双核Pt(Ⅱ)配合物的光谱结构和激发态性质的密度泛函理论研究  

DFT Studies on the Spectroscopic and Excited-state Properties of Di-nuclear Pt(Ⅱ) Complexes

作　　者：张首才[1] 王嵩[2] 周欣[2] 张红星[2] 邵琛[3] 李传碧[1] 

机构地区：[1]吉林师范大学化学学院,四平136000 [2]吉林大学理论化学研究所理论化学计算国家重点实验室,长春130061 [3]东北师范大学化学学院,长春130024

出　　处：《化学学报》2008年第8期841-846,共6页Acta Chimica Sinica

基　　金：国家自然科学基金(Nos.20573042,20333050)资助项目

摘　　要：采用基于第一性原理的密度泛函理论对单核和双核三联吡啶Pt(Ⅱ)配合物[Pt(trpy)C≡CH]+(1)和[Pt(trpy)C≡CH]22+(2)的基态和激发态以及光谱性质进行了系统研究.结果揭示了双体配合物中Pt—Pt间距离在激发态时明显短于基态时的距离,而且双体聚合后最低能吸收和发射波长相对单体配合物发生了明显红移,这种激发的本质被指认为是来自于[dσ*(dδ*π*)]的MMLCT(metal-to-metal-to-ligand charge transfer)电荷转移跃迁.另外,对研究的配合物,用VWN(Vosko-Wilk-Nusair)泛函优化得到的几何和用SAOP(轨道势的统计平均)计算的光谱能量和实验值符合得很好,能够准确反映实验现象.The ground and excited states of mono- and di-nuclear terpyridyl Pt（Ⅱ） complexes [Pt（trpy）C≡CH]＋ （1） and [Pt（trpy）C≡CH]2^2＋ （2） were explored by using the first principle based on a DFr method. The results show that the Pt-Pt bond length is obviously shortened in the excited state relative to that in the ground state and the wavelength of the lowest-energy absorption and emission for the dimer is red-shifted compared with the monomer. The origin of the excitation was attributed to the 【d13＋（dδ·π＊）】 charge transfer transition. In addition, the calculations show that, for the complexes investigated in this work, the optimized geometries by the VWN （Vosko-Wilk-Nusair） functional and spectroscopic energy by the SAOP （statistical average of orbital potentials） functional are in agreement with the experimental values.

关 键 词：双核发光铂(Ⅱ)配合物 激发态 电荷转移跃迁 密度泛函 

分 类 号：O641.4[理学—物理化学]