A novel coumarin Schiff base fluorescent probe ethyl 7-hydroxycoumarin-3-carboxylate-8-formaldehyde benzoyl hydrazone （EBH） has been designed and synthesized which shows solvent dependent dual sensing, viz., recogni...A novel coumarin Schiff base fluorescent probe ethyl 7-hydroxycoumarin-3-carboxylate-8-formaldehyde benzoyl hydrazone （EBH） has been designed and synthesized which shows solvent dependent dual sensing, viz., recognition of Ca^2＋ in DMF-H20 （9 ： 1, V/V） solution based on C=N isomerization, photoinduced electron transfer （PET） inhibition and chelation-enhanced fluorescence （CHEF） mechanism as well as detection of Zn^2＋ in HzO-CH3OH （9 ： 1, V/V） solution by excited-state intramolecular proton transfer （ESIPT） and CHEF processes. The structure of the probe EBH has been confirmed by single-crystal X-ray diffraction analysis. Meanwhile, the probe was also used to image intracellular Zn^2＋ ions in MCF-7 cells with a good performance.展开更多
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
基金Acknowledgement This work was supported by the National Natural Science Foundation of China （Nos. 21472148 and 21072158）, Overseas Students Science and Technology Activities Project Merit Funding of Shaanxi Province （No. 20151190） and Academic Backbone of Northwest University Outstanding Youth Support Program.
文摘A novel coumarin Schiff base fluorescent probe ethyl 7-hydroxycoumarin-3-carboxylate-8-formaldehyde benzoyl hydrazone （EBH） has been designed and synthesized which shows solvent dependent dual sensing, viz., recognition of Ca^2＋ in DMF-H20 （9 ： 1, V/V） solution based on C=N isomerization, photoinduced electron transfer （PET） inhibition and chelation-enhanced fluorescence （CHEF） mechanism as well as detection of Zn^2＋ in HzO-CH3OH （9 ： 1, V/V） solution by excited-state intramolecular proton transfer （ESIPT） and CHEF processes. The structure of the probe EBH has been confirmed by single-crystal X-ray diffraction analysis. Meanwhile, the probe was also used to image intracellular Zn^2＋ ions in MCF-7 cells with a good performance.
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.
