Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 20, Issue 47, Pages 15349-15353Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201403811
Keywords
aggregation-induced emission; intramolecular motions; intramolecular rotations; intramolecular vibrations; tetraphenylethene
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Funding
- National Basic Research Program of China (973 Program) [2013CB834701]
- Research Grants Council of Hong Kong [HKUST2/CRF/10, N_HKUST620/11, 604711, 604913]
- University Grants Committee of HK [AoE/P-03/08]
- Guangdong Innovative Research Team Program [201101C0105067115]
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Aggregation-induced emission (AIE) has been harnessed in many systems through the principle of restriction of intramolecular rotations (RIR) based on mechanistic understanding from archetypal AIE molecules such as tetraphenylethene (TPE). However, as the family of AIE-active molecules grows, the RIR model cannot fully explain some AIE phenomena. Here, we report a broadening of the AIE mechanism through analysis of 10,10',11,11'-tetrahydro-5,5'-bidibenzo[a,d][7]annulenylidene (THBDBA), and 5,5'-bidibenzo[a, d][7] annulenylidene (BDBA). Analyses of the computational QM/MM model reveal that the novel mechanism behind the AIE of THBDBA and BDBA is the restriction of intramolecular vibration (RIV). A more generalized mechanistic understanding of AIE results by combining RIR and RIV into the principle of restriction of intramolecular motions (RIM).
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