Affiliation:
1. State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials (IAM) Nanjing University of Posts & Telecommunications 9 Wenyuan Road Nanjing 210023 China
2. Key Laboratory of Fine Chemical Application Technology Sichuan Vocational College of Chemical Technology 733 Huguo Road Luzhou 646300 China.
Abstract
AbstractThe interplay of host‐guest interactions and controlled modulation of spin‐crossover (SCO) behavior is one of the most exploited topics regarding data storage, molecular sensing, and optical technologies. This study examines the effect of solvents on the spin‐crossover (SCO) behavior of manganese(III) complexes [Mn(sal‐N‐1,5,8,12)]I•S (S=CH3OH, C2H5OH, CH3CN) (1) and [Mn(sal‐N‐1,5,8,12)]I3 (2), where (sal‐N‐1,5,8,12)2− is 2,2′‐((1E,13E)‐2,6,9,13‐tetraazatetradeca‐1,13‐diene‐1,14‐diyl)diphenol synthesized by salicylaldehyde and 1,2‐bis(3‐aminopropylamino)ethane. The complexes, crystallizing in orthorhombic or monoclinic systems, exhibit similar supramolecular arrangements with one‐dimensional cationic chains at low temperatures. Magnetic studies reveal that solvent inclusion sharpens the SCO transition and lowers the transition temperature. Specifically, 1⋅CH3OH shows a 13 K thermal hysteresis due to methanol‘s mobility through the channels in the cationic framework. Although the solvent‐free compound was not obtained, compound 2 with a linear I3− anion was synthesized, displaying extensive cation‐anion contacts and a distinct 13 K thermal hysteresis upon heating due to altered intermolecular cooperativity. This emphasizes the significant role of solvent introduction and variation in crystal packing and their impact on the SCO properties.
Funder
National Natural Science Foundation of China