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 synthes...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.展开更多
Three novel dithienylethenes modified by bifluoroboron β-diketonate fragments have been successfully developed. Upon blue light irradiation, they reached photostationary state within 2-5 s, as well as 100% conversion...Three novel dithienylethenes modified by bifluoroboron β-diketonate fragments have been successfully developed. Upon blue light irradiation, they reached photostationary state within 2-5 s, as well as 100% conversion ratio and photocyclization quantum yield of > 0.70. Such fascinating photochromism were endowed by collaborative role of electron-withdrawing effect of BF_(2)bdk group to reduce HOMO-LUMO electronic gap for the open isomer, together with intramolecular hydrogen bonds and CH-π interactions favoring antiparallel conformation fixation. Moreover, they displayed specific discrimination and photoswitchable bacterial imaging for S. aureus.展开更多
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)+1 种基金Sichuan Science and Technology Program(No.2020YJ0161 for Xiang-Yang Liu)the High Performance Computing Center of Sichuan Normal University。
文摘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.
基金financial support from the Natural Science Foundation of Henan Province(No.222300420501)the Science and Technology Project of Henan Province(No.212102210549)+1 种基金the Key Scientific Research Project of Higher Education of Henan Province(No.22A430007)National College Students Innovation and Entrepreneurship Training Program(No.202110482010)。
文摘Three novel dithienylethenes modified by bifluoroboron β-diketonate fragments have been successfully developed. Upon blue light irradiation, they reached photostationary state within 2-5 s, as well as 100% conversion ratio and photocyclization quantum yield of > 0.70. Such fascinating photochromism were endowed by collaborative role of electron-withdrawing effect of BF_(2)bdk group to reduce HOMO-LUMO electronic gap for the open isomer, together with intramolecular hydrogen bonds and CH-π interactions favoring antiparallel conformation fixation. Moreover, they displayed specific discrimination and photoswitchable bacterial imaging for S. aureus.
