Magnetic Coupling and Intermetallic Electron Transfer in the Heterodinuclear Bioctahedral Complexes MW III Cl 9 n- (M = V II , Cr III , Mn IV ): Tweaking the Balance between Ferromagnetism and Antiferromagnetism

Petrie, SimonStranger, Robert2015-12-130020-1669http://hdl.handle.net/1885/85745Density functional theory (DFT) calculations have been used to investigate the effect of intermetallic electron transfer on the mode of magnetic coupling in the face-shared bimetallic complexes MWCI9n- (M = V, Cr, Mn; all with a nominal d3 valence electronic configuration on each metal atom). These calculations illustrate a simple rule: when the oxidation state of M is lower than that of W, antiferromagnetic coupling is preferred, while ferromagnetism (via crossed exchange pathways) is favored when M has the higher oxidation state. This underlying trend in intermetallic interactions is seen to depend on the interplay among ligand field splitting, spin polarization splitting of α- and β-spin orbitals, and the relative energies of the M and W valence d orbitals, and is mirrored in the results seen in a wider survey of mixed-metal, face-shared complexes.Keywords: chromium; ferromagnetic material; manganese; vanadium; article; complex formation; density; electron transport; magnetism; molecular interaction; oxidation; polarizationMagnetic Coupling and Intermetallic Electron Transfer in the Heterodinuclear Bioctahedral Complexes MW III Cl 9 n- (M = V II , Cr III , Mn IV ): Tweaking the Balance between Ferromagnetism and Antiferromagnetism200210.1021/ic01097032015-12-12