[Ir(ppy)_(2)(X-ppz)]^(+)配合物结构和光谱性质的量子理论研究  

Theoretical Studies on the Electronic Structures and Spectroscopic Properties for a Series of[Ir(ppy)_(2)(X-ppz)]^(+)Complexes

作　　者：聂建航 王子轩 贲虹博 张建坡[1] 金丽[1] NIE Jianhang;WANG Zixuan;BEN Hongbo;ZHANG Jianpo;JIN Li(School of Chemical and Pharmaceutical Engineering,Jilin Institute of Chemical Technology,Jilin 132022,China)

机构地区：[1]吉林化工学院化学与制药工程学院,吉林吉林132022

出　　处：《吉林化工学院学报》2021年第11期5-9,共5页Journal of Jilin Institute of Chemical Technology

摘　　要：从理论上研究了一系列[Ir(ppy)_(2)(ppz)]^(+)(1),[Ir(ppy)_(2)(ph-ppz)]^(+)(2),[Ir(ppy)_(2)(ph-ppz)]^(+)(3)(3与2的区别在于苯环的连接位置不同),[ppy=苯基吡啶,ppz=2-吡啶基吡唑,ph=苯基]配合物的几何构型和光谱特征.采用B3LYP泛函和单激发组态相互作用(CIS)方法计算了基态(S0)和最低能三重激发态(T1)结构,用含时密度泛函方法结合PCM溶剂模型计算3个分子在二氯甲烷溶剂中的吸收和发射光谱.研究结果表明,Ir-N3和Ir-N4优化结构数据与相应的实验值近似相同.配合物1-3的最低能吸收在447.91、456.52和516.90 nm,磷光发射在512.02、501.14和562.29 nm.它们的最高占据轨道(HOMO)主要由金属Ir和配体ppy占据,而最低空轨道(LUMO)均为占据在ppz配体上的π*型轨道,因此该跃迁属于金属到ppz配体和ppy配体到ppz配体的(MLCT/LLCT)电荷转移跃迁.并且,此类配合物的吸收和发射受ppy和ppz配体影响较大.The geometries and spectroscopic properties of[Ir(ppy)_(2)(X-ppz)]^(+)(1),[Ir(ppy)_(2)(X-ppz)]^(+)(2),[Ir(ppy)_(2)(X-ppz)]^(+)(3)(3 and 2 are different in the connection position of benzene ring)[ppy=phenylpyridine,ppz=(2-pyridyl)pyrazole,ph=phenyl]complexes were studied theoretically.B3LYP functional and single excited configuration interaction(CIS)methods were used to optimize the S0 and T,structures.The absorption and emission spectra of the complexes in CH2C12 solution were calculated by time dependent density functional theory(TD-DFT)and polarized continuum model(PCM).The results show that Ir-N3 and Ir-N4 obtained by the ground state optimization are in good agreement with the corresponding experimental values.The lowest energy absorption of complexes 1-3 is 447.91 nm,456.52 nm and 516.90 nm,and the phosphorescence emission is 512.02 nm,501.14 nm and 562.29 nmRespectively.The highest occupied molecule orbit(HOMO)of complexes 1-3 is mainly occupied by Ir and ppy,and the lowest unoccupied orbit(LUMO)is occupied by ppz ligandsπ*orbit.Therefore,this transition is referred to as the metal to ppz ligand and ppy ligand to ppz ligand charge transfer(MLCT/LLCT)transition.Moreover,the absorption and emission of these complexes are greatly influenced by ppy and ppz ligands.

关 键 词：铱配合物 光谱特征 电子结构 理论计算 

分 类 号：O641.3[理学—物理化学]