The solvents and substituents of two similar fluorescent sensors for cyanide, 7-diethylamino- 3-formylcoumarin (sensor a) and 7-diethylamino-3-(2-nitrovinyl)coumarin (sensor b), are proposed to account for their...The solvents and substituents of two similar fluorescent sensors for cyanide, 7-diethylamino- 3-formylcoumarin (sensor a) and 7-diethylamino-3-(2-nitrovinyl)coumarin (sensor b), are proposed to account for their distinct sensing mechanisms and experimental phenomena. The time-dependent density functional theory has been applied to investigate the ground states and the first singlet excited electronic states of the sensor as well as their possible Michael reaction products with cyanide, with a view to monitoring their geometries and photophysieal properties. The theoretical study indicates that the protic water solvent could lead to final Michael addition product of sensor a in the ground state, while the aprotic acetonitrile solvent could lead to carbanion as the final product of sensor b. Furthermore, the Michael reaction product of sensor a has been proved to have a torsion structure in its first singlet excited state. Correspondingly, sensor b also has a torsion structure around the nitrovinyl moiety in its first singlet excited state, while not in its carbanion structure. This could explain the observed strong fluorescence for sensor a and the quenching fluorescence for the sensor b upon the addition of the cyanide anions in the relevant sensing mechanisms.展开更多
基金This work was supported by the National Key Basic Research Special Foundation (No.2007CB815202 and No.2009CB220010) and the National Natural Science Foundation of China (No.20833008).
文摘The solvents and substituents of two similar fluorescent sensors for cyanide, 7-diethylamino- 3-formylcoumarin (sensor a) and 7-diethylamino-3-(2-nitrovinyl)coumarin (sensor b), are proposed to account for their distinct sensing mechanisms and experimental phenomena. The time-dependent density functional theory has been applied to investigate the ground states and the first singlet excited electronic states of the sensor as well as their possible Michael reaction products with cyanide, with a view to monitoring their geometries and photophysieal properties. The theoretical study indicates that the protic water solvent could lead to final Michael addition product of sensor a in the ground state, while the aprotic acetonitrile solvent could lead to carbanion as the final product of sensor b. Furthermore, the Michael reaction product of sensor a has been proved to have a torsion structure in its first singlet excited state. Correspondingly, sensor b also has a torsion structure around the nitrovinyl moiety in its first singlet excited state, while not in its carbanion structure. This could explain the observed strong fluorescence for sensor a and the quenching fluorescence for the sensor b upon the addition of the cyanide anions in the relevant sensing mechanisms.