Fluorescent probes based on intramolecular charge transfer(ICT) have obvious advantages for accurate quantitative analysis.To obtain high-performance ratiometric probes requires distinct photophysical properties durin...Fluorescent probes based on intramolecular charge transfer(ICT) have obvious advantages for accurate quantitative analysis.To obtain high-performance ratiometric probes requires distinct photophysical properties during recognition reaction process,which is closely related to their ICT characteristics.1,8-Naphthalimide is known as a typical fluorophore with desirable ICT property when functionalized with an electron-donating moiety at the para-position of the naphthalene chromophore.Although the photophysical properties of para-substituted 1,8-naphthalimide have been well studied,its meta-substituted counterpart has not been fully evaluated since the meta-position is conventionally thought to be weakly conjugated.Herein,combined experimental and theoretical studies are performed which consistently indicate that stronger charge transfer(CT) is exhibited by the meta-amino substituted 1,8-naphthalimide(m-NH_(2)) compared to the para-amino substituted one(p-NH_(2)).The ratiometric response of fluorescence with significant changes in wavelength and intensity upon acetylation(m-NAc and p-NAc) can be attributed to the larger ICT and stronger-NH_(2) vibrations.This observation is further demonstrated by deuterium oxide experiments,viscosity experiments and quantum chemical calculations.The practical application of meta-amino-1,8-naphthalimide ICT-based probes is also confirmed.This research is expected to bring an in-depth understanding of π-conjugated systems with ICT characteristics,and facilitates the design of sensitive ICT fluorescent probes with meta-amino substitution.展开更多
基金financially supported by National Key Research and Development Programs (Nos.2022YFD1700403 and 2023YFD1700303)National Natural Science Foundation of China (Nos.12274128 and 12250003)+2 种基金Shanghai Rising-Star Program (No.21QA1402600)the support of NYU-ECNU Center for Computational Chemistry at NYU Shanghaithe University of Bath and the Open Research Fund of the School of Chemistry and Chemical Engineering,Henan Normal University (No.2020ZD01) for support。
文摘Fluorescent probes based on intramolecular charge transfer(ICT) have obvious advantages for accurate quantitative analysis.To obtain high-performance ratiometric probes requires distinct photophysical properties during recognition reaction process,which is closely related to their ICT characteristics.1,8-Naphthalimide is known as a typical fluorophore with desirable ICT property when functionalized with an electron-donating moiety at the para-position of the naphthalene chromophore.Although the photophysical properties of para-substituted 1,8-naphthalimide have been well studied,its meta-substituted counterpart has not been fully evaluated since the meta-position is conventionally thought to be weakly conjugated.Herein,combined experimental and theoretical studies are performed which consistently indicate that stronger charge transfer(CT) is exhibited by the meta-amino substituted 1,8-naphthalimide(m-NH_(2)) compared to the para-amino substituted one(p-NH_(2)).The ratiometric response of fluorescence with significant changes in wavelength and intensity upon acetylation(m-NAc and p-NAc) can be attributed to the larger ICT and stronger-NH_(2) vibrations.This observation is further demonstrated by deuterium oxide experiments,viscosity experiments and quantum chemical calculations.The practical application of meta-amino-1,8-naphthalimide ICT-based probes is also confirmed.This research is expected to bring an in-depth understanding of π-conjugated systems with ICT characteristics,and facilitates the design of sensitive ICT fluorescent probes with meta-amino substitution.
