Origin of Anomalous Electronic Circular Dichroism Spectrum of RuPt₂(tppz)₂Cl₂(PF₆)₄ in Acetonitrile

Abstract

We report a theoretical study of the structures, energetics, and electronic spectra of the Pt^II/Ru^II mixed-metal complex RuPt₂(tppz)₂Cl₂(PF₆)₄ (tppz = 2,3,5,6-tetra­(2-pyridyl)­pyrazine) in acetonitrile. The hybrid B3LYP density functional theory and its TDDFT methods were used with a complete basis set (CBS) extrapolation scheme and a conductor polarizable continuum model (C-PCM) for solvation effects. Results showed that the trinuclear complex has four types of stable conformers and/or enantiomers. They are separated by high barriers owing to the repulsive H/H geometrical constraints in tppz. A strong entropy effect was found for the dissociation of RuPt₂(tppz)₂Cl₂(PF₆)_n in acetonitrile. The UV–visible and emission spectra of the complex were also simulated. They are in good agreement with experiments. In this work we have largely focused on exploring the origin of anomalous electronic circular dichroism (ECD) spectra of the RuPt₂(tppz)₂Cl₂(PF₆)₄ complex in acetonitrile. As a result, a new mechanism has been proposed together with a clear illustration by using a physical model