Assembling Smallest Prussian Blue Analogs Using Chiral Hydrogen Bond-Donating Unit toward Complete Phase Transition.

Exploring methods for assembling functional materials at the molecular level may yield functional expressions derived from the assembly method. This study developed novel switchable molecular assemblies characterized by abrupt, complete phase transitions promoted via hydrogen bonding with a chiral carboxylic acid. These assemblies were prepared by aggregating discrete molecules that are unresponsive to external stimuli. Furthermore, enantiopure hydrogen-bond donor (HBD) molecules provide switchable compounds with cooperative and abrupt phase transitions, whereas the racemic mixture of the HBD provides a hydrogen-bonded one-dimensional compound with a broad and incomplete phase transition when structural disordering is observed. This study presents a novel strategy for observing metal-to-metal electron-transfer-coupled spin transitions via hydrogen-bond formation.