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

Harrison, Daniel P. and Grotjahn, Robin and Naher, Masnun and Ghazvini, Seyed M. B. H. and Mazzucato, Daniel M. and Korb, Marcus and Moggach, Stephen A. and Lambert, Colin and Kaupp, Martin and Low, Paul J. (2022) Quantum Interference in Mixed‐Valence Complexes:Tuning Electronic Coupling Through Substituent Effects. Angewandte Chemie International Edition. ISSN 1433-7851 (In Press)

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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.

Item Type:
Journal Article
Journal or Publication Title:
Angewandte Chemie International Edition
Uncontrolled Keywords:
/dk/atira/pure/subjectarea/asjc/1500/1503
Subjects:
ID Code:
175608
Deposited By:
Deposited On:
07 Sep 2022 08:35
Refereed?:
Yes
Published?:
In Press
Last Modified:
09 Sep 2022 02:15