Molecular Design of Organometallic Materials: Effect of the Metallophilic Interactions, Ligand, Metal, and Oxidation State

The present book chapter is devoted to metal (M) homoleptic complexes with pyridyl–triazolate ligands (L) and their importance for the molecular design of optical and conducting materials. It summarizes our recently published, as well as new DFT/TD-DFT results on the role of the ligand, metal and oxidation state for tuning of molecular and supramolecular properties in ML 2 complexes. The intermolecular interactions are taken into account by comparison between monomer (ML 2 ) and dimer organometallic complexes (ML 2 … ML 2 ). The ligand effect is demonstrated in Pt(II)-complexes by modifying the electronic structure of the pyridyl-triazolate ligands. The role of the metal is estimated in the case of Pd(II) and Pt(II)-complexes with the same pyridyl-triazolate ligand. The effect of the oxidation state is revealed by simulations on Pt(II)-dimers in mixed valence [ML 2 … ML 2 ] +• and doubly oxidized [ML 2 … ML 2 ] 2+ states. The obtained structure-property relationships are interpreted with respect to available experimental data and are used for the formulation of molecular design strategies.