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Quantum Interference in Mixed-Valence Complexes: Tuning Electronic Coupling Through Substituent Effects.
- Source :
-
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. - Publication Year :
- 2022
-
Abstract
- Whilst 2- or 5-OMe groups on the bridging phenylene ring in [{Cp*(dppe)RuC≡C} <subscript>2</subscript> (μ-1,3-C <subscript>6</subscript> H <subscript>4</subscript> )] <superscript>+</superscript> 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 <subscript>2</subscript> Cl <subscript>2</subscript> )) on ([{Cp*(dppe)RuC≡C} <subscript>2</subscript> (μ-1,3-C <subscript>6</subscript> H <subscript>3</subscript> -n-OMe)] <superscript>+</superscript> (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.<br /> (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Details
- Language :
- English
- ISSN :
- 1521-3773
- Volume :
- 61
- Issue :
- 45
- Database :
- MEDLINE
- Journal :
- Angewandte Chemie (International ed. in English)
- Publication Type :
- Academic Journal
- Accession number :
- 36031588
- Full Text :
- https://doi.org/10.1002/anie.202211000