Uncovering the sensing mechanism of a zinc ion sensor: Fluorescence enhancement induced by the elimination of the TICT state.

Precise detection of zinc ion is of fundamental importance in the fields of environment protection and food safety. A comprehensive understanding of the sensing mechanism will help to the design of such sensors. The detailed photophysical process of a zinc ion sensor as well as the sensing mechanism are uncovered with the aid of density functional theory (DFT) and time-dependent density functional theory (TDDFT). Both the ground state and first excited state potential energy surfaces (PES) of the sensor are carefully explored to reveal the photo-physical process of the sensor. Excited state intramolecular proton transfer (ESIPT) is observed on the S state PES. Then, the twist motion of C=N double bond is triggered after the ESIPT process, which leads to a twisted intramolecular charge transfer (TICT) state. This TICT state is found to make the sensor non-emissive. With the addition of Zn, the TICT state is eliminated which greatly enhances the fluorescence of the sensor and achieves zinc ion detection. The interaction of the sensor with Cd and Hg are also explored, which well explains the good selectivity of the sensor.