Infrared spectra (500-20 cm−1) of some metal-thiocyanate linkage isomers

Goodgame, D. M. L.; Malerbi, B.W.

doi:10.1016/0584-8539(68)80147-3

Cited by 10 publications

(1 citation statement)

References 8 publications

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“…We note that there are no other calculated vibrational modes (Raman or IR) in the 490 cm –1 region, as the two nearest are at 799 cm –1 (SCN stretches) and 285 cm –1 (UO bending) (Table S18). Moreover, we have ruled out the possibility of coupling that originates from the U–N stretching frequencies, as these are expected to be lower in energy. − …”

Section: Discussionsupporting

confidence: 65%

Thermochromic Uranyl Isothiocyanates: Influencing Charge Transfer Bands with Supramolecular Structure

et al. 2018

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The synthesis and structural characterization of seven new [UO(NCS)]- and [UO(NCS)Cl]-containing materials charge balanced by 4-phenylpyridinium or 4,4'-bipyridinium cations are reported. Assembly of these materials occurs via a diverse set of noncovalent interactions, with the most prevalent involving the terminal sulfur atoms, which can both accept hydrogen bonds and/or form S···S and S···O interactions. The electrostatic potential of the [UO(NCS)] and [UO(NCS)Cl] anions was calculated and mapped on the 0.001 au isodensity surface to rationalize the observed assembly modes and to provide an electrostatic basis to elucidate the role of the S atoms as both donors and acceptors of noncovalent interactions. Compounds 1-7 display a range of colors (red to yellow) as well as pronounced thermochromism. A computational treatment (time-dependent density functional theory, TDDFT) of the absorbance properties supports the temperature dependence on the ratio of inter- to intramolecular ligand to metal charge transfer (LMCT) bands as obtained from UV-vis diffuse reflectance analysis. Finally, the luminescence profiles of these materials feature additional peaks atypical for most uranyl-containing materials, and a combined spectroscopic (Raman, IR, and fluorescence) and computational (harmonic frequency calculations) effort assigns these as originating from vibronic coupling between the ν U═O symmetric stretch and bending modes of the isothiocyanate ligands.

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Section: Discussionsupporting

confidence: 65%