Deciphering the working mechanism of aggregation-induced emission of tetraphenylethylene derivatives by ultrafast spectroscopy

Aggregation-induced emission (AIE) is the long-sought solution to the problem of aggregation-caused quenching that has hampered efficient application of fluorescent organic materials. An important goal on the way to fully understand the working mechanism of the AIE process was, for more than a decade, and still remains obtaining more comprehensive insights into the correlation between the ultrafast excited-state dynamics in tetraphenylethylene (TPE)-based molecules and the AIE effect in them. Here we report a number of TPE-based derivatives with varying structural rigidities and AIE properties. Using a combination of ultrafast time-resolved spectroscopy and computational studies, we observe a direct correlation between the state-dependent coupling motions and inhibited fluorescence, and prove the existence of photocyclized intermediates in them. We demonstrate that the dominant non-radiative relaxation dynamics, <i>i.e.</i> formation of intermediate or rotation around the elongated C[double bond, length as m-dash]C bond, is responsible for the AIE effect, which is strongly structure-dependent but not related to structural rigidity.