Cs3Se22, a Selenium‐rich Caesium Polyselenide containing Se8 Crowns and $^{3}_{\infty}\rm [Se_{6}^{3-}]$ Anions with Radical Character

Abstract

AbstractCs3Se22 can be prepared together with the known compounds Cs2Sn2Se6 and Cs4Sn2Se6 by reacting Cs2CO3 and Sn in a CH3OH/en solution at 120 °C. The presence of CuCl and the macrocyclic ligand 1,10‐dithia‐18‐crown‐6 are essential for product formation. The caesium polyselenide consists of anionic nets $^{3}_{\infty}\rm [Se_{6}^{3-}]$ that are separated by two layers of discrete Se8 rings. Within the polymeric anions pairs of Se3·− radical anions and Se32− anions are linked through secondary interactions.