CN113121500A - Phosphorescent platinum complex serving as OLED (organic light emitting diode) doping material and application thereof - Google Patents

Phosphorescent platinum complex serving as OLED (organic light emitting diode) doping material and application thereof Download PDF

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CN113121500A
CN113121500A CN201911390035.XA CN201911390035A CN113121500A CN 113121500 A CN113121500 A CN 113121500A CN 201911390035 A CN201911390035 A CN 201911390035A CN 113121500 A CN113121500 A CN 113121500A
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platinum complex
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叶中华
张兆超
崔明
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Jiangsu Sunera Technology Co Ltd
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Abstract

The invention discloses a phosphorescent platinum complex serving as an OLED (organic light emitting diode) doping material and application thereof, belonging to the technical field of semiconductors. The structure of the phosphorescence platinum complex is shown as a general formula (1):
Figure DDA0002344705490000011
the invention also discloses application of the phosphorescent platinum complex serving as the OLED doping material. The organic electroluminescent material takes metal platinum as a structural core, is applied to an OLED device, is used as a doping material of a luminescent layer material, and can emit phosphorescence under the action of an electric field, so that the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improved; meanwhile, the service life of the device is obviously prolonged. The phosphorescent platinum complex has good application effect in OLED light-emitting devices and good industrialization prospect.

Description

Phosphorescent platinum complex serving as OLED (organic light emitting diode) doping material and application thereof
Technical Field
The invention relates to the technical field of semiconductor materials, in particular to a phosphorescent platinum complex serving as an OLED (organic light emitting diode) doping material and application thereof.
Background
The research on the improvement of the performance of the OLED light emitting device includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED device, not only the innovation of the structure and the manufacturing process of the OLED device but also the continuous research and innovation of the OLED photoelectric functional material are needed to create the functional material of the OLED with higher performance.
Organic electroluminescent materials fall into two broad categories: organic electroluminescent materials and organic electrophosphorescent materials. Wherein the organic electroluminescence is the result of radiative deactivation of singlet excitons. In the organic electroluminescent process, triplet excitons and singlet excitons are generated simultaneously, the ratio of the generation of the singlet excitons to the generation of the triplet excitons is usually 1:3, while according to the forbidden effect of quantum statistics, the triplet excitons are subject to important non-radiative decay, have little contribution to luminescence, and only the singlet excitons emit luminescence by radiation,
the fundamental reason that the luminous efficiency is difficult to improve for the OLED device is that the light emitting process is the light emission of singlet excitons, so that the maximum internal quantum efficiency of the light emitting device is only 25 percent, and the maximum external quantum efficiency of the light emitting device is about 5 percent at most.
How to utilize singlet state and triplet state to emit light at the same time to improve the luminous efficiency becomes an important research subject in the OLED field, the phosphorescent material is used for replacing fluorescent material to realize the basic method of phosphorescent emission, in order to improve the yield of phosphorescent quantum of triplet excited state, heavy metal atoms are usually introduced into the phosphorescent material to improve the spin-orbit coupling of excited state molecules, shorten the phosphorescent service life, change the transition from the latest excited triplet state of the original spin forbidden resistance to the singlet ground state into the allowable transition, and greatly improve the luminous efficiency of the material. The Forrest group dopes octaethylporphyrin platinum (PtOEP) in a small molecular host material 8-hydroxyquinoline aluminum to manufacture a red electrophosphorescent device, the external quantum efficiency reaches 4%, so the research on electrophosphorescence is greatly concerned, but the service life of the existing organic electrophosphorescent complex is not ideal and needs to be further improved.
Disclosure of Invention
One of the purposes of the invention is to provide a phosphorescent platinum complex used as an OLED doping material. When the phosphorescence platinum complex is used as the luminescent layer doping material of the OLED luminescent device, the current efficiency and the external quantum efficiency of the device are both greatly improved, and the service life of the device is obviously prolonged.
The technical scheme for solving the technical problems is as follows: a phosphorescent platinum complex used as an OLED doping material has a structure shown as a general formula (1):
Figure BDA0002344705470000011
in the general formula (1), Z independently represents a nitrogen atom, a carbon atom or C-H at each occurrence;
X0is represented by a single bond, sulfurAtom, oxygen atom, -N (R)6) -or-C (R)7R8) -one of the above;
i represents 0 or 1;
R1-R5each independently represents a hydrogen atom, a halogen, a cyano group, or C1-10The alkyl of the formula (2) or the structure of the formula (3), wherein R is1And R2At least one of the structures is represented by a general formula (2) or a general formula (3);
Figure BDA0002344705470000021
in the general formulae (2) and (3), Z1Each occurrence is independently represented as a nitrogen atom or C-R12；
X1And X2Each independently represents a single bond, a sulfur atom, an oxygen atom, -N (R)9) -or-C (R)10R11) -one of (A) and X1And X2Not simultaneously represent a single bond;
R6-R11each occurrence is independently represented as C1-10Alkyl, substituted or unsubstituted C6-30One of aryl, substituted or unsubstituted 5 to 30 membered heteroaryl;
R12represented by hydrogen atom, protium atom, deuterium atom, tritium atom, halogen, cyano group, C1-10Alkyl radical, C2-20Alkylene radical, C1-20Alkyl substituted silyl, substituted or unsubstituted C6-30One of aryl, substituted or unsubstituted 5 to 30 membered heteroaryl;
the general formula (2) and the general formula (3) are respectively and independently connected with the adjacent site marked with the letter in the general formula (1) in a ring-by-ring mode through two adjacent sites marked with the letter; the substituent of the substitutable group is optionally selected from deuterium atom, halogen atom, cyano, C1-10Alkyl of (C)6-30One or more of aryl or 5-to 30-membered heteroaryl;
the hetero atom in the heteroaryl is any one or more selected from N, O or S.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, R is1And R2And simultaneously represented by a structure represented by the general formula (2) or simultaneously represented by a structure represented by the general formula (3).
Further, at least one Z in the general formula (2) or the general formula (3)1Represented as a nitrogen atom.
Further, R is3-R5At least one of which is represented by a tert-butyl group.
Further, said C1-10The alkyl is one of methyl, ethyl, isopropyl and tert-butyl;
said C is6-30The aryl group is one of phenyl, naphthyl, biphenyl, terphenyl and anthryl;
the 5-to 30-membered heteroaryl is represented by one of pyridyl, carbazolyl, furyl, pyrimidinyl, pyrazinyl, pyridazinyl, thienyl, dibenzofuryl, 9-dimethylfluorenyl, N-phenylcarbazolyl, quinolyl, isoquinolyl, naphthyridinyl, oxazolyl, imidazolyl, benzoxazolyl and benzimidazolyl.
Further, the structure of the phosphorescent platinum complex is shown as any one of general formula (1-1) -general formula (1-4):
Figure BDA0002344705470000022
further, the structure of the phosphorescent platinum complex is shown as any one of general formula (1-5) -general formula (1-8):
Figure BDA0002344705470000031
further, the specific compound of the general formula (1) is represented by any one of the following specific structures:
Figure BDA0002344705470000032
Figure BDA0002344705470000041
Figure BDA0002344705470000051
Figure BDA0002344705470000061
Figure BDA0002344705470000071
Figure BDA0002344705470000081
Figure BDA0002344705470000091
Figure BDA0002344705470000101
Figure BDA0002344705470000111
Figure BDA0002344705470000121
the second objective of the present invention is to provide an organic electroluminescent device. The compound has good application effect in an OLED luminescent device, can effectively improve the luminescent efficiency and the service life of the OLED device, and has good application effect and industrialization prospect.
The technical scheme for solving the technical problems is as follows: an organic electroluminescent device comprises a cathode, an anode and an organic functional layer, wherein the organic functional layer contains the phosphorescent platinum complex serving as the OLED doping material.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the organic functional layer comprising the phosphorescent platinum complex as the OLED doping material is a light emitting layer.
It is a further object of the present invention to provide an illumination or display device. The organic electroluminescent device can be applied to display elements, so that the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improved; meanwhile, the service life of the device is obviously prolonged, and the OLED luminescent device has a good application effect and a good industrialization prospect.
The technical scheme for solving the technical problems is as follows: a lighting or display element comprising an organic electroluminescent device as described above.
The invention has the beneficial technical effects that:
when the phosphorescent platinum complex is used as a luminescent layer doping material of an OLED luminescent device, compared with the traditional doped phosphorescent material, the organic electroluminescent material has higher luminous efficiency, lower triplet state service life, narrower spectral half-peak width and good material stability. The metal platinum-containing organic electroluminescent material is applied to OLED devices as a luminescent layer doping material, the luminous efficiency of the devices is greatly improved, the service life of the devices is obviously prolonged, and the metal platinum-containing organic electroluminescent material has unexpected technical effects.
Drawings
FIG. 1 is a schematic structural diagram of an OLED device of the present invention;
in the figure: 1. a substrate layer, 2, an anode layer, 3, a hole injection layer, 4, a hole transport layer, 5, a light emitting layer, 6, an electron transport layer, 7, an electron injection layer, 8 and a cathode electrode layer.
Detailed Description
The technical solutions in the embodiments of the present invention are described below clearly and completely, and it is obvious that the described implementations
The embodiments are merely a few embodiments of the invention, rather than all embodiments.
The specific types of reactions involved in the preparation of the compounds of the invention are classified as follows:
reaction conditions 1:
in a 250mL three-neck flask, under the protection of nitrogen, 0.02mol of reactant A, 0.022mol of reactant B, 0.05mol of sodium tert-butoxide and 0.2mmol of Pd2(dba)3Adding 0.2mmol of tri-tert-butylphosphine into 150mL of toluene, stirring and mixing, heating to 110-120 ℃, and carrying out reflux reaction for 12-16 hours until the reaction is complete; naturally cooling to room temperature, filtering, decompressing and rotary steaming the filtrate until no fraction is produced, and passing through a neutral silica gel column to obtain the product.
Reaction conditions 2:
0.05mol of reactant C, 41.6g N-bromosuccinimide (NBS), 500mL of dichloromethane and 500mL of acetonitrile are sequentially added into a three-neck flask, the mixture is stirred for 24 hours at normal temperature, after the reaction is finished, a precipitated solid product is subjected to vacuum filtration, and the obtained solid product is washed by methanol to obtain a product.
Reaction conditions 3:
to a 200mL three-necked flask, 0.01mol of reactant D, 0.025mol of reactant E, 0.05mol of potassium carbonate, and 1.5X 10 were added under a nitrogen atmosphere-4mol Pd(PPh3)Cl2And 1.8X 10-4And (3) mol of triphenylphosphine, adding 180mL of mixed solution of toluene, ethanol and water in a volume ratio of 1:1:1, heating and refluxing for 24 hours, observing the reaction by using TLC (thin layer chromatography) until the reaction is complete, naturally cooling to room temperature, filtering, and rotatably evaporating the filtrate until no fraction is obtained. The resulting material was passed through a silica gel column (V)Methylene dichloride：VPetroleum etherMixed solvent of 1:5 as eluent) to obtain the product.
Reaction conditions 4:
a 250mL three-neck flask, under the protection of nitrogen, is added with 0.01mol of reactant F, 0.0005mol of palladium acetate and 0.02mol of PhCO3Bu-t, 100mL of dimethylDissolving ether, heating to 150 ℃ under microwave, and reacting for 0.5 hour to complete the reaction; extracting with ethyl acetate, separating liquid, drying the organic phase with anhydrous sodium sulfate, decompressing and rotary distilling until no fraction is produced, and passing the obtained crude product through a neutral silica gel column to obtain the product.
Reaction conditions 5:
1mmol of reactant G, 2.5mmol of sodium tert-butoxide, 1.12mg of palladium acetate and 38.05mg of cuprous iodide were weighed into a vial containing a stirrer and a perforated cap with a polytetrafluoroethylene pad attached was screwed on. 0.8mL of dioxane was added as a solvent using a syringe, and the vial was placed in a well of a heating plate and heated to 120 ℃ for 10 hours. The vial was then removed from the well of the heating plate, cooled to room temperature, and the reaction quenched with water. The product was extracted with dichloromethane and the solution was dried over anhydrous sodium sulfate. Spin-drying solvent, and performing column chromatography (mixed solvent as developing solvent at 30-60 deg.C and V)Petroleum ether:VEther (A)10:1) to yield the product.
Reaction conditions 6:
under the protection of nitrogen, 0.01mol of reactant H is weighed and concentrated by using concentrated H containing 0.05mol of phosphoric acid and having the volume ratio of 1 (2.0-4.0)3PO4The mixed solution of the water and the solvent is dissolved and reacts for 6 to 8 hours at room temperature, and the reaction is complete; adding NaOH aqueous solution to neutralize until the pH value is 7, adding dichloromethane to extract, layering, taking an organic phase to filter, decompressing and rotary-steaming the filtrate until no fraction is produced, and passing through a neutral silica gel column to obtain a product;
reaction conditions 7:
adding 0.02mol of reactant I into a 250mL three-necked bottle under the protection of nitrogen, dissolving with 50mL of acetic acid, and cooling to 0 ℃ by using an ice salt bath; weighing 0.025mol of liquid bromine, dissolving in 50mL of glacial acetic acid, slowly dropwise adding into an acetic acid solution of a reactant I, stirring at room temperature for 5h, after the reaction is finished, adding alkali liquor into the reaction solution for neutralization, extracting with dichloromethane, layering, filtering an organic phase, decompressing and rotary-steaming the filtrate until no fraction is obtained, and passing through a silica gel column to obtain a product.
Reaction conditions 8:
under the protection of nitrogen, 25mmol of a reactant J, 2.0g of [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, 300mL of 1M tert-butyl magnesium bromide and 300mL of 1, 4-dioxane are sequentially added into a 1L three-neck flask, the mixture is stirred at 90 ℃ for 12 hours, reaction liquid is cooled, water and dichloromethane are used for extraction and separation to obtain an organic layer, the organic layer is concentrated to obtain a solid, and the solid is recrystallized and then washed by methanol to obtain a product.
Reaction conditions 9:
in a 200mL three-necked flask, 0.01mol of reactant K and 0.015mol of PtCl are added2(DMSO)2And 0.02mol of sodium carbonate are added into 50mL of 1, 2-dimethoxyethane, the mixture is heated and refluxed for 24 hours at the temperature of 130 ℃, the reaction is completed, the mixture is naturally cooled to the room temperature, 70mL of water is added, dichloromethane is used for extraction, an organic phase is collected, and the product is obtained by silica gel column purification.
Reaction conditions 10:
weighing 0.01mol of reactant S under the nitrogen atmosphere, dissolving the reactant S in 45mL of tetrahydrofuran, cooling to-78 ℃, slowly dripping a cyclohexane solution containing 0.02mol of n-butyllithium, and keeping the temperature and stirring for 30 minutes after dripping is finished; slowly dripping tetrahydrofuran solution containing 0.035mol trimethyl borate, after dripping, slowly heating to room temperature, and reacting for 10 hours under the condition of heat preservation; after the reaction is finished, cooling to 0 ℃, slowly dripping distilled water, stirring for 1 hour after no gas is generated, and then heating to room temperature; the reaction mixture was extracted with 150mL of ethyl acetate, the extract was washed with 150mL of saturated brine three times, dried over anhydrous magnesium sulfate, the solution was distilled under reduced pressure, and the obtained solid was distilled off with 400mL of VToluene：VEthanolThe mixture at 3:1 was recrystallized to give the product.
The above reaction types involved in the preparation of the compound of the present invention are all used in one reaction, and when there are multiple reactions, the reactants are replaced correspondingly, and the reaction is repeated for multiple times.
The synthetic procedures for the preparation of examples 1-24 are now given, and the reaction conditions involved in the specific reactions of each step are referred to above.
Preparation example 1:
Figure BDA0002344705470000141
weighing 0.01mol of reactant S-1 in a nitrogen atmosphere, dissolving in 45mL of tetrahydrofuran, cooling to-78 ℃, slowly dripping a cyclohexane solution containing 0.02mol of n-butyllithium, and keeping the temperature and stirring for 30 minutes after dripping is finished; slowly dripping tetrahydrofuran solution containing 0.035mol trimethyl borate, after dripping, slowly heating to room temperature, and reacting for 10 hours under the condition of heat preservation; after the reaction is finished, cooling to 0 ℃, slowly dripping distilled water, stirring for 1 hour after no gas is generated, and then heating to room temperature; the reaction mixture was extracted with 150mL of ethyl acetate, the extract was washed with 150mL of saturated brine three times, dried over anhydrous magnesium sulfate, the solution was distilled under reduced pressure, and the obtained solid was distilled off with 400mL of VToluene：VEthanolRecrystallization was performed on the mixed solution at a ratio of 3:1 to obtain E-1.
In a 250mL three-necked flask, under the protection of nitrogen, 0.02mol of reactant A-1, 0.022mol of reactant B-1, 0.05mol of sodium tert-butoxide and 0.2mmol of Pd2(dba)30.2mmol of tri-tert-butylphosphine is added into 150mL of toluene and stirred for mixing, the mixture is heated to 110-120 ℃, and the reflux reaction is carried out for 12-16 hours, thus the reaction is complete; naturally cooling to room temperature, filtering, performing reduced pressure rotary distillation on the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain C-1.
0.05mol of reactant C-1, 41.6g N-bromosuccinimide (NBS), 500mL of dichloromethane and 500mL of acetonitrile are sequentially added into a three-neck flask, the mixture is stirred for 24 hours at normal temperature, after the reaction is finished, a precipitated solid product is subjected to vacuum filtration, and the obtained solid product is washed by methanol to obtain D-1.
To a 200mL three-necked flask, 0.01mol of the reactant D-1, 0.025mol of the reactant E-1, 0.05mol of potassium carbonate, and 1.5X 10 mol of the mixture were added under a nitrogen atmosphere-4mol Pd(PPh3)Cl2And 1.8X 10-4And (3) mol of triphenylphosphine, adding 180mL of mixed solution of toluene, ethanol and water in a volume ratio of 1:1:1, heating and refluxing for 24 hours, observing the reaction by using TLC (thin layer chromatography) until the reaction is complete, naturally cooling to room temperature, filtering, and rotatably evaporating the filtrate until no fraction is obtained. The resulting material was passed through a silica gel column (V)Methylene dichloride：VPetroleum etherMixed solvent of 1:5 as eluent) to obtain K-1.
In a 200mL three-necked flask, 0.01mol of the reactant K-1 and 0.015mol of PtCl are added2(DMSO)2And 0.02mol of sodium carbonate were added to 50mL of 1, 2-dimethoxyethane, and the mixture was heated under reflux at 130 ℃ for 24 hours to complete the reaction, cooled to room temperature naturally, added with 70mL of water, extracted with dichloromethane, and the organic phase was collected and purified by silica gel column to obtain Compound 1.
Preparation example 2:
Figure BDA0002344705470000151
weighing 0.01mol of reactant S-2 under the nitrogen atmosphere, dissolving in 45mL of tetrahydrofuran, cooling to-78 ℃, slowly dripping a cyclohexane solution containing 0.02mol of n-butyllithium, and keeping the temperature and stirring for 30 minutes after dripping is finished; slowly dripping tetrahydrofuran solution containing 0.035mol trimethyl borate, after dripping, slowly heating to room temperature, and reacting for 10 hours under the condition of heat preservation; after the reaction is finished, cooling to 0 ℃, slowly dripping distilled water, stirring for 1 hour after no gas is generated, and then heating to room temperature; the reaction mixture was extracted with 150mL of ethyl acetate, the extract was washed with 150mL of saturated brine three times, dried over anhydrous magnesium sulfate, the solution was distilled under reduced pressure, and the obtained solid was distilled off with 400mL of VToluene：VEthanolRecrystallization was performed on the mixed solution at a ratio of 3:1 to obtain E-2.
In a 250mL three-necked flask, under the protection of nitrogen, 0.02mol of reactant A-1, 0.022mol of reactant B-2, 0.05mol of sodium tert-butoxide and 0.2mmol of Pd2(dba)30.2mmol of tri-tert-butylphosphine is added into 150mL of toluene and stirred for mixing, the mixture is heated to 110-120 ℃, and the reflux reaction is carried out for 12-16 hours, thus the reaction is complete; naturally cooling to room temperature, filtering, decompressing and rotary steaming the filtrate until no fraction is produced, and passing through a neutral silica gel column to obtain the product.
0.05mol of reactant C-2, 41.6g N-bromosuccinimide (NBS), 500mL of dichloromethane and 500mL of acetonitrile are sequentially added into a three-neck flask, the mixture is stirred for 24 hours at normal temperature, after the reaction is finished, a precipitated solid product is subjected to vacuum filtration, and the obtained solid product is washed by methanol to obtain D-2.
To a 200mL three-necked flask, 0.01mol of reactant D-2, 0.025mol of reactant E-2, 0.05mol of potassium carbonate, and 1.5X 10 under a nitrogen atmosphere were added-4mol Pd(PPh3)Cl2And 1.8X 10-4And (3) mol of triphenylphosphine, adding 180mL of mixed solution of toluene, ethanol and water in a volume ratio of 1:1:1, heating and refluxing for 24 hours, observing the reaction by using TLC (thin layer chromatography) until the reaction is complete, naturally cooling to room temperature, filtering, and rotatably evaporating the filtrate until no fraction is obtained. The resulting material was passed through a silica gel column (V)Methylene dichloride：VPetroleum etherMixed solvent of 1:5 as eluent) to obtain K-2.
In a 200mL three-necked flask, 0.01mol of the reactant K-2 and 0.015mol of PtCl are added2(DMSO)2And 0.02mol of sodium carbonate were added to 50mL of 1, 2-dimethoxyethane, and the mixture was heated under reflux at 130 ℃ for 24 hours to complete the reaction, cooled to room temperature naturally, added with 70mL of water, extracted with dichloromethane, and the organic phase was collected and purified by silica gel column to obtain compound 62.
Preparation example 3:
Figure BDA0002344705470000161
in a 250mL three-necked flask, under the protection of nitrogen, 0.02mol of reactant A-3, 0.022mol of reactant B-3, 0.05mol of sodium tert-butoxide and 0.2mmol of Pd2(dba)30.2mmol of tri-tert-butylphosphine is added into 150mL of toluene and stirred for mixing, the mixture is heated to 110-120 ℃, and the reflux reaction is carried out for 12-16 hours, thus the reaction is complete; naturally cooling to room temperature, filtering, decompressing and rotary steaming the filtrate until no fraction is produced, and passing through a neutral silica gel column to obtain F-4.
A 250mL three-neck flask, under the protection of nitrogen, adding 0.01mol of reactant F-4, 0.0005mol of palladium acetate and 0.02mol of PhCO3Bu-t, adding 100mL of dimethyl ether for dissolving, heating to 150 ℃ under microwave, and reacting for 0.5 hour until the reaction is complete; extracting with ethyl acetate, separating, drying the organic phase with anhydrous sodium sulfate, vacuum rotary distilling to remove distillate, and passing the obtained crude product through neutral silica gel column to obtain A-5.
At 250mLIn a three-neck flask, under the protection of nitrogen, 0.02mol of reactant A-5, 0.022mol of reactant B-1, 0.05mol of sodium tert-butoxide and 0.2mmol of Pd2(dba)30.2mmol of tri-tert-butylphosphine is added into 150mL of toluene and stirred for mixing, the mixture is heated to 110-120 ℃, and the reflux reaction is carried out for 12-16 hours, thus the reaction is complete; naturally cooling to room temperature, filtering, performing reduced pressure rotary distillation on the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain C-5.
0.05mol of reactant C-5, 41.6g N-bromosuccinimide (NBS), 500mL of dichloromethane and 500mL of acetonitrile are sequentially added into a three-neck flask, the mixture is stirred for 24 hours at normal temperature, after the reaction is finished, a precipitated solid product is subjected to vacuum filtration, and the obtained solid product is washed by methanol to obtain D-5.
To a 200mL three-necked flask, 0.01mol of the reactant D-5, 0.025mol of the reactant E-1, 0.05mol of potassium carbonate, and 1.5X 10 mol of the mixture were added under a nitrogen atmosphere-4mol Pd(PPh3)Cl2And 1.8X 10-4And (3) mol of triphenylphosphine, adding 180mL of mixed solution of toluene, ethanol and water in a volume ratio of 1:1:1, heating and refluxing for 24 hours, observing the reaction by using TLC (thin layer chromatography) until the reaction is complete, naturally cooling to room temperature, filtering, and rotatably evaporating the filtrate until no fraction is obtained. The resulting material was passed through a silica gel column (V)Methylene dichloride：VPetroleum etherMixed solvent of 1:5 as eluent) to obtain K-5.
In a 200mL three-necked flask, 0.01mol of reactant K and 0.015mol of PtCl are added2(DMSO)2And 0.02mol of sodium carbonate into 50mL of 1, 2-dimethoxyethane, heating and refluxing for 24 hours at 130 ℃, completing the reaction, naturally cooling to room temperature, adding 70mL of water, extracting with dichloromethane, collecting an organic phase, and purifying by a silica gel column to obtain a compound 11.
Preparation example 4:
Figure BDA0002344705470000162
in a 250mL three-necked flask, under the protection of nitrogen, 0.02mol of reactant A-4, 0.022mol of reactant B-4, 0.05mol of sodium tert-butoxide and 0.2mmol of Pd2(dba)30.2mmol of tri-tert-butylphosphine is added into 150mL of toluene and stirred for mixing, the mixture is heated to 110-120 ℃, and the reflux reaction is carried out for 12-16 hours, thus the reaction is complete; naturally cooling to room temperature, filtering, decompressing and rotary steaming the filtrate until no fraction is produced, and passing through a neutral silica gel column to obtain C-4.
0.05mol of reactant C-4, 41.6g of N-bromosuccinimide (NBS), 500mL of dichloromethane and 500mL of acetonitrile are sequentially added into a three-neck flask, the mixture is stirred for 24 hours at normal temperature, after the reaction is finished, a precipitated solid product is subjected to vacuum filtration, and the obtained solid product is washed by methanol to obtain D-4.
To a 200mL three-necked flask, 0.01mol of the reactant D-4, 0.025mol of the reactant E-1, 0.05mol of potassium carbonate, and 1.5X 10 mol of the mixture were added under a nitrogen atmosphere-4mol Pd(PPh3)Cl2And 1.8X 10-4And (3) mol of triphenylphosphine, adding 180mL of mixed solution of toluene, ethanol and water in a volume ratio of 1:1:1, heating and refluxing for 24 hours, observing the reaction by using TLC (thin layer chromatography) until the reaction is complete, naturally cooling to room temperature, filtering, and rotatably evaporating the filtrate until no fraction is obtained. The resulting material was passed through a silica gel column (V)Methylene dichloride：VPetroleum etherMixed solvent of 1:5 as eluent) to obtain K-4.
In a 200mL three-necked flask, 0.01mol of reactant K-4 and 0.015mol of PtCl are added2(DMSO)2And 0.02mol of sodium carbonate were added to 50mL of 1, 2-dimethoxyethane, and the mixture was heated under reflux at 130 ℃ for 24 hours to complete the reaction, cooled to room temperature naturally, added with 70mL of water, extracted with dichloromethane, and the organic phase was collected and purified by silica gel column to obtain compound 61.
Preparation example 5:
Figure BDA0002344705470000171
weighing 0.01mol of reactant S-5 under the nitrogen atmosphere, dissolving in 45mL of tetrahydrofuran, cooling to-78 ℃, slowly dripping a cyclohexane solution containing 0.02mol of n-butyllithium, and keeping the temperature and stirring for 30 minutes after dripping is finished; slowly dripping tetrahydrofuran solution containing 0.035mol trimethyl borate, slowly heating to room temperature after dripping, and keeping the temperatureReacting for 10 hours; after the reaction is finished, cooling to 0 ℃, slowly dripping distilled water, stirring for 1 hour after no gas is generated, and then heating to room temperature; the reaction mixture was extracted with 150mL of ethyl acetate, the extract was washed with 150mL of saturated brine three times, dried over anhydrous magnesium sulfate, the solution was distilled under reduced pressure, and the obtained solid was distilled off with 400mL of VToluene：VEthanolRecrystallization was performed on the mixed solution at a ratio of 3:1 to obtain E-5.
To a 200mL three-necked flask, 0.01mol of reactant D-1, 0.025mol of reactant E-5, 0.05mol of potassium carbonate, and 1.5X 10 under a nitrogen atmosphere were added-4mol Pd(PPh3)Cl2And 1.8X 10-4And (3) mol of triphenylphosphine, adding 180mL of mixed solution of toluene, ethanol and water in a volume ratio of 1:1:1, heating and refluxing for 24 hours, observing the reaction by using TLC (thin layer chromatography) until the reaction is complete, naturally cooling to room temperature, filtering, and rotatably evaporating the filtrate until no fraction is obtained. The resulting material was passed through a silica gel column (V)Methylene dichloride：VPetroleum etherMixed solvent of 1:5 as eluent) to obtain K-5.
In a 200mL three-necked flask, 0.01mol of reactant K-5 and 0.015mol of PtCl are added2(DMSO)2And 0.02mol of sodium carbonate were added to 50mL of 1, 2-dimethoxyethane, and the mixture was heated under reflux at 130 ℃ for 24 hours to complete the reaction, cooled to room temperature naturally, added with 70mL of water, extracted with dichloromethane, and the organic phase was collected and purified by silica gel column to obtain compound 94.
Preparation example 6:
Figure BDA0002344705470000172
preparation example 7:
Figure BDA0002344705470000181
preparation example 8:
Figure BDA0002344705470000182
preparation example 9:
Figure BDA0002344705470000183
preparation example 10:
Figure BDA0002344705470000184
preparation example 11:
Figure BDA0002344705470000191
preparation example 12:
Figure BDA0002344705470000192
preparation example 13:
Figure BDA0002344705470000193
preparation example 14:
Figure BDA0002344705470000194
Figure BDA0002344705470000201
preparation example 15:
Figure BDA0002344705470000202
preparation example 16:
Figure BDA0002344705470000203
preparation example 17:
Figure BDA0002344705470000204
preparation example 18:
Figure BDA0002344705470000205
preparation example 19:
Figure BDA0002344705470000206
Figure BDA0002344705470000211
preparation example 20:
Figure BDA0002344705470000212
preparation example 21:
Figure BDA0002344705470000213
preparation example 22:
Figure BDA0002344705470000214
preparation example 23:
Figure BDA0002344705470000215
preparation example 24:
Figure BDA0002344705470000216
characterization of the compounds prepared in the various preparation examples:
TABLE 1
Figure BDA0002344705470000221
Figure BDA0002344705470000231
Figure BDA0002344705470000241
The organic compound of the present invention is used in a light-emitting device as a doping material for a light-emitting layer. The compounds of the present invention were tested for various aspects of HOMO/LUMO energy level, glass transition temperature (Tg), decomposition temperature (Td), cyclic voltammetric stability, etc., as shown in Table 2 below:
TABLE 2
Figure BDA0002344705470000242
Note: the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the thermogravimetric temperature Td is a temperature at which 1% of the weight loss is observed in a nitrogen atmosphere, and is measured on a TGA-50H thermogravimetric analyzer of Shimadzu corporation, Japan, and the nitrogen flow rate is 20 mL/min; the highest occupied molecular orbital HOMO energy level was tested by the ionization energy test system (AC-3) in an air environment, and the test values were absolute values. The LUMO energy level is the absolute value of the energy at the longest wavelength (Eg) of the ultraviolet absorption spectrum of a material minus the HOMO energy level. The cyclic voltammetry test adopts CS350H electrochemical workstation of Costet instruments Co., Ltd, tetrabutyl hexafluorophosphate is used as electrolyte and is dissolved into dichloromethane solution; the scanning speed is 100 mv/s.
As can be seen from the data in the table, compared with the conventional red light doping material TLEC-025, the compound of the invention has higher glass transition temperature and decomposition temperature; and has good reversible redox characteristics. The luminescent layer is used as a doping material of the luminescent layer, and can inhibit the crystallization and the film phase separation of the material; meanwhile, the decomposition of the material under high brightness can be inhibited, and the service life of the device is prolonged. In addition, the compound has a lower HOMO energy level, and is doped in a host material as a doping material, so that generation of carrier traps is inhibited, energy transfer efficiency of a host and an object is improved, and luminous efficiency of a device is improved.
To further illustrate the excellent properties of the materials of the present invention, a comparison was made of the fluorescence quantum efficiency (PLYQ) of the materials doped in the host material Bebq2 at a doping concentration of 6 wt% of the total mass, full width at half maximum (FWHM) of the spectrum, the lowest triplet state (T1) lifetime and thermal stability.
The detailed results are shown in table 3 below:
TABLE 3
Figure BDA0002344705470000251
Note: the fluorescence quantum efficiency is that the material is co-evaporated on a high-transmittance quartz glass sheet through double sources, the film thickness is 60nm, and a Fluorolog-3 series fluorescence spectrometer (integrating sphere) of Horiba is adopted for testing; the full width at half maximum (FWHM) of the spectrum is that the material is co-evaporated on a high-transmittance quartz glass sheet through double sources, the film thickness is 60nm, and a Fluorolog-3 series fluorescence spectrometer of Horiba is adopted for testing; the triplet state lifetime τ was tested using a Fluorolog-3 series fluorescence spectrometer from Horiba; the thermal stability is that the material is in a vacuum state (10)-4pa) to a temperature at which the material decomposes to 1%.
As can be seen from Table 3, the compound of the invention has higher fluorescence quantum efficiency as a doping material, and the fluorescence quantum efficiency of part of the materials is close to more than 90%, which shows that the compound of the invention has higher triplet state radiation rate and lower triplet state non-radiation rate; meanwhile, the spectrum FWHM of the material is narrow, so that the color purity of the device can be effectively improved, and the luminous efficiency of the device is improved; the triplet state life of the material is between 1us and 3.5us, the triplet state-triplet state quenching effect can be effectively inhibited, and the luminous efficiency and the service life of a device are improved. And finally, the decomposition temperature of the material is higher, the evaporation decomposition of the material can be inhibited, and the service life of the device is effectively prolonged. Spin orbit coupling coefficient (SOC), radiation rate, non-radiation rate of the triplet-ground state (T1-S0) of the material were calculated as shown in table 4 below:
TABLE 4
Figure BDA0002344705470000261
From the above table, it can be seen that the compound of the present application has a large SOC coefficient, and the triplet state is easily transited to the ground state by the spin-orbit coupling effect, and emits phosphorescence. Meanwhile, the luminescent material has higher radiation rate and lower non-radiation rate, thereby ensuring that the luminescent material can improve the luminous efficiency when being used as a luminescent layer doping material.
The OLED device is manufactured, the driving voltage, the efficiency and the service life of the OLED device are tested, and the material is comprehensively evaluated.
Preparation of the organic electroluminescent device of the present invention
The effect of the synthesized compound of the present invention as a doping material for a light emitting layer in a device is explained in detail by device examples 1 to 24 and device comparative example 1 below. Device examples 2-24 and device comparative example 1 compared with device example 1, the manufacturing process of the device is completely the same, and the same substrate material and electrode material are adopted, and the film thickness of the electrode material is kept consistent. Except that the doping material of the light emitting layer was changed. The structural composition of the resulting device of each example is shown in table 5. The test results of the resulting devices are shown in table 6.
Device example 1
Cleaning the ITO anode layer 2 on the transparent glass substrate layer 1, respectivelyUltrasonically cleaning deionized water, acetone and ethanol for 30 minutes respectively, and then treating in a plasma cleaner for 2 minutes; drying an ITO glass substrate, spin-coating PEDOT (PSS) with the thickness of 30nm by a wet method, taking the layer as a hole injection layer 3, drying, placing in a vacuum cavity, and keeping the vacuum degree to be less than 1 multiplied by 10- 6Torr, depositing α -NPD with a film thickness of 40nm on the hole injection layer 3 as a hole transport layer 4; further, a 35nm light emitting layer 5 is evaporated, wherein the light emitting layer comprises a host material Bebq2And an object doping material compound 1 of the present invention, the mass percentage of the doping material is 6%, the selection of the specific material is shown in table 5, and the rate control is performed by a film thickness meter according to the mass percentage of the host material and the doping dye; further evaporating a TPBI layer of organic material with the thickness of 35nm on the light-emitting layer 5 to form an electron transport layer 6; vacuum evaporating LiF with the thickness of 1nm on the electron transport layer 6, wherein the layer is an electron injection layer 7; on top of the electron injection layer 7, a cathode Al (100nm) is vacuum evaporated, which is a cathode electrode layer 8. Example 1 relates to the prior material structure as shown below:
Figure BDA0002344705470000271
examples 2 to 24 and comparative example 1 were fabricated in the same manner as example 1 except that the doping material of the light emitting layer was changed. The device structures of examples 1-24 and comparative example 1 are shown in table 5 below:
TABLE 5
Figure BDA0002344705470000272
Figure BDA0002344705470000281
After the OLED light emitting device was completed as described above, the anode and cathode were connected by a known driving circuit, and the driving voltage, current efficiency, and lifetime of the device were measured.
TABLE 6
Figure BDA0002344705470000282
The external quantum efficiency is a test value of the device at a luminance of 1000cd/m2, tested using an IVL (Current-Voltage-luminance) test system (Frashda scientific instruments, Suzhou); LT80 refers to the time taken for the luminance of the device to decay to 80% at a luminance of 1000cd/m 2; the life test system is an EAS-62C type OLED device life tester of Japan System research company.
From the results of table 6, it can be seen that the compound of the present invention can be applied to the fabrication of an OLED light emitting device, and compared to comparative example 1, the driving voltage is effectively reduced at the same current density; meanwhile, the external quantum efficiency and the service life of the device are greatly improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A phosphorescent platinum complex used as an OLED doping material is characterized in that the structure of the phosphorescent platinum complex is shown as a general formula (1):
Figure FDA0002344705460000011
in the general formula (1), Z independently represents a nitrogen atom, a carbon atom or C-H at each occurrence;
X0is represented by a single bond, a sulfur atom, an oxygen atom, -N (R)6) -or-C (R)7R8) -one of the above;
i represents 0 or 1;
R1-R5each independently represents a hydrogen atom, a halogen, a cyano group, or C1-10Alkyl group of (2), a junction represented by the general formula (2) or the general formula (3)One of the structures, the R1And R2At least one of the structures is represented by a general formula (2) or a general formula (3);
Figure FDA0002344705460000012
in the general formulae (2) and (3), Z1Each occurrence is independently represented as a nitrogen atom or C-R12；
X1And X2Each independently represents a single bond, a sulfur atom, an oxygen atom, -N (R)9) -or-C (R)10R11) -one of (A) and X1And X2Not simultaneously represent a single bond;
R6-R11each occurrence is independently represented as C1-10Alkyl, substituted or unsubstituted C6-30One of aryl, substituted or unsubstituted 5 to 30 membered heteroaryl;
R12represented by hydrogen atom, protium atom, deuterium atom, tritium atom, halogen, cyano group, C1-10Alkyl radical, C2-20Alkylene radical, C1-20Alkyl substituted silyl, substituted or unsubstituted C6-30One of aryl, substituted or unsubstituted 5 to 30 membered heteroaryl;
the general formula (2) and the general formula (3) are respectively and independently connected with the adjacent site marked with the letter in the general formula (1) in a ring-by-ring mode through two adjacent sites marked with the letter;
the substituent of the substitutable group is optionally selected from deuterium atom, halogen atom, cyano, C1-10Alkyl of (C)6-30One or more of aryl or 5-to 30-membered heteroaryl;
the hetero atom in the heteroaryl is any one or more selected from N, O or S.
2. The phosphorescent platinum complex as an OLED doping material according to claim 1, wherein R is1And R2And simultaneously represented by a structure represented by the general formula (2) or simultaneously represented by a structure represented by the general formula (3).
3. The phosphorescent platinum complex as an OLED doping material according to claim 1, wherein at least one Z in the general formula (2) or the general formula (3)1Represented as a nitrogen atom.
4. The phosphorescent platinum complex as an OLED doping material according to claim 1, wherein R is3-R5At least one of which is represented by a tert-butyl group.
5. The phosphorescent platinum complex as an OLED doping material according to claim 1,
said C is1-10The alkyl is one of methyl, ethyl, isopropyl and tert-butyl;
said C is6-30The aryl group is one of phenyl, naphthyl, biphenyl, terphenyl and anthryl;
the 5-to 30-membered heteroaryl is represented by one of pyridyl, carbazolyl, furyl, pyrimidinyl, pyrazinyl, pyridazinyl, thienyl, dibenzofuryl, 9-dimethylfluorenyl, N-phenylcarbazolyl, quinolyl, isoquinolyl, naphthyridinyl, oxazolyl, imidazolyl, benzoxazolyl and benzimidazolyl.
6. The phosphorescent platinum complex as an OLED doping material according to claim 1, wherein the structure of the phosphorescent platinum complex is as shown in any one of general formula (1-1) -general formula (1-4):
Figure FDA0002344705460000021
7. the phosphorescent platinum complex as an OLED doping material according to claim 1, wherein the structure of the phosphorescent platinum complex is as shown in any one of general formula (1-5) -general formula (1-8):
Figure FDA0002344705460000022
Figure FDA0002344705460000031
8. the phosphorescent platinum complex as an OLED doping material according to claim 1, wherein the specific compound of the general formula (1) is represented by any one of the following specific structures:
Figure FDA0002344705460000032
Figure FDA0002344705460000041
Figure FDA0002344705460000051
Figure FDA0002344705460000061
Figure FDA0002344705460000071
Figure FDA0002344705460000081
Figure FDA0002344705460000091
Figure FDA0002344705460000101
Figure FDA0002344705460000111
Figure FDA0002344705460000121
9. an organic electroluminescent device comprising a cathode, an anode and an organic functional layer, characterized in that the organic functional layer comprises the phosphorescent platinum complex as a dopant material for OLEDs as claimed in any of claims 1 to 8.
10. The organic electroluminescent device according to claim 9, wherein the light-emitting layer comprises the phosphorescent platinum complex as a dopant material for OLEDs according to any one of claims 1 to 8.
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CN113816966A (en) * 2021-10-25 2021-12-21 温州大学 Guest material of phosphorescent material, phosphorescent material and method for regulating luminescent property of phosphorescent material

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