Single‐Molecule Conductance Studies of Organometallic Complexes Bearing 3‐Thienyl Contacting Groups

Abstract

The compounds and complexes 1,4-C₆ H₄ (C≡C-cyclo-3-C₄ H₃ S)₂ (2), trans-[Pt(C≡C-cyclo-3-C₄ H₃ S)₂ (PEt₃ )₂ ] (3), trans-[Ru(C≡C-cyclo-3-C₄ H₃ S)₂ (dppe)₂ ] (4; dppe=1,2-bis(diphenylphosphino)ethane) and trans-[Ru(C≡C-cyclo-3-C₄ H₃ S)₂ {P(OEt)₃ }₄ ] (5) featuring the 3-thienyl moiety as a surface contacting group for gold electrodes have been prepared, crystallographically characterised in the case of 3-5 and studied in metal|molecule|metal junctions by using both scanning tunnelling microscope break-junction (STM-BJ) and STM-I(s) methods (measuring the tunnelling current (I) as a function of distance (s)). The compounds exhibit similar conductance profiles, with a low conductance feature being more readily identified by STM-I(s) methods, and a higher feature by the STM-BJ method. The lower conductance feature was further characterised by analysis using an unsupervised, automated multi-parameter vector classification (MPVC) of the conductance traces. The combination of similarly structured HOMOs and non-resonant tunnelling mechanism accounts for the remarkably similar conductance values across the chemically distinct members of the family 2-5.