Preparation and use of tetradentate platinum(II) complex
View Patent ↗The present invention relates to preparation and application of a novel quadridentate platinum (II) complex, and belongs to the field of OLED organic electroluminescent materials. The complex of the present invention has NCNC chelating coordination, a stable structure, a spiro ring structure in the skeleton, a strong molecular stereoscopic property, and weak intermolecular interaction, so that mutual stacking between complex molecules is avoided, the formation of an excimer is greatly inhibited, and thus the efficiency of an OLED device is improved. The complex of the present invention has high fluorescence quantum efficiency, great thermal stability and low quenching constant, and can be used for manufacturing a red-light OLED device with high luminescence efficiency and low roll-off.
1 . A quadridentate platinum (II) complex, having the structure as shown in the following formula:
wherein R 1 -R 22 are independently selected from hydrogen, deuterium, sulfur, halogen, hydroxyl, acyl, alkoxy, acyloxy, amino, nitro, acyl amino, cyano, carboxyl, styryl, amino carbonyl, carbamoyl, benzyl carbonyl, aryloxy, diarylamino, saturated alkyl containing 1-30 C atoms, unsaturated alkyl containing 2-20 C atoms, substituted or unsubstituted aryl containing 5-30 C atoms, and substituted or unsubstituted heteroaryl containing 5-30 C atoms; or adjacent R 1 -R 21 are mutually connected into a ring by a covalent bond; the substituted refers to substitution with halogen, deuterium, C 1 -C 20 alkyls, C 1 -C 10 silyls, and cyano; and a heteroatom in the heteroaryl comprises one or more of N, O, and S.
2 . The complex according to claim 1 , wherein the R 1 -R 21 are independently selected from hydrogen, halogen, amino, nitro, cyano, diarylamino, saturated alkyl containing 1-10 C atoms, aryl containing 5-20 C atoms unsubstituted or substituted with halogen or one or more of C 1 -C 4 alkyls, and heteroaryl containing 5-20 C atoms unsubstituted or substituted with halogen or one or more of C 1 -C 4 alkyls; or adjacent R 1 -R 21 are mutually connected into a ring by a covalent bond; and the halogen comprises F, Cl, and Br.
3 . The complex according to claim 2 , wherein among 22 groups, namely the R 1 -R 22 , 0-3 groups are independently represented as diarylamino, aryl containing 5-10 C atoms unsubstituted or substituted with halogen or 1-3 C 1 -C 4 alkyls, and N-heteroaryl containing 5-10 C atoms unsubstituted or substituted with halogen or 1-3 C 1 -C 4 alkyls; the other groups are independently represented as hydrogen or saturated alkyl containing 1-8 C atoms; and the halogen comprises F and Cl.
4 . The complex according to claim 3 , wherein among the 22 groups, namely the R 1 -R 22 , 0-3 groups are independently represented as diphenylamino, phenyl unsubstituted or substituted with halogen or 1-3 C 1 -C 4 alkyls, pyridyl unsubstituted or substituted with halogen or 1-3 C 1 -C 4 alkyls, and carbazolyl unsubstituted or substituted with halogen or 1-3 C 1 -C 4 alkyls; and the other groups are independently represented as hydrogen, fluorine, or saturated alkyl containing 1-4 C atoms.
5 . The complex according to claim 1 , having the structure as shown in the following formula:
wherein R 1 ′-R 5 ′ are independently selected from hydrogen, halogen, diarylamino, saturated alkyl containing 1-10 C atoms, aryl containing 5-20 C atoms unsubstituted or substituted with halogen or one or more of C 1 -C 4 alkyls, and heteroaryl containing 5-20 C atoms unsubstituted or substituted with halogen or one or more of C 1 -C 4 alkyls; or adjacent R 1 ′-R 5 ′ are mutually connected into a ring by a covalent bond; the halogen comprises F, Cl, and Br; and a heteroatom in the heteroaryl comprises any one of N, O, and S.
6 . The complex according to claim 5 , wherein among 5 groups, namely the 0-3 groups are independently represented as diarylamino, aryl containing 5-10 C atoms unsubstituted or substituted with halogen or 1-3 C 1 -C 4 alkyls, and heteroaryl containing 5-10 C atoms unsubstituted or substituted with halogen or 1-3 C 1 -C 4 alkyls; the other groups are independently represented as hydrogen, halogen, or saturated alkyl containing 1-8 C atoms; and the halogen comprises F and Cl.
7 . The complex according to claim 6 , wherein among the 5 groups, namely the R 1 ′-R 5 ′, 0-3 groups are independently represented as diphenylamino, phenyl unsubstituted or substituted with C 1 -C 4 alkyls, pyridyl unsubstituted or substituted with C 1 -C 4 alkyls, and carbazolyl unsubstituted or substituted with C 1 -C 4 alkyls; and the other groups are independently represented as hydrogen, fluorine, or saturated alkyl containing 1-4 C atoms.
8 . The complex according to claim 1 , having one of the following structures:
9 . A precursor, that is ligand, of the complex according to any one of claims 1 to 8 , having the following structural formula:
wherein R 1 -R 22 are independently selected from hydrogen, deuterium, sulfur, halogen, hydroxyl, acyl, alkoxy, acyloxy, amino, nitro, acyl amino, cyano, carboxyl, styryl, amino carbonyl, carbamoyl, benzyl carbonyl, aryloxy, diarylamino, saturated alkyl containing 1-30 C atoms, unsaturated alkyl containing 2-20 C atoms, substituted or unsubstituted aryl containing 5-30 C atoms, and substituted or unsubstituted heteroaryl containing 5-30 C atoms; or adjacent R 1 -R 21 are mutually connected into a ring by a covalent bond; the substituted refers to substitution with halogen, deuterium, C 1 -C 20 alkyls, C 1 -C 10 silyls, and cyano; and a heteroatom in the heteroaryl comprises one or more of N, O, and S.
10 . A method for synthesizing the quadridentate platinum (II) complex according to claim 5 , comprising the following steps:
subjecting initial substrates S1 and S2 to a Suzuki coupling reaction to obtain a substrate S3; subjecting the S3 and S4 to a Buchwald-Hartwig coupling reaction to obtain a substrate S5; subjecting the S5 and S6 to a reaction to obtain a substrate S7; and subjecting the S7 and K 2 PtCl 4 to a chelating reaction to obtain the target platinum (II) complex TM.
11 . Application of the complex according to any one of claims 1 to 8 in an OLED light-emitting device.
12 . The application according to claim 11 , wherein the complex according to any one of claims 1 to 8 is used as a phosphorescent doping material with a photon emission effect in a light-emitting layer.