摘要
采用密度泛函方法对[(tpy)Ru(tHI-X)]^(2+)配合物[(tpy=2,2′:6′,2″-三联吡啶,tHI=三联吡啶-4′-苯基-1H-菲[9,10-d]-咪唑,X=None(1),F^(-)(2)]的结构和光谱特性进行详细的理论研究。使用高斯09软件包中密度泛函方法下的B3LYP和UB3LYP泛函分别优化了两个配合物的基态和激发态几何构型,利用含时密度泛函方法结合极化连续介质模型得到了两个分子在二甲基亚砜溶液中的吸收和发射光谱。计算结果表明:配合物1的基态键长和吸收光谱与相应实验值高度吻合。当引入F^(-)后,F^(-)与N_(7)-H键上的H原子发生强得相互作用,形成新的F—H键。在TD-DFT和PCM计算水平下,得到配合物1-2的最低能吸收和发射分别出现在505、628 nm和713、744 nm。1-2的HOMOs主要占据在tHI配体上,而LUMOs为tpy配体的π反键轨道,因此该跃迁被指认为[π(tHI)]→[π*(tpy)]电荷转移跃迁,其~3LLCT跃迁属性是导致该类配合物辐射跃迁的主要因素。
The geometrical and spectral characteristics of[(tpy)Ru(tHI-X)]^(2+)[(tpy=2,2′:6′,2″-terpyridine,tHI=2-(4-[2,2′:6′,2″]terpyridine-4-ylphenyl)-1H phenanthrene[9,10-d]-imidazole,X=none(1),F(2)]complexes were studied by the density functional theory(DFT)method.The geometric configuration of the ground and excited state of the complexes 1 and 2 was optimized by using the B3LYP and UB3LYP functional in the density functional method of Gaussian 09 program,respectively.The absorption and emission spectra of the two molecules in DMSO solution were obtained by combining the polarization continuum model.The calculated results showed that the ground state bond lengths and absorption spectrum of complex 1 were in good agreement with the corresponding experimental values,when F-groups were introduced,the H atoms on the F^(-)and N_(7)-H have strong interaction,to generate a new F-H bond.At the TD-DFT and PCM levels,1-2 give rise to absorptions at 505 and 628 nm and phosphorescent emissions at 713 and 744 nm,respectively.The HOMOs of 1-2 were mainly localized on the tHI ligand,while the LUMOs are theπ^(*)(tpy)type orbital.Therefore,the transitions of 1-2 were all attributed to[π(tHI)]→[π^(*)(tpy)]charge transfer.The ^(3)LLCT transition property of the lowest excited state was the main factor leading to the radiation transition.
作者
聂建航
贾永涛
曲珈慧
张建坡
金丽
NIE Jianhang;JIA Yongtao;QU Jiahui;ZHANG Jianpo;JIN Li(School of Chemical and Pharmaceutical Engineering,Jilin Institute of Chemical Technology,Jilin City 132022,China;Chemical Fertilizer Plant,PetroChina Jilin Petrochemical Company,Jilin City 132021,China)
出处
《吉林化工学院学报》
CAS
2023年第5期10-14,共5页
Journal of Jilin Institute of Chemical Technology
