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Bonding and Electronic Properties of Linear Diethynyl Oligothienoacene-Bridged Diruthenium Complexes and Their Oxidized Forms

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    Bonding and Electronic Properties of Linear Diethynyl Oligothienoacene-Bridged Diruthenium Complexes and Their Oxidized Forms
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    † Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University (CCNU), Wuhan 430079, P. R. China
    ‡ ⊥ ‡College of Chemistry and Material Science and ⊥Key Laboratory of Functional Organometallic Materials of Hunan Province College, Hengyang Normal University, Hengyang, Hunan 421008, P. R. China
    ∥ Department of Chemistry, University of Reading, Whiteknights, Reading RG6 6AD, U.K.
    *E-mail: [email protected];.
    *E-mail: [email protected]
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2017, 56, 18, 11074–11086
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    https://doi.org/10.1021/acs.inorgchem.7b01433
    Published August 29, 2017
    Copyright © 2017 American Chemical Society
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    Abstract

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    A series of five diruthenium diethynyl complexes based on α,β-fused oligothienoacenes in the core of the bridging ligands [{Ru(dppe)Cp*}2(μ-C≡C–L–C≡C)] [dppe = 1,2-bis(diphenylphosphino)ethane, Cp* = η5-C5Me5; L = thieno[3,2-b]thiophene (4), thieno[2,3-b]thiophene (5), 3,4-dimethylthieno[2,3-b]thiophene (6), dithieno[3,2-b:2′,3′-d]thiophene (7), and thieno[3,2-b]thieno[2′,3′:4,5]thieno[2,3-d]thiophene (8)] have been synthesized and fully characterized electrochemically and spectroscopically. Elongation of the redox noninnocent oligothienoacene bridge core causes a smaller potential difference between the initial two anodic steps, not seen for free dialkyl oligothienoacenes, and increased positive charge delocalization over the conjugated bridge backbone. The highest occupied molecular orbital of the parent complexes resides predominantly on the oligothienoacene core, with strong participation of the ethynyl linkers and slightly smaller contribution from the metallic termini. This bonding character makes the initial one-electron oxidation symmetrical, as revealed by combined voltammetric and spectroscopic (IR, UV–vis–near-IR, and electron paramagnetic resonance) methods as well as density functional theory (DFT) and time-dependent DFT calculations of truncated and selected nontruncated models of the studied series. The remarkable gradual appearance of two C≡C stretching absorptions in the IR spectra of the monocationic diethynyl complexes is ascribed to increasing vibronic coupling of the IR-forbidden νs(C≡C) mode of the oxidized −[C≡C–core–C≡C]+– bridge with a low-lying π–π*(intrabridge)/metal-to-ligand charge-transfer electronic transition in the near-to-mid-IR spectral region.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.7b01433.

    • IR and UV–vis–NIR spectra, calculated DFT data, and NMR information (PDF)

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    CCDC 1504782–1504783 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 [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2017, 56, 18, 11074–11086
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.7b01433
    Published August 29, 2017
    Copyright © 2017 American Chemical Society
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