Metal complex acceptor material, its exciplex and application

Abstract

The present application relates to metal complex acceptor material, its excited complex and application. A kind of metal complex acceptor material, it is the compound with the structure of formula (I), combined with organic donor material by the metal complex acceptor material to form excited complex luminescent material application in organic light emitting diode, with lower driving voltage and higher luminous efficiency, and can improve the service life of device, has potential application in the field of organic electroluminescence device.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of light-emitting materials, in particular to a metal complex acceptor material, a triplet exciton complex light-emitting material containing the metal complex acceptor material and application thereof in an organic light-emitting diode. BACKGROUND

[0002] Organic optoelectronic devices include, but are not limited to, organic light-emitting diodes (OLEDs), organic thin-film transistors (OTFTs), organic photovoltaic devices (OPVs), light-emitting electrochemical cells (LCEs) and chemical sensors.

[0003] In recent years, OLEDs have attracted extensive attention from both academia and industry as a promising lighting and display technology. OLEDs have the characteristics of self-illumination, wide viewing angle, short response time and flexible device, and have become a strong competitor for the next generation of display and lighting technology. However, OLEDs still have problems such as low efficiency and short lifetime, which need to be further studied. High efficiency and long lifetime of OLED devices usually require optimization of device structure and functional layer materials. Common functional layer materials include hole injection materials, hole transport materials, electron injection materials, electron transport materials, electron blocking materials, host materials and light-emitting materials, etc. In order to prepare OLEDs with better light-emitting efficiency and longer service life, academia and industry have been committed to developing new light-emitting materials.

[0004] The singlet-triplet energy gap (ΔE ST ) of the triplet exciton complex light-emitting material is small (<0.2 eV), and the triplet exciton can be converted into a singlet exciton to emit delayed fluorescence (TADF) through reverse intersystem crossing (RISC), and the internal quantum efficiency of the device can reach 100%. In addition, the triplet exciton complex can also reduce the driving voltage of the device, which has attracted widespread attention from the scientific community and industry. The triplet exciton complex systems reported in the literature are mainly based on pure organic electron donors and acceptor materials. The photophysical and electrochemical properties of common hole transport, electron transport and bipolar materials have been reported in detail, and the combination of these materials can achieve triplet exciton complex light-emitting, and the external quantum efficiency (EQE) of the device is mostly between 5-20%. The delayed fluorescence lifetime (τ DF ) of these pure organic systems is generally long, which can easily lead to the annihilation of light-emitting excitons, and has an adverse effect on the efficiency and stability of the device. In theory, using transition metal complexes (such as iridium, platinum, gold, palladium, copper, etc.) to construct triplet exciton complex systems can utilize the heavy atom effect of the metal and the interaction between the metal center and the ligand to obtain high-efficiency light-emitting materials. However, compared with the above-mentioned pure organic donor-acceptor combination system, the current TADF-type triplet exciton complex system using metal complexes has not received enough attention from the academic community, and there are few related reports. SUMMARY

[0005] In view of the above problems existing in the prior art, the present application provides a metal complex acceptor material which can form an exciplex luminescent material with an organic donor material, the exciplex luminescent material is applied in an organic light-emitting diode, has a lower driving voltage and a higher luminescent efficiency, and can improve the service life of the device.

[0006] The present application also provides an organic light-emitting diode based on the exciplex luminescent material.

[0007] The metal complex acceptor material has a compound with the structure of formula (I):

[0008]

[0009] wherein:

[0010] R 1 to R 6 are substituents, each independently selected from deuterium, halogen, aldehyde group, cyano group, substituted or unsubstituted alkylsulfonyl group with 1-6 carbon atoms, substituted or unsubstituted arylsulfonyl group with 6-30 carbon atoms, substituted or unsubstituted alkyl group with 1-6 carbon atoms, substituted or unsubstituted cycloalkyl group with 3-20 carbon atoms, substituted or unsubstituted alkoxy group with 1-20 carbon atoms, substituted or unsubstituted aryl group with 6-30 carbon atoms, substituted or unsubstituted heteroaryl group with 3-30 carbon atoms, or connected or fused into a ring between any two adjacent substituents;

[0011] the heteroatom in the heteroaryl group is N, S or O, and the substitution is substituted by D, F, C1-C4 alkyl;

[0012] M is selected from gold, silver, palladium or copper; X1, X2 are each independently C or N.

[0013] a1 to a4 are integers from 0 to 5, and when a1 is 2 or more, two R 1 groups are the same or different from each other, when a2 is 2 or more, two R 2 groups are the same or different from each other, when a3 is 2 or more, two R 3 groups are the same or different from each other, when a4 is 2 or more, two R 4 groups are the same or different from each other;

[0014] a5 and a6 are integers from 0 to 4, and when a5 is 2 or more, two R 5 groups are the same or different from each other, when a6 is 2 or more, two R 6 groups are the same or different from each other;

[0015] a1to a6are zero, R 1 to R 6 The substituents are absent, i.e. there are no substituents on the respective aromatic or heteroaromatic ring.

[0016] Preferably: R 1 to R 6 each independently selected from the group consisting of: deuterium, halogen, cyano, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms.

[0017] Further preferably: R 1 to R 2 each independently selected from the group consisting of deuterium, halogen, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, a3to a6are zero.

[0018] Further preferably: X1, X2are both N.

[0019] Further preferably: M is gold.

[0020] A metal complex acceptor material consisting of a mass ratio of 5% to 95% of a metal complex acceptor material and 95% to 5% of an organic donor material, said organic donor material molecule having one of the following structures:

[0021]

[0022] Preferably: consisting of a mass ratio of 5% to 20% of the above gold complex acceptor material: 95% to 80% of an organic donor material molecule. Further preferably: consisting of a mass ratio of 20% gold complex acceptor material and 80% of an organic donor material.

[0023] The following list examples of metal complex acceptor material molecules according to the present application, but is not limited to the structures listed:

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035] The present invention also provides an application of the excitocomplex constructed based on the above-mentioned donor and acceptor combination in organic optoelectronic devices, wherein the optoelectronic devices include, but are not limited to, organic light-emitting diodes (OLEDs), organic thin-film transistors (OTFTs), organic photovoltaic devices (OPVs), light-emitting electrochemical cells (LCEs), and chemical sensors, preferably OLEDs.

[0036] Organic light-emitting diodes (OLEDs) include a cathode, an anode, and an organic layer, wherein the organic layer is one or more of a hole injection layer, a hole transport layer, an emissive layer, a hole blocking layer, an electron injection layer, and an electron transport layer, and these organic layers need not be present in every layer; at least one of the hole injection layer, hole transport layer, hole blocking layer, electron injection layer, emissive layer, and electron transport layer contains the excitocomplex.

[0037] The excitocomplex serves as the luminescent material in the luminescent layer.

[0038] The total thickness of the organic layer of the device of the present invention is 1-1000 nm, preferably 1-500 nm, and more preferably 5-300 nm.

[0039] The organic layer can be formed into a thin film by evaporation or solution method.

[0040] The series of luminescent materials based on excitocomplexes of metal complex acceptors and organic donors disclosed in this invention have shown high luminescence quantum yields and have the potential to be applied to commercial organic light-emitting diode devices.

[0041] Using the excimer complex of the present invention as the luminescent material of organic electroluminescent optoelectronic devices has the advantages of low device start-up voltage and high luminous efficiency. Attached Figure Description

[0042] Figure 1 Emission spectra of TAPC, complex 4, and 4:TAPC (20:80) films.

[0043] Figure 2 Emission spectra of TAPC, complex 60, and 60:TAPC (20:80) films.

[0044] Figure 3Emission spectra of TAPC, complex 116 and 116:TAPC (20:80) films

[0045] Figure 4 The structure of the organic light emitting diode device of the present application, wherein 10 represents a glass substrate, 20 represents an anode, 30 represents a hole injection layer, 40 represents a light emitting layer, 50 represents an electron transport layer, 60 represents an electron injection layer, and 70 represents a cathode. DETAILED DESCRIPTION

[0046] The present application does not require a specific method for synthesizing the material. In order to describe the present application in more detail, the following examples are provided, but the present application is not limited thereto. The raw materials used in the following synthesis are commercially available unless otherwise specified.

[0047] Example 1: Synthesis of complex 1

[0048] Synthesis of intermediate 1

[0049]

[0050] Chloroauric acid trihydrate (3.75 g, 9.52 mmol) was dissolved in 6 mL of water and 30 mL of ethanol, and then tetrahydrothiophene (2.10 mL, 23.81 mmol) was added dropwise. At this time, a coarse yellow precipitate was immediately formed. The addition was continued, and the solid changed to white. Then, 24 mL of ethanol was added to make the stirring of the reaction mixture easier. After stirring at 40°C for 20 min, the white precipitate was filtered, washed with a large amount of ethanol, and then the solvent was removed in vacuo. This resulted in 2.75 g of a white solid. Yield 90%. MS (m / z): 321.58 (M+1)

[0051] Synthesis of compound 1a:

[0052]

[0053] Palladium acetate (0.036 g, 0.339 mmol), tri-tert-butylphosphonium tetrafluoroborate (0.295 g, 1.017 mmol) were dissolved in 30 mL of toluene under nitrogen. Then, 1,2-dibromobenzene (2.00 g, 8.48 mmol), aminobenzene (1.58 g, 16.96 mmol), and sodium tert-butoxide (3.26 g, 33.91 mmol) were added to the suspension, and refluxed at 120°C for 12 h. After the reaction was completed, ammonium chloride solution was added, and the extraction was performed. The organic phase was dried using anhydrous sodium sulfate, adsorbed on silica gel, and then purified by column chromatography (dichloromethane: petroleum ether = 1:9). This resulted in 1.503 g of a solid. Yield 68%. MS (m / z): 261.34 (M+1)

[0054] Synthesis of compound 1b:

[0055]

[0056] Compound 1a (2.00 g, 7.68 mmol) and NH4BF4(0.926 g, 8.83 mmol) were added to 25 mL of triethyl orthoformate in a high pressure reactor, followed by 2 mL of acetic acid. The resulting mixture was heated at 120 °C for 12 h. After the reaction was completed, n-hexane was added, the solid was precipitated and filtered, and then slurried with ethyl acetate and methyl tert-butyl ether, and the solvent was removed under vacuum to give 2.063 g of solid. Yield 75%. MS (m / z): 359.15 (M+1) Synthesis of compound 1c:

[0057]

[0058] Compound 1b (1.00 g, 2.79 mmol) was added to 17 mL of THF under nitrogen, followed by 1.4 mL of KHMDS (1 M in THF) at 0 °C. After stirring for 20 min, it was allowed to warm to room temperature, and then intermediate 1 (0.895 g, 2.79 mmol) was added and the reaction was carried out at 40 °C for 12 h. After the reaction was completed, it was evaporated to dryness, dissolved in dichloromethane, filtered through celite, and then slurried with dichloromethane:n-hexane (1 :4), and the solvent was removed under vacuum to give 0.525 g of solid. Yield 38%. MS (m / z): 503.76 (M+1)

[0059] Synthesis of complex 1:

[0060]

[0061] Compound 1c (0.450 g, 0.895 mmol), 2,4-diphenyl-6-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3,5-triazine (0.354 g, 0.814 mmol), and potassium carbonate (0.562 g, 4.07 mmol) were added to 45 mL of ethanol under nitrogen. The reaction was carried out at 40 °C for 12 h. After the reaction was completed, it was filtered, the solid was dissolved in dichloromethane and filtered through celite, the filtrate was evaporated to dryness, and then slurried with dichloromethane:ethanol (1 :4), and the solvent was removed under vacuum to give 0.359 g of solid. Yield 57%. MS (m / z): 776.67 (M+1)

[0062] Example 2: Synthesis of complex 3

[0063] Synthesis of compound 3a:

[0064]

[0065] The synthesis of compound 3a was similar to compound la: 4-tert- butylaniline (2.53 g, 16.96 mmol) was used instead of aminobenzene. 2.560 g of solid was obtained with a yield of 81%. MS (m / z): 373.56 (M+1)

[0066] Synthesis of compound 3b:

[0067]

[0068] The synthesis of compound 3b was similar to compound lb: compound 3a (2.00 g, 5.37 mmol) was used instead of compound la. 1.973 g of solid was obtained with a yield of 78%. MS (m / z): 471.36 (M+1)

[0069] Synthesis of compound 3c:

[0070]

[0071] The synthesis of compound 3c was similar to compound lc: compound 3b (1.00 g, 2.13 mmol) was used instead of compound lb. 0.406 g of solid was obtained with a yield of 31%. MS (m / z): 615.97 (M+1)

[0072] Synthesis of complex 3:

[0073]

[0074] The synthesis of complex 3 was similar to complex 1 : compound 3c (0.45 g, 0.732 mmol) was used instead of compound lc. 0.266 g of solid was obtained with a yield of 41%. MS (m / z): 888.33 (M+1)

[0075] Example 3: Synthesis of complex 4

[0076] Synthesis of compound 4a:

[0077]

[0078] The synthesis of compound 4a was similar to compound la: 3,5- dimethylaniline (2.05 g, 16.96 mmol) was used instead of aminobenzene. 1.903 g of solid was obtained with a yield of 71%. MS (m / z): 317.45 (M+1)

[0079] Synthesis of compound 4b:

[0080]

[0081] The synthesis of compound 4b was similar to compound lb: compound 4a (2.00 g, 6.32 mmol) was used instead of compound la. 1.939 g of solid was obtained, yield 74%. MS (m / z): 415.25 (M+1)

[0082] Synthesis of compound 4c:

[0083]

[0084] The synthesis of compound 4c was similar to compound lc: compound 4b (1.00 g, 2.41 mmol) was used instead of compound lb. 0.513 g of solid was obtained, yield 38%. MS (m / z): 559.86 (M+1)

[0085] Synthesis of complex 4:

[0086]

[0087] The synthesis of complex 4 was similar to complex 1 : compound 4c (0.20 g, 0.358 mmol) was used instead of compound lc. 0.110 g of solid was obtained, yield 37%. MS (m / z): 832.77 (M+1)

[0088] Example 4: Synthesis of complex 57

[0089] Synthesis of compound 57a:

[0090]

[0091] Palladium acetate (0.056 g, 0.25 mmol), 2,2'-bis(diphenylphosphino)-1,1 '-binaphthyl (0.164 g, 0.25 mmol) were dissolved in 30 mL of toluene under nitrogen. 2-chloro-3-iodopyridine (2.00 g, 8.35 mmol) and aminobenzene (1.94 g, 20.88 mmol) and cesium carbonate (13.61 g, 41.76 mmol) were added to the suspension and refluxed at 120 °C for 12 h. After the reaction was completed, it was cooled to room temperature, filtered through celite, the filtrate was extracted with water, the organic phase was dried over anhydrous sodium sulfate and adsorbed on silica gel, purified by column chromatography (pure dichloromethane) and finally washed with methanol. The solvent was removed under vacuum. 1.215 g of white solid was obtained. Yield 56%. MS (m / z): 262.33 (M+1 )

[0092] Synthesis of compound 57b:

[0093]

[0094] The synthesis of compound 57b was similar to compound 1b: compound 57a (2.00 g, 7.65 mmol) was used instead of compound 1a. 1.953 g of solid was obtained with a yield of 71%. MS (m / z): 360.13 (M+1)

[0095] The synthesis of compound 57c:

[0096]

[0097] The synthesis of compound 57c was similar to compound 1c: compound 57b (1.00 g, 2.78 mmol) was used instead of compound 1b. 0.614 g of solid was obtained with a yield of 44%. MS (m / z): 504.74 (M+1)

[0098] The synthesis of complex 57:

[0099]

[0100] The synthesis of complex 57 was similar to complex 1: compound 57c (0.45 g, 0.893 mmol) was used instead of compound 1c. 0.281 g of solid was obtained with a yield of 45%. MS (m / z): 777.65 (M+1)

[0101] Example 5: Synthesis of complex 59

[0102] The synthesis of compound 59a:

[0103]

[0104] The synthesis of compound 59a was similar to compound 57a: 4-tert- butylaniline (3.12 g, 20.88 mmol) was used instead of aminobenzene. 2.215 g of solid was obtained with a yield of 71%. MS (m / z): 374.54 (M+1)

[0105] The synthesis of compound 59b:

[0106]

[0107] The synthesis of compound 59b was similar to compound 1b: compound 59a (2.00 g, 5.35 mmol) was used instead of compound 1a. 1.664 g of solid was obtained with a yield of 66%. MS (m / z): 472.35 (M+1)

[0108] The synthesis of compound 59c:

[0109]

[0110] The synthesis of compound 59c was similar to compound 1c: compound 59b (1.00 g, 2.41 mmol) was used instead of compound 1b. 0.513 g solid was obtained in 39% yield. MS (m / z): 616.96 (M+1)

[0111] Synthesis of complex 59:

[0112]

[0113] The synthesis of complex 59 was similar to complex 1: compound 59c (0.45 g, 0.731 mmol) was used instead of compound 1c. 0.241 g solid was obtained in 41% yield. MS (m / z): 889.87 (M+1)

[0114] Example 6: Synthesis of complex 60

[0115] Synthesis of compound 60a:

[0116]

[0117] The synthesis of compound 60a was similar to compound 57a: 3,5-dimethylaniline (2.53 g, 20.88 mmol) was used instead of aminobenzene. 1.464 g solid was obtained in 55% yield. MS (m / z): 318.44 (M+1)

[0118] Synthesis of compound 60b:

[0119]

[0120] The synthesis of compound 60b was similar to compound 1b: compound 60a (2.00 g, 6.30 mmol) was used instead of compound 1a. 2.017 g solid was obtained in 77% yield. MS (m / z): 416.24 (M+1)

[0121] Synthesis of compound 60c:

[0122]

[0123] The synthesis of compound 60c was similar to compound 1c: compound 60b (1.00 g, 2.41 mmol) was used instead of compound 1b. 0.513 g solid was obtained in 38% yield. MS (m / z): 560.85 (M+1)

[0124] Synthesis of complex 60:

[0125]

[0126] The synthesis of complex 60 was similar to complex 1 : compound 60c (0.45 g, 0.804 mmol) was used instead of compound 1c. 0.312 g solid was obtained, yield 47%. MS (m / z): 833.76 (M+1)

[0127] Example 7: Synthesis of complex 113

[0128] Synthesis of compound 113a:

[0129]

[0130] 2,3-dichloropyrazine (6.00 g, 40.28 mmol) and aminobenzene (8.25 g, 88.61 mmol) were mixed and reacted at 160 °C for 3 h. After the reaction was completed, it was cooled to room temperature, dissolved with an appropriate amount of 25% aqueous sodium hydroxide solution and dichloromethane, and the organic phase was adsorbed on silica gel and purified by column chromatography (dichloromethane: petroleum ether = 1:9) to obtain 6.610 g of solid. Yield 63%. MS (m / z): 263.32 (M+1)

[0131] Synthesis of compound 113b:

[0132]

[0133] The synthesis of compound 113b was similar to compound 1b: compound 113a (2.00 g, 7.62 mmol) was used instead of compound 1a. 2.228 g of solid was obtained, yield 81%. MS (m / z): 361.12 (M+1)

[0134] Synthesis of compound 113c:

[0135]

[0136] The synthesis of compound 113c was similar to compound 1c: compound 113b (1.00 g, 2.78 mmol) was used instead of compound 1b. 0.714 g of solid was obtained, yield 51%. MS (m / z): 505.73 (M+1)

[0137] Synthesis of complex 113:

[0138]

[0139] The synthesis of complex 113 was similar to complex 1 : compound 113c (0.45 g, 0.892 mmol) was used instead of compound 1c. 0.291 g of solid was obtained, yield 46%. MS (m / z): 778.64 (M+1)

[0140] Example 8: Synthesis of complex 115

[0141] Synthesis of compound 115a:

[0142]

[0143] Synthesis of compound 115a was similar to compound 113a: 4-tert- butylaniline (13.22 g, 88.61 mmol) was used instead of aminobenzene. 6.948 g of solid was obtained with a yield of 46%. MS (m / z): 375.53 (M+1)

[0144] Synthesis of compound 115b:

[0145]

[0146] Synthesis of compound 115b was similar to compound 1b: compound 115a (2.00 g, 5.34 mmol) was used instead of compound 1a. 1.664 g of solid was obtained with a yield of 66%. MS (m / z): 473.34 (M+1)

[0147] Synthesis of compound 115c:

[0148]

[0149] Synthesis of compound 115c was similar to compound 1c: compound 115b (1.00 g, 2.12 mmol) was used instead of compound 1b. 0.613 g of solid was obtained with a yield of 47%. MS (m / z): 617.94 (M+1)

[0150] Synthesis of complex 115:

[0151]

[0152] Synthesis of complex 115 was similar to complex 1: compound 59c (0.45 g, 0.731 mmol) was used instead of compound 1c. 0.206 g of solid was obtained with a yield of 35%. MS (m / z): 890.86 (M+1)

[0153] Example 9: Synthesis of complex 116

[0154] Synthesis of compound 116a:

[0155]

[0156] Synthesis of compound 116a was similar to compound 113a: 3,5- dimethylaniline (10.74 g, 88.61 mmol) was used instead of aminobenzene. 6.501 g of solid was obtained with a yield of 51%. MS (m / z): 319.42 (M+1)

[0157] Synthesis of compound 116b:

[0158]

[0159] Synthesis of compound 116b was similar to compound 1b: compound 116a (2.00 g, 6.28 mmol) was used instead of compound 1a. 2.170 g solid was obtained, yield 83%. MS (m / z): 417.23 (M+1)

[0160] Synthesis of compound 116c:

[0161]

[0162] Synthesis of compound 116c was similar to compound 1c: compound 116b (1.00 g, 2.40 mmol) was used instead of compound 1b. 0.627 g solid was obtained, yield 46%. MS (m / z): 561.84 (M+1)

[0163] Synthesis of complex 116:

[0164]

[0165] Synthesis of complex 116 was similar to complex 1: compound 116c (0.40 g, 0.712 mmol) was used instead of compound 1c. 0.249 g solid was obtained, yield 42%. MS (m / z): 834.75 (M+1)

[0166] Example 10: Synthesis of complex 169

[0167] Synthesis of compound 169c:

[0168]

[0169] Compound 1b (0.50 g, 1.40 mmol), palladium chloride (0.396 g, 2.23 mmol), sodium tert-butoxide (0.268 g, 2.79 mmol) were added into 10 mL THF under nitrogen condition, refluxed at 80 °C for 12 h. After reaction, the solid was washed with n-hexane and the solvent was removed under vacuum. 0.391 g solid was obtained, yield 68%. MS (m / z): 413.21 (M+1)

[0170] Synthesis of compound 169:

[0171]

[0172] The synthesis of complex 181 was similar to complex 1 : compound 181c (0.450 g, 1.22 mmol) was used instead of compound 1c. 0.446 g of solid was obtained, yield 60%. MS (m / z): 687.57 (M+1)

[0173] Example 11 : Synthesis of complex 181

[0174] Synthesis of compound 181c:

[0175]

[0176] Compound 1b (0.50 g, 1.40 mmol), silver oxide (0.196 g, 0.846 mmol) were added to 10 mL of DCM under nitrogen condition, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solid was washed with n-hexane and the solvent was removed under vacuum. 0.281 g of solid was obtained, yield 40%. MS (m / z): 370.33 (M+1)

[0177] Synthesis of compound 181:

[0178]

[0179] The synthesis of complex 181 was similar to complex 1 : compound 181c (0.450 g, 1.22 mmol) was used instead of compound 1c. 0.446 g of solid was obtained, yield 60%. MS (m / z): 687.57 (M+1)

[0180] Example 12: Synthesis of complex 193

[0181] Synthesis of compound 193c:

[0182]

[0183] The synthesis of compound 193c was similar to compound 169c: compound 193c (0.276 g, 2.79 mmol) was used instead of compound 169c. 0.421 g of solid was obtained, yield 82%. MS (m / z): 370.33 (M+1)

[0184] Synthesis of compound 193:

[0185]

[0186] The synthesis of complex 193 was similar to complex 1 : compound 193c (0.450 g, 1.22 mmol) was used instead of compound 1c. 0.401 g of solid was obtained, yield 56%. MS (m / z): 643.25 (M+1)

[0187] Those skilled in the art should understand that the above preparation methods are only a few exemplary examples, and those skilled in the art can obtain other compound structures of the present invention by improving them.

[0188] Examples 13-24 and Comparative Example 1:

[0189] Mixed films of gold complexes (1, 3, 4, 57, 59, 60, 113, 115, 116, 169, 181, 193) doped with the organic donor TAPC were prepared by solution spin coating, with a weight ratio of complex-acceptor / TAPC = 20% / 80%. Solid films of organic acceptor TRZ (structure shown below) doped with the organic donor TAPC were prepared by solution spin coating, with a weight ratio of complex-acceptor / organic donor = 20% / 80%.

[0190] The photophysical properties of the above-mentioned thin films are listed in Table 1.

[0191]

[0192] Table 1

[0193]

[0194]

[0195] The doped complex acceptor material and organic donor material emit strong light, and exhibit a significant redshift compared to the donor or acceptor (see appendix). Figures 1-3 (A selection of representative emission spectra is listed, indicating that the two materials form an excitocomplex.) The excitocomplex formed by the organic donor and complex acceptor materials in this invention is significantly higher than that of the mixture film of organic donor TAPC and organic acceptor (TRZ), and has a shorter excited-state lifetime, confirming the feasibility of constructing high-performance excitocomplex luminescent materials using gold complex acceptors.

[0196] Example 25:

[0197] Organic light-emitting diodes (OLEDs) are fabricated using an exciton complex luminescent material constructed from the donor and acceptor material mixture of the present invention. The device structure is shown in the appendix. Figure 4 .

[0198] First, the transparent conductive ITO glass substrate 10 (with an anode 20 on it) is washed sequentially with detergent solution and deionized water, ethanol, acetone, and deionized water, and then treated with oxygen plasma for 30 seconds.

[0199] Then, a 40 nm thick layer of PEDOT:PSS (poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate)) was spin-coated onto ITO as a hole injection layer 30. PEDOT:PSS is a mixture.

[0200] Then, a 30 nm thick light-emitting layer 40 was spin-coated over the hole injection layer, and consisted of gold complex 1 (20%) doped with TAPC (80%).

[0201] Then, a 40 nm thick TmPyPB was evaporated as an electron transport layer 50 over the light-emitting layer.

[0202] Finally, 1 nm of LiF was evaporated as an electron injection layer 60 and 100 nm of Al as a device cathode 70.

[0203] Example 26: An organic light-emitting diode was prepared using complex 3 in place of complex 1, using the method described in Example 25.

[0204] Example 27: An organic light-emitting diode was prepared using complex 4 in place of complex 1, using the method described in Example 25.

[0205] Example 28: An organic light-emitting diode was prepared using complex 57 in place of complex 1, using the method described in Example 25.

[0206] Example 29: An organic light-emitting diode was prepared using complex 59 in place of complex 1, using the method described in Example 25.

[0207] Example 30: An organic light-emitting diode was prepared using complex 60 in place of complex 1, using the method described in Example 25.

[0208] Example 31: An organic light-emitting diode was prepared using complex 113 in place of complex 1, using the method described in Example 25.

[0209] Example 32: An organic light-emitting diode was prepared using complex 115 in place of complex 1, using the method described in Example 25.

[0210] Example 33: An organic light-emitting diode was prepared using complex 116 in place of complex 1, using the method described in Example 25.

[0211] Example 34: An organic light-emitting diode was prepared using complex 169 in place of complex 1, using the method described in Example 25.

[0212] Example 35: An organic light-emitting diode was prepared using complex 181 in place of complex 1, using the method described in Example 25.

[0213] Example 36: An organic light-emitting diode was prepared using complex 193 in place of complex 1, using the method described in Example 25.

[0214] Comparative Example 2:

[0215] Using TRZ instead of complex 1, organic light emitting diodes were prepared using the method described in Example 25.

[0216] The device performance of the organic electroluminescent devices in Examples 25-36 and Comparative Example 2 at a current density of 10 mA / cm2is listed in Table 2:

[0217] Table 2

[0218]

[0219] As can be seen from the data in Table 2, the metal complex acceptor material of the present application in combination with the organic donor used in the organic light emitting diode has a lower driving voltage and higher luminous efficiency under the same conditions. In addition, the device lifetime of the organic light emitting diode based on the complex of the present application is significantly better than the exciplex light emitting material in the comparative example, and has a good application prospect.

[0220] The above-described various embodiments are only as part of representative examples, and are not used to limit the scope of the present application. Various materials and structures in the present application can be replaced by other materials and structures without departing from the spirit of the present application. It should be understood that those skilled in the art can make many modifications and changes without creative labor according to the idea of the present application. Therefore, the technical solutions that can be obtained by analysis, reasoning or partial research on the basis of the prior art should be within the protection scope limited by the claims.

Claims

1. A metal complex acceptor material, which is a compound having the structure of formula (I): ###0001### wherein: the heteroatom in the heteroaryl group is N, S or O; M is selected from the group consisting of gold, silver, palladium or copper; X1, X2 are each independently C or N; X1, X2 are both N.

2. The metal complex acceptor material of claim 1, wherein M is gold. R 1 to R 6 are each independently selected from the group consisting of: deuterium, halogen, aldehyde, cyano, substituted or unsubstituted alkylsulfonyl having from 1 to 6 carbon atoms, substituted or unsubstituted arylsulfonyl having from 6 to 30 carbon atoms, substituted or unsubstituted alkyl having from 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having from 3 to 20 carbon atoms, substituted or unsubstituted alkoxy having from 1 to 20 carbon atoms, substituted or unsubstituted aryl having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having from 3 to 30 carbon atoms, or any two adjacent substituents are linked or fused to form a ring, which is substituted with D, F, C1-C4 alkyl; 3. The metal complex acceptor material of claim 1, having one of the following structures: ###0002### ###0003### 4. The metal complex acceptor material of claim 1, having one of the following structures: ###0004### ###0005### a1 to a4 are integers from 0 to 5, and when a1 is 2 or more, two R 1 groups are the same or different from each other, and when a2 is 2 or more, two R 2 groups are the same or different from each other, and when a3 is 2 or more, two R 3 groups are the same or different from each other, and when a4 is 2 or more, two R 4 groups are the same or different from each other; a5and a6are integers from 0 to 4, and when a5is 2 or more, two R 5 groups are the same or different from each other, and when a6is 2 or more, two R 6 groups are the same or different from each other; a1to a6are zero, R 1 to R 6 substituents are absent.

2. The metal complex acceptor material of claim 1, wherein R 1 to R 6 each independently is selected from the group consisting of: deuterium, a substituted or unsubstituted alkyl group of 1-6 carbon atoms, a substituted or unsubstituted cycloalkyl group of 3-20 carbon atoms, a substituted or unsubstituted aryl group of 6-30 carbon atoms, a substituted or unsubstituted heteroaryl group of 3-30 carbon atoms.

3. The metal complex acceptor material of claim 1, wherein: R 1 to R 2 each independently selected from hydrogen, deuterium, substituted or unsubstituted alkyl having from 1-6 carbon atoms, substituted or unsubstituted cycloalkyl having from 3-20 carbon atoms, a3to a6are zero.

4. The metal complex acceptor material of claim 1, wherein:

5. The metal complex acceptor material of claim 1, having one of the following structures: ###0006### ###0007### 5. The metal complex acceptor material of any one of claims 1-4, wherein:

6. The metal complex acceptor material of claim 1, having one of the following structures: ###0008### ###0009### 7. An exciplex light emitting material, which is composed of 5% to 95% of the metal complex acceptor material of any one of claims 1 to 6 and 95% to 5% of an organic donor material, wherein the organic donor material molecule has one of the following structures: ###0010### ###0011### 8. The exciplex light emitting material of claim 7, which is composed of 5% to 20% of the metal complex acceptor material and 95% to 80% of the organic donor material molecule.

9. Use of the exciplex light emitting material of claim 7 or 8 in an organic optoelectronic device, which is an organic light emitting diode, an organic thin film transistor, an organic photovoltaic device, a light emitting electrochemical cell and a chemical sensor.

10. An organic light emitting diode, which comprises a cathode, an anode and an organic layer, wherein the organic layer is one or more of a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron injection layer, an electron transport layer, and wherein at least one of the hole injection layer, the hole transport layer, the hole blocking layer, the electron injection layer, the light emitting layer, the electron transport layer contains the exciplex light emitting material of claim 7 or 8. ​

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