Theoretical studies on the structural and spectroscopic properties of an iminocoumarin-based probe and its metal...

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 g1, g2, a1 and a2) for each of them have been optimized, except for CaL having only three without the g2 isomer. All of these structures have been confirmed by frequency calculations. In the aqueous solution, the a2 isomer of the L probe was calculated to be the most stable, while the g1 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.