Quantum Interference in Mixed-Valence Complexes: Tuning Electronic Coupling Through Substituent Effects.

Autor: Harrison DP; School of Molecular Sciences, University of Western Australia, 35 Stirling Highway, Crawley, WA, 6009, Australia., Grotjahn R; Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, 10623, Berlin, Germany.; Present address: Department of Chemistry, University of California, Irvine, 1102 Natural Science II, Irvine, CA 92697-2025, USA., Naher M; School of Molecular Sciences, University of Western Australia, 35 Stirling Highway, Crawley, WA, 6009, Australia., Ghazvini SMBH; School of Molecular Sciences, University of Western Australia, 35 Stirling Highway, Crawley, WA, 6009, Australia., Mazzucato DM; School of Molecular Sciences, University of Western Australia, 35 Stirling Highway, Crawley, WA, 6009, Australia., Korb M; School of Molecular Sciences, University of Western Australia, 35 Stirling Highway, Crawley, WA, 6009, Australia., Moggach SA; School of Molecular Sciences, University of Western Australia, 35 Stirling Highway, Crawley, WA, 6009, Australia., Lambert C; Department of Physics, University of Lancaster, Lancaster, LA1 4YB, UK., Kaupp M; Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, 10623, Berlin, Germany., Low PJ; School of Molecular Sciences, University of Western Australia, 35 Stirling Highway, Crawley, WA, 6009, Australia.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2022 Nov 07; Vol. 61 (45), pp. e202211000. Date of Electronic Publication: 2022 Oct 11.
DOI: 10.1002/anie.202211000
Abstrakt: Whilst 2- or 5-OMe groups on the bridging phenylene ring in [{Cp*(dppe)RuC≡C} 2 (μ-1,3-C 6 H 4 )] + have little influence on the electronic structure of this weakly coupled mixed-valence complex, a 4-OMe substituent enhances ground state electron delocalization, and increases the intensity of the IVCT transition. Vibrational frequency and TDDFT calculations (LH20t-D3(BJ), def2-SVP, COSMO (CH 2 Cl 2 )) on ([{Cp*(dppe)RuC≡C} 2 (μ-1,3-C 6 H 3 -n-OMe)] + (n=2, 4, 5) models are in excellent agreement with the experimental results. The stronger ground state coupling is attributed to the change in composition of the β-HOSO brought about by the 4-OMe group, which is ortho or para to each of the metal fragments. The intensity of the IVCT transition increases with the greater overlap of the β-HOSO and β-LUSO, whilst the relative phases of the β-HOSO and β-LUSO in the 4-OMe substituted complex are consistent with predictions of constructive quantum interference from molecular circuit rules.
(© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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