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

Research output: Contribution to journalArticle

20 Citations (Scopus)

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, 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
Volume52
Issue number9
DOIs
Publication statusPublished - May 6 2013

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Crystallography
Electrochemistry
electrochemistry
spacers
crystallography
communication
Spectroelectrochemistry
X ray crystallography
Communication
Molecular orbitals
synthesis
Ultraviolet spectroscopy
electronics
Cyclic voltammetry
Charge transfer
molecular orbitals
charge transfer
Nuclear magnetic resonance
nuclear magnetic resonance
spectroscopy

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Long-range intramolecular electronic communication in bis(ferrocenylethynyl) complexes incorporating conjugated heterocyclic spacers : Synthesis, crystallography, and electrochemistry. / Shah, Hakikulla H.; Al-Balushi, Rayya A.; Al-Suti, Mohammed K.; Khan, Muhammad S.; Woodall, Christopher H.; Molloy, Kieran C.; Raithby, Paul R.; Robinson, Thomas P.; Dale, Sara E C; Marken, Frank.

In: Inorganic Chemistry, Vol. 52, No. 9, 06.05.2013, p. 4898-4908.

Research output: Contribution to journalArticle

Shah, Hakikulla H. ; Al-Balushi, Rayya A. ; Al-Suti, Mohammed K. ; Khan, Muhammad S. ; Woodall, Christopher H. ; Molloy, Kieran C. ; Raithby, Paul R. ; Robinson, Thomas P. ; Dale, Sara E C ; Marken, Frank. / Long-range intramolecular electronic communication in bis(ferrocenylethynyl) complexes incorporating conjugated heterocyclic spacers : Synthesis, crystallography, and electrochemistry. In: Inorganic Chemistry. 2013 ; Vol. 52, No. 9. pp. 4898-4908.
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