Fluorescent Rotary Switches: Four- vs Three-Substituted Phthalimide Boron Difluoride Schiff Base Complexes

Abstract

The influence of the substitution pattern in phthalimide boron difluoride Schiff base complexes as fluorescent molecular rotors has been investigated. Due to their ground-state zwitterionic structures, they have exhibited negative solvatochromism in absorption and blue-green emission with moderate to satisfactory photoluminescence quantum yields in solution. Ground-state and excited-state theoretical calculations and time-resolved emission spectroscopy revealed that the excited-state rotation is triggered by planar-induced charge transfer, resulting in switched emission toward the green region. Fluorescence lifetime measurements and species-associated emission spectra exhibited two emitting excited species in equilibrium via a planar transition-state barrier. The substitution pattern models showed different behavior in solid-state mechanochromic switching and were analyzed by subcell unit packing obtained from X-ray structure data. We have attempted to gain in-depth insight into the fluorescence mechanism and photoluminescence properties associated with the substitution pattern of the phthalimide motif in order to understand the structure-property-function relationship.