Rational Design of Electronically Labile Dinuclear Fe and Co complexes with 1,10-Phenanthroline-5,6-Diimine: A DFT study.

A series of coordination compounds of redox-active 1,10-phenanthroline-5,6-diimine with Co bis-diketonates and Fe dihydrobis(pyrazolyl)borates has been computationally designed by means of density functional theory (DFT UB3LYP*/6-311++G(d,p)) calculations of their electronic structure, energy characteristics, and magnetic properties. Four types of complexes differing by the nature and position of the terminal metal-centered fragments have been considered. The performed systematic calculations have revealed the systems capable of undergoing thermally initiated spin-state switching rearrangements, including those governed by the synchronized mechanisms of spin crossover and valence tautomerism. The predicted magnetic characteristics allow one to consider the dinuclear cobalt complexes and heterometallic Co/Fe compounds with 1,10-phenanthroline-5,6-diimine as building blocks for molecular and quantum electronics devices. © 2019 Wiley Periodicals, Inc.