Correlation between structural, physical and chemical properties of three new tetranuclear NiII clusters

Abstract

Based on a new family of Ni^II cubane-like clusters, this work addresses current challenges in the synthesis, analysis and dynamics of single-molecule-magnet (SMM) systems. Investigation of various synthetic routes and desorption–sorption processes yielded a series of isomorphous compounds: [Ni₄L₄(CH₃OH)₄]·xsolv, [Ni₄L₄(CH₃OH)₄] and [Ni₄L₄]. In order to analyze these deceivingly simple materials, several analytical and quantum mechanical methods had to be used. This revealed materials with mixed lattice solvents, statistical disorder of the solvent, and disordered [Ni₄L₄] cores which offered an insight into the risks of the self-assembly process and interconversion dynamics of the investigated Ni^II family. These findings also allowed structural–magnetic relationships to be established, and the outcomes were exploited in two ways: first, the effect of the coordinated and lattice solvent on the magnetic properties was examined, and second, magnetic properties were used to facilitate crystal structure determination.