Phenol- and catechol-based ruthenium(II) polypyridyl complexes as colorimetric sensors for fluoride ions
D Amilan Jose1, Prasenjit Kar, Debasis Koley
1Central Salt and Marine Chemicals Research Institute, Bhavnagar 364002, Gujarat, India.
Abstract:
We report two ruthenium(II) polypyridyl complexes with pendant phenol/catechol functionality that act as colorimetric sensors for fluoride ions. Experiments have revealed that hydrogen bond formation occurs with a slight excess of fluoride ion. However, in higher [F-], deprotonation of the O-H functionality resulted. Time-dependent (TD-DFT) calculations at the B3LYP/LANL2DZ level have shown that new bands appear at longer wavelengths upon complexation with fluoride ions. These are of mixed character, MLCT (dpi(Ru)-->pi*(L1/bpy)), and intra- and interligand [pi(L1)-->pi*(bpy) and pi(L1)-->pi*(L1)] transitions. These complexes also act as sensors for fluoride ions in solvent-water mixtures.
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When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human eye.


