NDLI: Theoretical studies on the structural and spectroscopic properties of an iminocoumarin-based probe and its metal complexation: an implication for a fluorescence probe

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Li, Xing-rui Pan, Qing-jiang Sun, Zhong-ming Guo, Yuan-ru Zhang, Ming-jing
Description	Author Affiliation: Guo YR ( Key Laboratory of Bio-based Material Science and Technology of Education Ministry, College of Material Science and Engineering, Northeast Forestry University, Harbin 150040, China.)
Abstract	To understand the sensing behaviors of molecular fluorescent probes , an N,N-di(picolyl)aminoethyl-iminocoumarin probe (L) and its complexation with metal(II) ions (ML, M = Mg, Ca, Zn, Cd and Hg) were examined by relativistic density functional theory (DFT). Four stable conformational isomers (labeled as g1g1g1, g2g2, a1a1 and a2a2) for each of them have been optimized, except for CaL having only three without the g2g2 isomer. All of these structures have been confirmed by frequency calculations. In the aqueous solution, the a2a2 isomer of the L probe was calculated to be the most stable, while the g1g1g1 isomer turns out to be energetically favorable upon binding with metal ions. At these isomeric geometries, the experimentally obtained absorption was well reproduced by calculations of time-dependent DFT (TD-DFT) and a conductor-like polarized continuum model (CPCM). A slight red-shifting from L (508 nm) to ML (516–528 nm) was found. This is due to the metal affinity that stabilizes the LUMOs of ML greater than the HOMOs. Singlet excited-state structures of L and ML (M = Zn, Cd and Hg) were fully optimized using the TD-DFT approach, giving more relaxed geometries than their respective ground-state ones. Their fluorescent emissions in the aqueous solution were calculated to be 543 and 551–560 nm, respectively, agreeing with experimental values of 543 nm for L and 558 nm for ZnL. The present study also presents theoretical support for a sensing mechanism of photo-induced charge transfer of the L probe that was proposed in the previous experiment.
ISSN	14779226
Issue Number	36
Volume Number	42
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2013-09-28
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Benzothiazoles Chemistry Cations, Divalent Coordination Complexes Coumarins Fluorescent Dyes Picolines Models, Molecular Molecular Dynamics Simulation Comparative Study Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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