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Abstract
The electronic structures of the prototypical bimetallic buta-1,3-diyn-1,4-diyl-bridged radical cation complexes [{M(dppe)Cp'}(2)(mu-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 v(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.
Original language | English |
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Pages (from-to) | 1432-1445 |
Number of pages | 14 |
Journal | Organometallics |
Volume | 37 |
Issue number | 9 |
DOIs | |
Publication status | Published - 14 May 2018 |
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Dive into the research topics of 'Iron versus Ruthenium: Clarifying the Electronic Differences between Prototypical Mixed-Valence Organometallic Butadiyndiyl Bridged Molecular Wires'. Together they form a unique fingerprint.Projects
- 2 Finished
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From the Electronics of Molecules to Molecular Electronics
Low, P. & Nichols, R.
1/01/14 → 31/12/17
Project: Research
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