Electronic Structures of Cr(III) and V(II) Polypyridyl Systems: Undertones in an Isoelectronic Analogy

A recently reported description of the photophysical properties of V²⁺ polypyridyl systems has highlighted several distinctions between isoelectronic, d³, Cr³⁺, and V²⁺ tris-homoleptic polypyridyl complexes of 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen). Here, we combine theory and experimental data to elucidate the differences in electronic structures. We provide the first crystallographic structures of the V²⁺ complexes [V(bpy)₃](BPh₄)₂ (V-1B) and [V(phen)₃](OTf)₂ (V2) and observe pronounced trigonal distortion relative to analogous Cr³⁺ complexes. We use electronic absorption spectroscopy in tandem with TD-DFT computations to assign metal-ligand charge transfer (MLCT) properties of V-1B and V2 that are unique from the intraligand transitions, ⁴(³IL), solely observed in Cr³⁺ analogues. Our newly developed natural transition spin density (NTρ^α,β) plots characterize both the Cr³⁺ and V²⁺ absorbance properties. A multideterminant approach to DFT assigns the energy of the ²E state of V-1B as stabilized through electron delocalization. We find that the profound differences in excited state lifetimes for Cr³⁺ and V²⁺ polypyridyls arise from differences in the characters of their lowest doublet states and pathways for intersystem crossing, both of which stem from trigonal structural distortion and metal-ligand π-covalency.