期刊
CHEMICAL SCIENCE
卷 12, 期 32, 页码 10710-10723出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1sc02168k
关键词
-
资金
- National Natural Science Foundation of China [21775139, 21675143]
- Natural Science Foundation of Zhejiang Province [LR18B050001]
This study successfully demonstrates the controllable regulation of photophysical and photochemical processes by designing new AIEgens, including emission efficiency, color tuning, and photochemical reactions. By introducing heavy halogens and electron-donating groups, efficient emission control and color changes in the luminogens are achieved.
It is extremely challenging but desirable to regulate the photophysical and photochemical processes of aggregation-induced emission luminogens (AIEgens) in distinct states in a controllable manner. Herein, we design two groups of AIEgens based on a triphenylacrylonitrile (TPAN) skeleton with through-space conjugation (TSC) property, demonstrate controlled regulation of photophysical emission efficiency/color and photochemical photochromic and photoactivatable fluorescence behaviours of these compounds, and further validate design principles to achieve highly efficient and emission-tuning AIEgens and to accomplish photo-dependent color switches and fluorescence changes. It is surprisingly found that the introduction of heavy halogens like bromine into a TPAN skeleton dramatically enhances the emission efficiency, and such an abnormal phenomenon against the heavy-atom effect is attributed to the specific through-space conjugation nature of the AIE-active skeleton, effective intermolecular halogen-bond-induced restriction of intramolecular motions, and heavy atom-induced vibration reduction. The incorporation of two electron-donating amino groups into the TPAN skeleton cause the luminogens to undergo a bathochromic shifted emission due to the formation of a D-A pattern. Apart from the regulation of photophysical processes in the solid state, the construction of the D-A pattern in luminogens also results in extremely different photochemical reactions accompanying reversible/irreversible photochromism and photoactivatable fluorescence phenomena in a dispersed state. It is revealed that photo-triggered cyclization and decyclization reactions dominantly contribute to reversible photochromism of the TPAN family, and the photo-induced cyclization-dehydrogenation reaction is responsible for the irreversible color changes and photoactivatable fluorescence behaviours of the NTPAN family. The demonstrations of multiple-mode signaling in photoswitchable patterning and information encryption highlight the importance of controlled regulation of photophysics and photochemistry of fused chromic and AIE-active luminogens in distinct states.
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