Six-Membered Electron Transfer Series [V(dithiolene)3]z (z = 1+, 0, 1−, 2−, 3−, 4−). An X-ray Absorption Spectroscopic and Density Functional Theoretical Study

摘要: The electronic structures of vanadium centers coordinated by three dithiolene ligands have been elucidated using a host physical methods: X-ray crystallography, cyclic voltammetry, absorption, electron paramagnetic resonance (EPR), and absorption spectroscopies, augmented density functional theoretical (DFT) calculations. consensus structure derived from this approach is V(IV) central ion for the neutral, monoanionic, dianionic members transfer series, where tris(dithiolene) ligand units are (L(3))(4-), (L(3))(5-*), (L(3))(6-), respectively. trigonal prismatic monoanions, [V(IV)(L(3)(5-*))](1-) (S = 0), defined as singlet diradicals crystallographically observed fold results strong antiferromagnetic coupling between metal- ligand-based magnetic orbitals. These contrasted with corresponding tris(dioxolene)vanadium series toward establishing factors that govern molecular or octahedral geometries in systems redox noninnocent ligands.