期刊
JOURNAL OF PHYSICAL CHEMISTRY B
卷 120, 期 27, 页码 6730-6738出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcb.6b04474
关键词
-
资金
- European Research Council (ERC) [278845]
- ERC [278845]
- Research and Development Operational Programme - ERDF [26230120002, 26210120002]
- European Research Council (ERC) [278845] Funding Source: European Research Council (ERC)
A recently synthesized Schiff base used as a probe for aluminum cations was studied with ab initio models. The primary reason for the lack of fluorescence in aprotic solvents was found to be the presence of an efficient conical intersection (CI) between the ground-states and the first singlet excited-states close to the Franck-Condon geometry. The excited-state pathway leading to this CI is barrierless but implies large amplitude motions, explaining why the fluorescence was observed in frozen acetonitrile matrix. Our calculations suggest that constraining the molecule by impending the rotation around the imino bond enables excited-state intramolecular proton transfer. A similar stiffening mechanism is responsible for the strong fluorescence turn-on after formation of complexes between Al3+ cations and dehydrogenated Schiff base. Finally, the analysis of the possible fluorescence mechanisms in water indicates that the anion of 1 is the likely fluorescence source. Overall, this work allows one to disentangle the various origins of fluorescence switching in a probe.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据