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Long-range intramolecular electronic communication in bis(ferrocenylethynyl) complexes incorporating conjugated heterocyclic spacers:Synthesis, crystallography, and electrochemistry


Reference:

Shah, H.H., Al-Balushi, R.A., Al-Suti, M.K., Khan, M.S., Woodall, C. H., Molloy, K.C., Raithby, P.R., Robinson, T.P., Dale, S.E.C. and Marken, F., 2013. Long-range intramolecular electronic communication in bis(ferrocenylethynyl) complexes incorporating conjugated heterocyclic spacers:Synthesis, crystallography, and electrochemistry. Inorganic Chemistry, 52 (9), pp. 4898-4908.

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    Official URL:

    http://dx.doi.org/10.1021/ic3024887

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    Abstract

    A new series of bis(ferrocenylethynyl) complexes, 3–7, and a mono(ferrocenylethynyl) complex, 8, have been synthesized incorporating conjugated heterocyclic spacer groups, with the ethynyl group facilitating an effective long-range intramolecular interaction. The complexes were characterized by NMR, IR, and UV–vis spectroscopy as well as X-ray crystallography. The redox properties of these complexes were investigated using cyclic voltammetry and spectroelectrochemistry. Although there is a large separation of 14 Å between the two redox centers, ΔE1/2 values in this series of complexes ranged from 50 to 110 mV. The appearance of intervalance charge-transfer bands in the UV–vis–near-IR region for the monocationic complexes further confirmed effective intramolecular electronic communication. Computational studies are presented that show the degree of delocalization across the Fc–C≡C–C≡C–Fc (Fc = C5H5FeC5H4) highest occupied molecular orbital.

    Details

    Item Type Articles
    CreatorsShah, H.H., Al-Balushi, R.A., Al-Suti, M.K., Khan, M.S., Woodall, C. H., Molloy, K.C., Raithby, P.R., Robinson, T.P., Dale, S.E.C. and Marken, F.
    DOI10.1021/ic3024887
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    URLURL Type
    http://www.scopus.com/inward/record.url?scp=84877280690&partnerID=8YFLogxKUNSPECIFIED
    DepartmentsFaculty of Science > Chemistry
    Research Centres & Institutes > Institute for Sustainable Energy and the Environment
    Research CentresCentre for Sustainable Chemical Technologies
    Publisher StatementMolloy_2013_Inorganic_Chemistry_52_9_4898.pdf: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/ic3024887
    RefereedYes
    StatusPublished
    ID Code35840

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