DFT Investigation of the Molecular Properties of the Dimethylglyoximato Complexes [M(Hdmg)2] (M = Ni, Pd, Pt)

Important applications of the NiII, PdII and PtII complexes [M(Hdmg)2] (H2dmg = dimethylglyoxime) stem from their metal...metal stacked virtually insoluble aggregates. Given virtual insolubility materials, we postulated that rare reports on dissolved species in solution do not represent monomolecular but oligomers. We thus studied structural spectral properties entities these compounds using density functional theory (DFT) time-dependent DFT computations dimethyl sulfoxide (DMSO) as a solvent. The molecular geometries, IR UV-vis spectra, frontier orbitals were computed LANL2DZ ecp def2TZVP basis sets M06-2X functional. results are compared with available experimental other calculated data. optimised geometries proved asymmetric character two formed O–H…O bonds which connect Hdmg‒ ligands completely planar molecules. Calculated spectra revealed presence three absorptions range 180 to 350 nm red-shifted along series Ni–Pd–Pt. They assigned essentially ligand-centred π−π* transitions part metal(d) ligand(π*) charge transfer (MLCT) contributions. notorious d‒p dominating colour electronics solid-state oligomeric stacks negligible our models strongly supporting idea previously reported spectroscopic observations or biological effects solutions due rather species.