Topochemical intercalation reactions of ZrSe3

• Published in: Journal of solid state chemistry 2022-10, Vol.314, p.123436, Article 123436
• Main Authors: Elgaml, Mahmoud, Cassidy, Simon J., Clarke, Simon J.
• Format: Article
• Language: English
• Subjects: Intercalation; Stacking faults; Transition metal trichalcogenides; Zirconium triselenide
• ISSN: 0022-4596; 1095-726X
• DOI: 10.1016/j.jssc.2022.123436

Intercalation of alkali and alkaline earth metals into ZrSe3 via soft chemical routes injects electrons and has a significant effect on the selenide-selenide bonding. K, Rb and Cs intercalates of ZrSe3 prepared at low temperatures (−78 ​°C) from metal ammonia solutions contrast with related polymorphs obtained at high temperature (850 ​°C). KxZrSe3 synthesised at low temperatures crystallises in orthorhombic Cmc21, while the polymorph obtained at high temperatures crystallises in Immm. The two structures prepared under drastically different conditions differ by relative shifting of ZrSe3 layers. In contrast, CsxZrSe3 shows the Immm polymorph at low temperature and the Cmc21 polymorph at high temperatures, while a single RbxZrSe3 polymorph in Immm is formed at both temperatures. Intercalation of Ca from liquid ammonia facilitates the co-intercalation of the solvent because of the strong solvation of Ca2+. This compound has severe faulting due to the flexibility in the relative shifts of adjacent ZrSe3 layers. [Display omitted] •Intercalates of ZrSe3 with K, Rb and Cs synthesised at low temperature using metal/ammonia solutions.•Alkali metal intercalates adopt two polymorphs, which differ by relative shifting of ZrSe3 layers.•Low temperature intercalation produces complementary polymorphs to those found at high temperature.•Intercalation of Ca incorporates the ammonia solvent, structure has severe stacking faults.