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Heteroleptic cuprous complexes of a diimine MePBO ligand and their structure influence on phosphorescent color: Syntheses, structure characterizations, properties and TD-DFT calculations
Zeitschrift für anorganische und allgemeine Chemie ( IF 1.4 ) Pub Date : 2021-08-16 , DOI: 10.1002/zaac.202100114
Ding‐Qiu Dai 1 , Li Song 2 , Yu Liang 1 , Jian‐Teng Wang 3 , Yi‐Ming Zhou 1 , Hang‐Yan Shen 1 , Wen‐Xiang Chai 1
Affiliation  

Three new heteroleptic [Cu(NN)P2]+ type cuprous complexes 13 were designed and synthesized by utilizing a diimine ligand 5-methyl-2-(2′-pyridyl)-benzoxazole (MePBO) and different phosphine ligands PPh3 (1), m-Tol3P (2) and POP (3), (PPh3=triphenylphosphine, m-Tol3P=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 13 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 13 also present similar blue-shift sequence (31/2). Their microsecond PL lifetime indicates that their PL behavior belongs to phosphorescence. TD-DFT calculation and wavefunction analysis illuminate that the S1 and T1 states of 13 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 S1 and T1 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 π−π stacking interactions should effectively inhibit nonradiative decay so that an abnormal PL emission blue-shift is observed from 1 to 2.

中文翻译:

二亚胺 MePBO 配体的杂配亚铜配合物及其对磷光颜色的结构影响:合成、结构表征、性质和 TD-DFT 计算

三个新的杂[铜(NN)p 2 ] +型亚铜络合物1 - 3被设计,并且通过利用一个二亚胺配体的合成5-甲基-2-(2'-吡啶基) -苯并唑(MePBO)和不同的膦配体PPH 3 ( 1 ),m-Tol 3 P( 2 )和POP( 3 ),(PPh 3 =三苯基膦,m-Tol 3P=三(3-甲基苯基)膦,POP=双[2-(二苯基膦基)苯基]醚),分别。所有配合物均通过单晶 X 射线衍射、光谱分析(IR、UV-Vis)、元素分析和光致发光研究进行表征。单晶X射线衍射分析表明,复合物1 - 3均采用离散阳离子配合物结构,其具有四面体寸2 P 2具有不同P-Cu-P合金的角度协调的几何形状。它们的紫外-可见吸收光谱在 P-Cu-P 角从32再到1的放大下表现出蓝移序列。PL 发射峰值波长为13也呈现类似的蓝移序列(31 / 2)。它们的微秒 PL 寿命表明它们的 PL 行为属于磷光。TD-DFT计算和波函数分析照射的S 1和T 1的状态的1 - 3都应该被指定为(ML + L'L)CT的状态。它们的 UV-Vis 吸收和磷光应归因于从 P-Cu-P 段到 MePBO 配体的电荷转移。因此,随着 P-Cu-P 角的增加(较低的 HOMO),S 1和 T 1的能量随着 PL 颜色的变化,状态也会增加。此外,膦配体取代基的空间位阻以及超强的分子内 π-π 堆积相互作用应有效抑制非辐射衰变,从而观察到异常的 PL 发射蓝移从12
更新日期:2021-10-01
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