loading . . . Experimental and Theoretical Studies of Isomeric Metal (N^C^N)Cl Coordination Complexes (Metal = Pt, Pd) with Multiple Conductance Pathways in Single-Molecule Junctions The present work provides insight into the effect of connectivity within isomeric 3,5-bis(pyridin-2-yl)phenyl (N^C^N) platinum and palladium complexes on their electron transmission properties within gold|molecule|gold junctions. The ligands 3,5-bis(4-(methylthio)pyridin-2-yl)phenyl hexanoate (LmH) and 3,5-bis(5-(methylthio)pyridin-2-yl)phenyl hexanoate (LpH) were synthesized and coordinated with either PtCl or PdCl to form complexes Ptm, Ptp, Pdm and Pdp. X-ray photoelectron spectroscopy (XPS) measurements evaluated the contacting modes of the molecules in the junctions. A combination of scanning tunneling microscopy-break junction (STM-BJ) measurements and density functional theory (DFT) calculations demonstrate that for the single-molecule S¡¡¡S contacted junctions metal coordination enhanced the conductance compared with the free ligands. Notably, the higher degree of orbital mixing between the metal center and the ligand Ď-orbitals in the metal complexes plays a greater role than quantum interference to the extent that the complexes that incorporate ligands substituted with thiomethyl groups in meta positions relative to the pyridine-benzene linkages have a higher conductance than their para-analogs, e.g., Ptp â3.8 log(G/G0) and Ptm â3.3 log(G/G0), in contrast to the usual conductance trend (para > meta) for purely organic Ď-electron systems. https://pubs.acs.org/doi/10.1021/acs.jpcc.5c07119