含有共轭炔基的发光Pt(Ⅱ)配合物发光性质的密度泛函理论研究  

DFT Studies on the Luminescent Pt(Ⅱ) Complexes Containing Conjugated Acetylide Ligand

作　　者：舒鑫[1] 周欣[1] 潘清江[2] 李明霞[2] 张红星[1] 孙家钟[1] 

机构地区：[1]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130023 [2]黑龙江大学化学化工与材料学院,哈尔滨150080

出　　处：《无机化学学报》2008年第6期971-976,共6页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金资助项目(No.20573042,20703015);黑龙江省自然科学基金资助项目(No.B200601);黑龙江大学杰出青年基金(No.JC2006L2)

摘　　要：本文利用密度泛函(DFT)和含时密度泛函(TDDFT)方法研究了一系列配合物Pt(ppy)(C≡C)nPh(ppy=6-phenyl-2,2′-bipyridinen=1～6)的基态和激发态的电子结构和发射光谱。计算揭示,当(C≡C)n链长n=1～3时,配合物1～3的磷光发射被指认为是3[π*(ppy)→Pt(5d),π((C≡C)nPh)](3LMCT/3LLCT)的混合电荷跃迁。而当n=4～6时,配合物4～6的磷光发射主要是来自于(C≡C)nPh配体内部3ππ*跃迁(3ILCT)和少部分的3LLCT微扰跃迁。通过分析前线轨道成份,可以预测当炔基链长n趋于∞时,电荷跃迁将完全发生在炔基链的π轨道之间。The properties of electronic structures in the ground and excited states and emission spectra of Pt（ppy）（C≡C）n Ph （ppy=6-phenyl-2,2′-bipyridine, n=1～6） were explored by using the DFT and TDDFT method, respectively. The calculations revealed that the lowest energy emissions of 1～3 were assigned as arising from the combinational transitions of ^3[π^＊（ppy） → Pt（5d）, π（（C≡C）nPh）] charge transfer （^3LMCT/^3LLCT）, whereas those of 4～6 mainly originated from ^3π → π^＊ （3ILCT） transition localized upon the （C≡C）n Ph moiety and perturbed by some ^3LLCT. It was predicted that, with increasing the chain length, the electrons transition would completely come from the ππ^＊ transition in Cn^2- chain.

关 键 词：环金属Pt(Ⅱ)配合物 激发态 发光 密度泛函 含时密度泛函 

分 类 号：O614.826[理学—无机化学] O641.121[理学—化学]