Solid State Luminescence Enhancement in π-Conjugated Materials: Unraveling the Mechanism beyond the Framework of AIE/AIEE

Solid state luminescence enhancement (SLE) of conjugated organic materials has had a great impact in materials science, but a deep understanding has been rather limited to date. Here, we investigate a prototype example of SLE materials, cyano-substituted distyrylbenzene (DCS), by varying systematically and subtly the substitution pattern (inter alia of the position of the cyano-substituent) to give largely different photoresponse in fluid and solid solution as well in the crystalline state. The combination of quantitative (ultra)fast optical spectroscopic techniques, appropriate quantum-chemical methods, and structural (X-ray) data allows us to elucidate and rationalize all details of the SLE process, including steric versus electronic factors, radiative versus nonradiative decay channels, and intra- versus intermolecular contributions, providing a first holistic picture of SLE.