A first principles study of the electronic structure and optical response of heterobimetallic M-dicyanoaurate-based coordination polymers (M = Mn, Co, Ni, Zn and Cd).

The electronic structure and derived optical properties of five synthesized metal-dicyanoaurate(I), (K)M[Au(CN) 2 ], (M = Mn, Co, Ni, Zn and Cd), coordination polymers are described from a combined experimental analysis and theoretical study based on density functional theory. In this sense, the topological features that influence the electronic structure, which in turn give rise to electronic transitions associated with the band gap energy, are studied from first principles calculations (with hybrid HSE06 and GGA-PBE density functionals) and electronic spectroscopy. The impact of gold (through spin-orbit coupling) and aurophilic interactions on the electronic transitions that gives rise to optical properties is described. The calculated projected density of states and band dispersion diagrams shed light on the molecular orbital distribution and the role of a dicyanoaurate(I) molecular block as the origin of the optical properties. Infrared, Raman and ultraviolet-visible spectroscopic analyses reveal the effect that charge transfer interactions, of a metal → ligand and metal → metal nature, have on the electronic behavior within the solids through association with the polarizing power of transition metals and gold atoms.