杂环戊二烯作为π⁃桥调控锌卟啉染料光电性能的理论研究  

Theoretical Study on Regulation of Photoelectric Properties of Zinc Porphyrin Dyes with Heterocyclopentadiene asπ⁃Bridge

作　　者：高倩倩 袁清堂 宋旭锋[1] 于艳敏[1] 郭静[1] GAO Qian‑Qian;YUAN Qing‑Tang;SONG Xu‑Feng;YU Yan‑Min;GUO Jing(Beijing Key Laboratory for Green Catalysis and Separation,Department of Environmental Chemical Engineering,Beijing University of Technology,Beijing 100124,China)

机构地区：[1]北京工业大学环境化工系,绿色催化与分离北京市重点实验室,北京100124

出　　处：《无机化学学报》2022年第2期295-303,共9页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21776021);北京高校卓越青年科学家计划项目(No.BJJWZYJH0201910005017)资助。

摘　　要：为了研究杂环戊二烯作为π‑桥对锌卟啉染料光电性能的影响,在染料YD2‑o‑C8的基础上,通过引入含有不同杂原子的杂环戊二烯作为π‑桥设计了6种新型锌卟啉染料。采用密度泛函理论(DFT)和含时密度泛函理论(TD‑DFT)方法对染料的前线分子轨道、吸收光谱和电子-空穴分离特性进行研究。结果表明,与染料YD2‑o‑C8相比,杂环戊二烯的引入可以提升卟啉染料的光电性能,且改变杂原子可以调控卟啉染料的光电性能。对杂环戊二烯性质与卟啉染料光电性能的相关性研究发现,杂环戊二烯的最低空轨道能级与卟啉染料光电性能之间具有较好的线性关系。杂环戊二烯的接受电子能力越强,相应卟啉染料的光电性能越好。硅杂环戊二烯由于具有最强的接受电子能力而使相应的卟啉染料具有最宽的光谱吸收范围以及最强的分子内电荷转移能力。To explore the regulation of photoelectric properties of zinc porphyrin dyes with heterocyclopentadiene asπ‑bridge,six new zinc porphyrin dyes were designed by introducing heterocyclopentadiene with different heteroatoms as theπ‑bridge based on the reference dye YD2‑o‑C8.The frontier molecular orbital energy levels,absorption spectra,and the hole‑electron separation characteristics of the designed dyes were investigated using the density functional theory(DFT)and time‑dependent density functional theory(TD‑DFT)methods.The results show that compared with the reference dye YD2‑o‑C8,the introduction of heterocyclopentadiene inπ‑bridge can improve the photoelectric performance of dyes.The photoelectric properties of porphyrin dyes can be regulated by changing heteroatoms.Further analysis on the relationship between the properties of heterocyclopentadienes and the photoelectric performance of the porphyrin dyes shows that the lowest unoccupied molecular orbital energy level of heterocyclopentadienes has a good linear relationship with the photoelectric properties of the designed porphyrin dyes.The stronger electron receiving ability of heterocyclopentadiene can lead to the better performance of the porphyrin dye.The silicon‑heterocyclopentadiene is of the strongest electron receiving ability,and the corresponding porphyrin dye has the widest absorption spectra and the strongest intramolecular charge transfer ability.

关 键 词：卟啉 染料 杂环戊二烯 π‑桥 密度泛函理论 

分 类 号：TM914.42[电气工程—电力电子与电力传动]