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

Research output: Contribution to Journal/MagazineJournal articlepeer-review

Forthcoming
  • Daniel P. Harrison
  • Robin Grotjahn
  • Masnun Naher
  • Seyed M. B. H. Ghazvini
  • Daniel M. Mazzucato
  • Marcus Korb
  • Stephen A. Moggach
  • Colin Lambert
  • Martin Kaupp
  • Paul J. Low
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<mark>Journal publication date</mark>26/08/2022
<mark>Journal</mark>Angewandte Chemie International Edition
Publication StatusAccepted/In press
<mark>Original language</mark>English

Abstract

Whilst 2- or 5-OMe groups on the bridging phenylene ring in [{Cp*(dppe)RuCΞC} 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)RuCΞC} 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 b-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.