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Published July 20, 2020 | Supplemental Material
Journal Article Open

Electronic Structures, Spectroscopy, and Electrochemistry of [M(diimine)(CN-BR₃)₄]²⁻ (M = Fe, Ru; R = Ph, C₆F₅) Complexes


Complexes with the formula [M(diimine)(CN-BR₃)₄]²⁻, where diimine = bipyridine (bpy), phenanthroline (phen), 3,5-trifluoromethylbipyridine (flpy), R = Ph, C₆F₅, and M = Fe^(II), Ru^(II), were synthesized and characterized by X-ray crystal structure analysis, UV–visible spectroscopy, IR spectroscopy, and voltammetry. Three highly soluble complexes, [Fe^(II)(bpy)(CN-B(C₆F₅)₃)₄]²⁻, [Ru^(II)(bpy)(CN-B(C₆F₅)₃)₄]²⁻, and [Ru^(II)(flpy)(CN-B(C₆F₅)₃)₄]²⁻, exhibit electrochemically reversible redox reactions, with large potential differences between the bpy^(0/–) or flpy^(0/–) and MIII/II couples of 3.27, 3.52, and 3.19 V, respectively. CASSCF+NEVPT2 calculations accurately reproduce the effects of borane coordination on the electronic structures and spectra of cyanometallates.

Additional Information

© 2020 American Chemical Society. Received: February 28, 2020; Published: June 25, 2020. We thank Jay Winkler for help in interpretation of transient absorption spectra. Larry Henling and Mike Takase provided invaluable assistance in collection and refinement of X-Ray crystal structures. We acknowledge the X-ray Crystallography Facility in the Beckman Institute at Caltech and the Dow Next Generation Instrumentation Grant for X-ray structure collection. We thank David van der Velde for assistance in NMR interpretation. Calculations were made on the Caltech High Performance Cluster, partially supported by a grant from the Gordon and Betty Moore Foundation. Accession Codes: CCDC 1986320, 1986326–1986327, and 1986331 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033. This work was supported by the National Science Foundation (CHE-1763429). Additional funding was provided by an Arthur A. Noyes SURF Fellowship (D.X.N.) and the Beckman Institute Laser Resource Center supported by the Arnold and Mabel Beckman Foundation. The authors declare no competing financial interest.

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