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

H.H. Shah, R.A. Al-Balushi, M.K. Al-Suti, M.S. Khan, Christopher H Woodall, K.C. Molloy, P.R. Raithby, T.P. Robinson, S.E.C. Dale, F. Marken

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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.
Original languageEnglish
Pages (from-to)4898-4908
Number of pages11
JournalInorganic Chemistry
Volume52
Issue number9
DOIs
Publication statusPublished - 6 May 2013

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