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Restriction of Conformation Transformation in Excited State: An Aggregation-Induced Emission Building Block Based on
Wentao Yu1, Han Zhang2, Ping-An Yin2
1Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology (SCUT), Guangzhou 510640, China.
Abstract:
The development of aggregation-induced emission (AIE) building block and deciphering its luminescence mechanism are of great significance. Here a feasible strategy for the construction of AIE unit based on E-Z isomerization (EZI) of exocyclic C=N double bond is proposed. Taking [1,2,4]thiadiazole[4,3-a]pyridine (TZP) derivative as an example, its aryl-substituted derivative (TZPP) shows obvious AIE character. The analysis of spectral data and theoretical calculations indicates that fast structural relaxation of TZPP in the emissive state plays a key role in a low fluorescence quantum yield in dilute solution, which should be caused by the small energy gap between locally excited (LE) state and twisted intramolecular charge transfer state. When in solid state, the bright emission with LE state characteristic reappears due to the large shift barrier of geometry transformation. As a potential building block for AIEgens with special heterocyclic structure, these findings would open up opportunities for developing various functional materials.
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