Heteroleptic cuprous complexes of a diimine MePBO ligand and their structure influence on phosphorescent color: Syntheses, structure characterizations, properties and TD-DFT calculations

被引:10
作者
Dai, Ding-Qiu [1 ]
Song, Li [2 ]
Liang, Yu [1 ]
Wang, Jian-Teng [3 ]
Zhou, Yi-Ming [1 ]
Shen, Hang-Yan [1 ]
Chai, Wen-Xiang [1 ]
机构
[1] China Jiliang Univ, Coll Mat & Chem, Hangzhou 310018, Peoples R China
[2] Zhejiang Sci Tech Univ, Dept Chem, Hangzhou 310018, Peoples R China
[3] China Tobacco Shandong Ind Co Ltd, Jinan Cigarettes Factory, Jinan 250101, Peoples R China
来源
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE | 2021年 / 647卷 / 19期
关键词
heteroleptic cuprous complex; P-Cu-P angle; phosphorescence color; TD-DFT calculation; charge transfer; MONONUCLEAR COPPER(I) COMPLEXES; LIGHT-EMITTING-DIODES; DELAYED FLUORESCENCE; PHOTOPHYSICAL PROPERTIES; CU(I) COMPLEXES; MECHANOCHROMIC LUMINESCENCE; PHENANTHROLINE LIGANDS; DIPHOSPHINE LIGANDS; RATIONAL DESIGN; METAL-COMPLEXES;
D O I
10.1002/zaac.202100114
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Three new heteroleptic [Cu(NN)P-2](+) type cuprous complexes 1-3 were designed and synthesized by utilizing a diimine ligand 5-methyl-2-(2 '-pyridyl)-benzoxazole (MePBO) and different phosphine ligands PPh3 (1), m-Tol(3)P (2) and POP (3), (PPh3=triphenylphosphine, m-Tol(3)P=tris(3-methylphenyl)phosphine, POP=bis[2-(diphenylphosphino)phenyl]ether), respectively. All complexes were characterized by single-crystal X-ray diffraction, spectroscopic analysis (IR, UV-Vis), elemental analysis, and photoluminescence study. Single-crystal X-ray diffraction revealed that complexes 1-3 all adopt discrete cation complex structure with a tetrahedral CuN2P2 coordination geometry with diverse P-Cu-P angles. Their UV-Vis absorption spectra exhibit a blue-shift sequence under the enlarging of P-Cu-P angle from 3 to 2 then to 1. The PL emission peak wavelengths of 1-3 also present similar blue-shift sequence (3 -> 1/2). Their microsecond PL lifetime indicates that their PL behavior belongs to phosphorescence. TD-DFT calculation and wavefunction analysis illuminate that the S-1 and T-1 states of 1-3 should all be assigned as (ML+L ' L)CT states. Their UV-Vis absorption and phosphorescence should be attributed to the charge transfer from the P-Cu-P segment to the MePBO ligand. Therefore, as P-Cu-P angle increases (lower HOMO), the energy of S-1 and T-1 states also increase, following the change of PL color. Additionally, the steric hindrance from substituents of phosphine ligand, as well as extra strong intra-molecular pi-pi stacking interactions should effectively inhibit nonradiative decay so that an abnormal PL emission blue-shift is observed from 1 to 2.
引用
收藏
页码:1896 / 1905
页数:10
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