Tuning the properties of M(diimine)(dithiolate) complexes – The role of the metal and solvent effect. A combined experimental, DFT and TDDFT study

A combined experimental and DFT/TDDFT study on a series of seven M(diimine)(dithiolate) complexes of Group VIII metals has been performed. This analysis focuses mainly on three aspects: (a) the role of the metal, (b) the connection of NLO properties, through the intrinsic hyperpolarizability, with the slope of solvatochromic plots and (c) the effect of solvation on the valence orbitals of the complexes. Besides, the molecular and the electronic structure as well as the bonding scheme of these complexes are also explored. The three aforementioned aspects were not satisfactorily clarified in the literature up to now. Moreover, as it is proved, they possess a central role in the experimental design of the reactions in which these complexes take place or in the design of the synthesis of compounds with pre-required properties.