Orbital Control and Coherent Charge Transport in Transition Metal Pt(II)-Pt(II) Lantern Complexes in Molecular Junctions

Platinum (II) dimers in organometallic complexes exhibit oscillatory vibrational charge transfer with optical excitation and whose nature depends strongly on the Pt-Pt distance. Yet the electronic transport of such devices has not been studied. We take a well-reported Pt(II) dimer complex that is ideal for transport in a molecular junction and subject it to a battery of electronic structure property calculations. With DFT, we find the orbital nature of the HOMO level to not be solely induced by the 5dz2 orbital as long thought, but rather a complex mixture with significant contributions from 6s orbital states from the Au electrodes that have not been considered before. We probe how the chemical tuning of the ligand affects the Pt-Pt bond length and thus conduction, by systematically modifying both the bridging ligands (BL) and cyclometallating ligands (CMLs) with donor (methyl) and acceptor (fluorine) derivatives. With nonequilibrium green’s functions (NEGF-DFT), we find patterns between the conductivity,...