- (2-naphthyl) -N4, N4-bis (4- (2-naphthyl (phenyl) amino) phenyl) -N1-phenylphenyl-1, 4-diamine), phthalocyanine and porphyrin compounds, conductive polymers, N-type semiconducting organic complexes, metal organic complexes; the thickness of the hole injection layer is preferably 10-500 nm;

the hole transport layer is one of NPB (namely N, N '-diphenyl-N, N' - (1-naphthyl) -1, 1 '-biphenyl-4, 4' -diamine), TPD (namely N, N '-diphenyl-N, N' - (3-methylphenyl) -1, 1 '-biphenyl-4, 4' -diamine), PAPB (namely N, N '-bis (phenanthrene-9-yl) -N, N' -diphenyl benzidine), arylamine carbazole compound and indolocarbazole compound; the thickness of the hole transport layer is preferably 10-500 nm;

the thickness of the electron blocking layer is preferably 10-500 nm;

the hole blocking layer is one of BAlq, BCP and BPhen; the thickness of the hole blocking layer is preferably 10-500 nm;

the electron transport layer is one of Alq3, coumarin No. 6, triazole derivatives, azole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives and anthrone derivatives; the thickness of the electron transmission layer is preferably 10-500 nm;

the electron injection layer is LiF, CsF or Li₂O、Al₂O₃MgO; the thickness of the electron injection layer is preferably 0.1-10 nm.

The thickness of the electron transmission-electron injection functional layer is preferably 10-500 nm.

In the present invention, the light-emitting layer and various other functional layers may be formed by vapor deposition.

Compared with the prior art, the invention has the beneficial effects that: the organic electroluminescent device provided by the invention has high luminous efficiency, low driving voltage and longer service life. The organic electroluminescent device according to the present invention may be applied to an Organic Light Emitting Device (OLED), an Organic Solar Cell (OSC), electronic paper (e-paper), an Organic Photoreceptor (OPC), or an Organic Thin Film Transistor (OTFT) using the same principle.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

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Organic phosphorus luminescent compound and preparation method and application thereof

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