Solvent Effects on Excited-State Relaxation Dynamics of Paddle-Wheel BODIPY-Hexaoxatriphenylene Conjugates:Insights from Non-adiabatic Dynamics Simulations  

采用非绝热动力学模拟探究溶剂效应对桨-轮形状的给体-受体复合物的激发态弛豫动力学的影响

作　　者：Wen-Kai Chen Ganglong Cui Xiang-Yang Liu 陈文恺;崔刚龙;刘向洋(北京师范大学化学学院,理论与计算光化学教育部重点实验室,北京100875;四川师范大学化学与材料科学学院,成都610068)

机构地区：[1]Key Laboratory of Theoretical and Computational Photochemistry,Ministry of Education,College of Chemistry,Beijing Normal University,Beijing 100875,China [2]College of Chemistry and Material Science,Sichuan Normal University,Chengdu 610068,China

出　　处：《Chinese Journal of Chemical Physics》2022年第1期117-128,I0015-I0034,I0063,共33页化学物理学报（英文）

基　　金：supported by the National Natural Science Foundation of China(No.22003043 for Xiang-Yang Liu);the National Natural Science Foundation of China(No.21688102,No.21590801,and No.21520102005 for Ganglong Cui);Sichuan Science and Technology Program(No.2020YJ0161 for Xiang-Yang Liu);the High Performance Computing Center of Sichuan Normal University。

摘　　要：Understanding the excited state dynamics of donor-acceptor(D-A)complexes is of fundamental importance both experimentally and theoretically.Herein,we have first explored the photoinduced dynamics of a recently synthesized paddle-wheel BODIPY-hexaoxatriphenylene(BODIPY is the abbreviation for BF_(2)-chelated dipyrromethenes)conjugates D-A complexes with the combination of both electronic structure calculations and nonadiabatic dynamics simulations.On the basis of computational results,we concluded that the BODIPY-hexaoxatriphenylene(BH)conjugates will be promoted to the local excited(LE)states of the BODIPY fragments upon excitation,which is followed by the ultrafast exciton transfer from LE state to charge transfer(CT).Instead of the photoinduced electron transfer process proposed in previous experimental work,such a exciton transfer process is accompanied with the photoinduced hole transfer from BODIPY to hexaoxatriphenylene.Additionally,solvent effects are found to play an important role in the photoinduced dynamics.Specifically,the hole transfer dynamics is accelerated by the acetonitrile solvent,which can be ascribed to significant influences of the solvents on the charge transfer states,i.e.the energy gaps between LE and CT excitons are reduced greatly and the non-adiabatic couplings are increased in the meantime.Our present work not only provides valuable insights into the underlying photoinduced mechanism of BH,but also can be helpful for the future design of novel donor-acceptor conjugates with better optoelectronic performance.

关 键 词：Donor-Acceptor conjugate BF_(2)-chelated dipyrromethene Solvent effect Non-adiabatic dynmamics EXCITED-STATE 

分 类 号：O643.1[理学—物理化学]