Abstract
We experimentally demonstrate that that nonradiative process, which competes with radiative decay, involves two main stages, namely the restricted intramolecular rotation and internal conversion process. The free rotation restriction of the unsaturated bond at the excited state is the key factor for AIE effects.
Highlights
Aggregation-induced emission (AIE) phenomena have been attracting more and more interest due to the colossal potential in chemo/biosensor, solid emitter, bioimaging, multistimuli response systems, and so on [1,2,3]
While the intramolecular rotation is generally related to the rotation of a single bond, this work speculated that the rotation of the unsaturated bond at the excited state would result in the fluorescence quenching of the AIEgen system in solution
The geometries of the ground and excited states of AIEgen system were optimized using the DFT and TDDFT with B3LYP functional and 6-31+G(d,p) basis set in gas phase and methanol, DMSO, and aniline solutions, respectively
Summary
Aggregation-induced emission (AIE) phenomena have been attracting more and more interest due to the colossal potential in chemo/biosensor, solid emitter, bioimaging, multistimuli response systems, and so on [1,2,3]. Due to the diversity and complexity of AIEgen systems, the mechanism that leads to AIE is sophisticated and uncertain from time to time for some specific AIE molecules. No any direct and convictive evidence has been provided to prove the rotation mechanism of the unsaturated bond at the excited state for AIEgen system. We can discuss fluorescence or fluorescence enhancement from RIR by intermolecular aggregation effect and from RIR by intramolecular rotation fixation. While the intramolecular rotation is generally related to the rotation of a single bond, this work speculated that the rotation of the unsaturated bond at the excited state would result in the fluorescence quenching of the AIEgen system in solution
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