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

Hakikulla H. Shah, Rayya A. Al-Balushi, Mohammed K. Al-Suti, Muhammad S. Khan, Christopher H. Woodall, Kieran C. Molloy, Paul R. Raithby, Thomas P. Robinson, Sara E C Dale, Frank Marken

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21 Citations (Scopus)


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, ΔE 1/2 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 = C 5H5FeC5H4) highest occupied molecular orbital.

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


ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

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