A Comprehensive Study on the Full Series of Alkali-Metal Selenocyanates AI [SeCN] (AI =Li-Cs)

Chemistry. 2021 Sep 24;27(54):13552-13557. doi: 10.1002/chem.202102058. Epub 2021 Aug 19.

Abstract

The full series of quasibinary alkali-metal selenocyanates was synthesized either by oxidation of the respective cyanides (A=Li-Rb) or by metathesis (A=Cs). For Li[SeCN] only ball-milling and subsequent annealing led to the isolation of the quasibinary selenocyanate. Their structures were refined from single-crystal and powder X-ray data. The respective solid-state IR and Raman spectra were interpreted with the aid of solid-state quantum-mechanical calculations and DSC-TGA measurements allowed for extraction of melting points. Only for Li[SeCN] a possible phase transition was observed that is discussed on the basis of VT-PXRD experiments. It is also the only quasibinary selenocyanate to form a hydrate (Li[SeCN] ⋅ 2H2 O).

Keywords: alkali-metals; crystallography; selenocyanates; solid-phase synthesis; vibrational spectroscopy.