Understanding the structure–property relationships in organic semiconductors is crucial for controlling their photophysical properties and developing new optoelectronic materials. Quadrupolar molecules, donor–acceptor–donor (DAD), have attracted extensive attention in various optoelectronic applications. However, the systematic studies on the differences on photophysical properties between DAD and simple donor–acceptor (DA) chromophores are rarely reported. Herein we present a comparative study on the excited state dynamics of DA and DAD fluorescence systems using theoretical calculation and transient absorption spectroscopy. Results show that DA and DAD molecules exhibit similar excited state dynamics, which are attributed to the distinctive excited-state symmetry breaking (ESSB) phenomenon observed in a DAD system. The strong photoluminescence (PL) and ultrafast charge separation (CS) from an ESSB-induced partial charge transfer (CT) state were clearly detected in different solvent environments. These results not only offer insight into the excited state dynamics of the DAD fluorescence system but also provide some basic guidelines for designing new optoelectronic materials.
