CsMnCl3(H2O)2 (CMCH) has been widely investigated for magnetic and optical applications, including anti-Stokes photoluminescence, microwave absorption, and magnon-assisted optical transitions. Herein, CMCH crystals, which are colorless and transparent (unlike the pink crystals reported previously), were obtained through a unique approach. Consequently, a high-resolution optical absorption spectrum and distinct thermal behavior were observed. The reversible (de)hydration of CMCH being accompanied by photoluminescence switching (mainly in terms of the color temperature) was rationalized using crystal structure analysis. As a result, water-soluble CMCH could be applied as a moisture-responsive luminescent ink. Moreover, density functional theory (DFT) calculations were performed to understand the optical absorption of CMCH.
