The compounds and complexes 1,4‐C6H4(C≡C‐cyclo‐3‐C4H3S)2 (2), trans‐[Pt(C≡C‐cyclo‐3‐C4H3S)2(PEt3)2] (3), trans‐[Ru(C≡C‐cyclo‐3‐C4H3S)2(dppe)2] (4; dppe=1,2‐bis(diphenylphosphino)ethane) and trans‐[Ru(C≡C‐cyclo‐3‐C4H3S)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.
Class II mixed-valenceb imetallic complexes {[Cp'(PP)M]CCÀCN[M'(PP)'Cp']} 2 + (M, M' = Ru, Fe;P P = dppe, (PPh 3 ) 2 ;C p ' = Cp*, Cp) exist as conformational ensembles in fluid solution, with ap opulationo fs tructures ranging from cis-t otrans-like geometries.E ach conformer gives rise to its own series of low-energy intervalence charge-transfer (IVCT) and local d-d transitions, which overlap in the NIR region,g iving complexb and envelopes in the NIR absorption spectrum,w hich prevent any meaningful attempta t analysis of the band shape. However,D FT and time-dependent (TD)DFT calculations with dispersion-corrected global-hybrid( BLYP35-D3) or local hybrid (lh-SsirPW92-D3) functionals on as malln umber of optimised structures chosen to sample the ground state potentiale nergy hypersurfaces of each of these complexes has proven sufficient to explain the majorf eatures of the electronic spectra. Although modesti n termso fc omputational expense, this approachp rovides a more accurated escription of the underlying molecular electronics tructure than would be possible through analysiso f the IVCT band by using the static point-charge model of Marcus-Hush theory and derivatives, or TDDFT calculations from as ingle (global)m inimum energy geometry.[a] S.Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.