doi:10.1021/acs.jpcc.5c07119engBastante, PabloDavidson, Ross J.Chelli, YahiaDaaoub, Abdalghani H. S.Cea, PilarMartin, SantiagoBatsanov, Andrei S.Sangtarash, SaraSadeghi, HatefBryce, Martin R.Agrait, NicolasExperimental and theoretical studies of isomeric metal (N^C^N)Cl coordination complexes (Metal = Pt, Pd) with multiple conductance pathways in single-molecule junctionsART-2026-148282The 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 (Lp H) 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 π-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 −3.8 log(G/G0) and Ptm −3.3 log(G/G0), in contrast to the usual conductance trend (para > meta) for purely organic π-electron systems.2026http://zaguan.unizar.es/record/16919510.1021/acs.jpcc.5c07119http://zaguan.unizar.es/record/169195oai:zaguan.unizar.es:169195info:eu-repo/grantAgreement/ES/DGA/E31-23R-PLATONinfo:eu-repo/grantAgreement/EC/H2020/767187/EU/Quantum Interference Enhanced Thermoelectricity/QuIETThis project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No H2020 767187-QuIETinfo:eu-repo/grantAgreement/ES/MICINN/PID2022-141433OB-I00Journal of physical chemistry. C. 130, 7 (2026), 2763-2772byhttps://creativecommons.org/licenses/by/4.0/deed.esinfo:eu-repo/semantics/openAccess