期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 144, 期 6, 页码 2726-2734出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c11874
关键词
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资金
- NSFC [22171291, 21720102007, 21821003, 21890380]
- Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program [2017BT01C161]
- Fundamental Research Funds for the Central Universities
In this study, a coordination polymer with ESIPT properties was synthesized, and the switching between thermally activated fluorescence and long persistent luminescence was achieved by controlling the temperature. The mechanism of ISC/RISC energy transfer in the coordination polymer was revealed, providing a new pathway for the design and application of advanced optical materials in the future.
Excited-state intramolecular proton transfer (ESIPT) molecules demonstrating specific enol-keto tautomerism and the related photoluminescence (PL) switch have wide applications in displaying, sensing, imaging, lasing, etc. However, an ESIPT-attributed coordination polymer showing alternative PL between thermally activated fluorescence (TAF) and long persistent luminescence (LPL) has never been explored. Herein, we report the assembly of a dynamic Cd(II) coordination polymer (LIFM-101) from the ESIPT-type ligand, HPI2C (5-(2-(2-hydroxyphenyl)-4,5-diphenyl-1H-imidazol-1-yl)isophthalic acid). For the first time, TAF and/or color-tuned LPL can be achieved by controlling the temperature under the guidance of ESIPT excited states. Noteworthily, the twisted structure of the HPI2C ligand in LIFM-101 achieves an effective mixture of the higher-energy excited states, leading to ISC (intersystem crossing)/RISC (reverse intersystem crossing) energy transfer between the high-lying keto-triplet state (T-n(K*)) and the first singlet state (S-1(K*)). Meanwhile, experimental and theoretical results manifest the occurrence probability and relevance among RISC, ISC, and internal conversion (IC) in this unique ESIPT-attributed coordination polymer, leading to the unprecedented TAF/LPL switching mechanism, and paving the way for the future design and application of advanced optical materials.
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