Water and Alcohol Vapor Sensitivity and Calorimetric Study on Magnetic Octacyano-Bridged Bimetallic Assemblies

This review describes unique magnetic functionalities observed in cyano-bridged bimetallic assemblies that are classified as molecule-based magnets. Copper octacyanotungstate (1) has a 3-dimensional network structure. As the temperature decreases, 1 exhibits a magnetic dimensional crossover from 2-dimensional Heisenberg-type magnetic ordering to 3-dimensional Heisenberg-type magnetic ordering, which originates from the switching of the dominant superexchange interaction from the intralayer to the interlayer. Cobalt octacyanoniobate (2) exhibits humidity-sensitive magnetism from ferromagnetism to antiferromagnetism as the humidity decreases. Copper octacyanotungstate (3), whose crystal structure differs from 1, displays an alcohol-sensitive magnetism with an extensive change in magnetization. The diverse spatial configurations and flexible coordination geometries are important to observe such magnetic functionalities because these features enable bimetallic assemblies to be altered using external stimuli.