Projects per year
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≡CC6H4C≡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-C6H4, 1,4-C6F4, 1,4-C6H2-2,5-Me2, 1,4-C6H2-2,5-(CF3)2, 1,4-C6H2-2,5-iPr2).
Original language | English |
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Article number | e202200926 |
Journal | Chemistry - A European Journal |
Volume | 28 |
Issue number | 44 |
DOIs | |
Publication status | Published - 4 Aug 2022 |
Fingerprint
Dive into the research topics of 'The Use of Bridging Ligand Substituents to Bias the Population of Localized and Delocalized Mixed-Valence Conformers in Solution'. Together they form a unique fingerprint.Projects
- 2 Finished
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Fill it, Squeeze it, Crush it: Extreme Gas Uptake in Microporous Materials
Moggach, S. (Investigator 01)
ARC Australian Research Council
1/10/20 → 30/09/24
Project: Research
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A radical approach to the design of components for molecular electronics
Low, P. (Investigator 01), Nichols, R. (Investigator 02), Lambert, C. (Investigator 03), Kaupp, M. (Investigator 04) & Becker, T. (Investigator 05)
ARC Australian Research Council
1/01/19 → 11/04/22
Project: Research
Research output
- 5 Citations
- 1 Doctoral Thesis
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Studies of Electronic Structures and Electron Transfer in Bi- and Multi-metallic Complexes
Safari, P., 2022, (Unpublished) 450 p.Research output: Thesis › Doctoral Thesis
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