Iron versus Ruthenium: Clarifying the Electronic Differences between Prototypical Mixed-Valence Organometallic Butadiyndiyl Bridged Molecular Wires

The electronic structures of the prototypical bimetallic buta-1,3-diyn-1,4-diyl-bridged radical cation complexes [{M(dppe)Cp′} 2 (μ-C≡CC≡C)] + (M= Fe, Cp′ = Cp* ( 1a ), Cp ( 1b ); M = Ru, Cp′ = Cp* ( 2a ), Cp ( 2b )) have been (re)investigated using a combination of UV–vis–NIR and IR spectroelectrochemistry, and quantum chemical calculations based on both dispersion-corrected global (BLYP35-D3) and local (Lh-SsirPW92-D3) hybrid functionals. Following analysis of new and existing data, including the IR-active ν(C≡C) bands, the iron compounds [ 1 ] + are reclassified as valence-trapped (Robin and Day Class II) mixed-valence complexes, in contrast to the ruthenium complexes [ 2 ] +, which are delocalized (Robin and Day Class III) systems. All members of the series exist as a thermally populated distribution of conformers in solution, and the overlapping spectroscopic profiles make the accurate extraction of the parameters necessary for the analysis of [ 1 ] + and [ 2 ] + within the framework of the Marcus–Hush model extremely challenging. Analysis of the spin-density distributions from a range of conformational minima provides an alternative representation of the degree of charge localization, and a comparison between members of the series is presented.