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

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

Research output: Contribution to journalArticlepeer-review

8 Citations (Scopus)


Whilst 2- or 5-OMe groups on the bridging phenylene ring in [{Cp*(dppe)RuC equivalent to C}(2)(mu-1,3-C6H4)](+) 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 (CH2Cl2)) on ([{Cp*(dppe)RuC equivalent to C}(2)(mu-1,3-C6H3-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 beta-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 beta-HOSO and beta-LUSO, whilst the relative phases of the beta-HOSO and beta-LUSO in the 4-OMe substituted complex are consistent with predictions of constructive quantum interference from molecular circuit rules.

Original languageEnglish
Article numbere202211000
Number of pages8
Issue number45
Publication statusPublished - 7 Nov 2022


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