期刊
CHEMICAL SCIENCE
卷 9, 期 20, 页码 4662-4670出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c8sc01170b
关键词
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资金
- National Natural Science Foundation of China [21788102]
- National Basic Research Program of China (973 Program) [2013CB834701, 2013CB834702]
- Research Grants Council of Hong Kong [16308016, 16305015, C2014-15G, N_HKUST604/14, A_HKUST605/16, HKU17301815]
- Areas of Excellence Scheme [AoE/P-03/08]
- UGC Special Equipment Grant [SEG-HKU-07]
- University of Hong Kong
- Innovation and Technology Commission [ITC-CNERC14SC01, ITCRD/17-9]
- Technology Plan of Shenzhen [JCYJ20160229205601482]
- China Postdoctoral Science Foundation [2016 M602463]
- Fundamental Research Funds for the Central Universities [2017MS015]
- National Science Foundation for Young Scientists [51703066, 21702016]
- National Science Foundation of USA (NSF) [CHE-0840494]
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.e. formation of intermediate or rotation around the elongated C?C bond, is responsible for the AIE effect, which is strongly structure-dependent but not related to structural rigidity.
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