Abstract
A family of metal dichloride complexes having a bisferrocenyl- substituted pyridinediimine ligand was systematically synthesized ((Fc2PDI)MCl2, M = Mg, Zn, Fe, and Co) and characterized crystallographically, spectroscopically, electrochemically, and computationally. Electronic coupling between the ligand ferrocene units is switched on upon binding to a MCl2 fragment, as evidenced by both sequential oxidation of the ferrocenes in cyclic voltammetry (ΔEox ≈ 200 mV) and by Inter-Valence Charge Transfer electronic excitations in the near IR. Additionally, UV-vis spectra are used to directly observe orbital mixing between the ferrocenyl units and the imine π system since breaking of the orbital symmetry results in allowed transitions (ϵ = 2800 M-1cm-1 vs ϵ ≈ 200 M-1cm-1 in free ferrocene) as well as broadening and red-shifting of the ferrocenyl transitions-indicating organic character in formerly pure metal-centered transitions. DFT analysis reveals that interaction between the ferrocenes and the MCl2 fragment is small and suggests that communication is mediated by better energy matching between the ferrocene and organic π∗ orbitals upon coordination, allowing superexchange coupling through the LUMO. Furthermore, single crystal diffraction data obtained from oxidation of one and both ferrocenes show distortions, introducing the empty dxy/dx2-y2 orbitals into the secondary coordination sphere of the MCl2 fragment. Such structural rearrangements are infrequent in ferrocenyl mixedvalent compounds, and implications for catalysis as well as electronic communication are discussed.
Original language | English (US) |
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Pages (from-to) | 18715-18729 |
Number of pages | 15 |
Journal | Journal of the American Chemical Society |
Volume | 142 |
Issue number | 43 |
DOIs | |
State | Published - Oct 28 2020 |
ASJC Scopus subject areas
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry
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Dive into the research topics of 'Bis-ferrocenyl-pyridinediimine trinuclear mixed-valent complexes with metal-binding dependent electronic coupling: Synthesis, structures, and redox-spectroscopic characterization'. Together they form a unique fingerprint.Datasets
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CCDC 2041909: Experimental Crystal Structure Determination
Carter, C. (Contributor), Kratish, Y. (Contributor), Jurca, T. (Contributor), Gao, Y. (Contributor) & Marks, T. J. (Contributor), Cambridge Crystallographic Data Centre, 2020
DOI: 10.5517/ccdc.csd.cc26js1l, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc26js1l&sid=DataCite
Dataset
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CCDC 2039892: Experimental Crystal Structure Determination
Carter, C. (Contributor), Kratish, Y. (Contributor), Jurca, T. (Contributor), Gao, Y. (Contributor) & Marks, T. J. (Contributor), Cambridge Crystallographic Data Centre, 2020
DOI: 10.5517/ccdc.csd.cc26gnzb, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc26gnzb&sid=DataCite
Dataset
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CCDC 2039890: Experimental Crystal Structure Determination
Carter, C. (Contributor), Kratish, Y. (Contributor), Jurca, T. (Contributor), Gao, Y. (Contributor) & Marks, T. J. (Contributor), Cambridge Crystallographic Data Centre, 2020
DOI: 10.5517/ccdc.csd.cc26gnx8, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc26gnx8&sid=DataCite
Dataset