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The Use of Bridging Ligand Substituents to Bias the Population of Localized and Delocalized Mixed-Valence Conformers in Solution. | LitMetric

AI Article Synopsis

  • The electronic properties of bimetallic mixed-valence complexes are influenced by the orbital overlaps between metal centers connected by a bridge, which affects their spectroscopic behavior.
  • In particular complexes like [{Cp*(dppe)Ru}(μ-C≡CC H C≡C){Ru(dppe)Cp*}], the flexibility of the metal fragments and the bridge leads to a variety of conformations that impact their electronic structure.
  • The study employs electronic structure calculations and spectroscopic techniques to demonstrate that the conformational diversity can be influenced by the steric and electronic characteristics of the bridging diethynylarylene groups.

Article Abstract

The electronic structure and associated spectroscopic properties of ligand-bridged, bimetallic 'mixed-valence' complexes of the general form {M}(μ-B){M } are dictated by the electronic couplings, and hence orbital overlaps, between the metal centers mediated by the bridge. In the case of complexes such as [{Cp*(dppe)Ru}(μ-C≡CC H C≡C){Ru(dppe)Cp*}] , the low barrier to rotation of the half-sandwich metal fragments and the arylene bridge around the acetylene moieties results in population of many energy minima across the conformational energy landscape. Since orbital overlap is also sensitive to the particular mutual orientations of the metal fragment(s) and arylene bridge through a Karplus-like relationship, the different members of the population range exemplify electronic structures ranging from strongly localized (weakly coupled Robin-Day Class II) to completely delocalized (Robin-Day Class III). Here, we use electronic structure calculations with the hybrid density functional BLYP35-D3 and a continuum solvent model in combination with UV-vis-NIR and IR spectroelectrochemical studies to show that the conformational population in complexes [{Cp*(dppe)Ru}(μ-C≡CArC≡C){Ru(dppe)Cp*] , and hence the dominant electronic structure, can be biased through the steric and electronic properties of the diethynylarylene (Ar) moiety (Ar=1,4-C H , 1,4-C F , 1,4-C H -2,5-Me , 1,4-C H -2,5-(CF ) , 1,4-C H -2,5- Pr ).

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Source
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC9401031PMC
http://dx.doi.org/10.1002/chem.202200926DOI Listing

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