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] ⋅ 2H2O).

Reawakening of a forgotten compound class: A researcher who has “rediscovered” the selenocyanates as an interesting compound class holds the starting materials of the principal chemical reaction (A = Li–Cs) in their hands. Against a background of a calculated precession image recorded after successful syntheses and characterization, she contemplates the flame colouration of the full series of quasibinary alkali‐metal selenocyanates that emerge from the oxidation of alkali‐metal cyanides with elemental selenium. More information can be found in the Full Paper by F. Tambornino et al. (DOI: 10.1002/chem.202102058). Artwork by Janina Ill.