New multi-ferrocenyl- and multi-ferricenyl- materials via coordination-driven self-assembly and via charge-driven electro-crystallization

Hakikulla H. Shah, Rayya A. Al-Balushi, Mohammed K. Al-Suti, Muhammad S. Khan, Christopher H. Woodall, Anna L. Sudlow, Paul R. Raithby, Gabriele Kociok-Köhn, Kieran C. Molloy, Frank Marken

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8 Citations (Scopus)

Abstract

Three new tetra-ferrocenylethynylpyridinyl copper complexes, L 4(CuI)4 (3), L4(CuBr)2 (4), and L4(CuCl)2 (5) have been prepared from the reaction of ferrocenylethynylpyridine (L)(2) with copper halides CuX (with X = I -, Br-, Cl-).The ligand 2 and the complexes 3-5 have been fully characterized by spectroscopic methods. The structures of 2-4 have been confirmed by single-crystal X-ray crystallography. 2 forms a dimer in the crystalline-state through C-H··N hydrogen bonds. 4 and 5 are dimers and 3 a tetramer, in all cases linked through Cu-X··Cu bridging interactions. Cyclic voltammetry in dichloroethane showed chemically reversible multiferrocenyl oxidation signals with evidence for product electro-crystallization. The oxidation products were isolated by electrodeposition onto a Pt disc electrode and investigated by scanning electron microscopy which confirmed the spontaneous formation of crystalline oxidation products with distinctive morphologies. Energy dispersive X-ray elemental analysis shows the presence of hexafluorophosphate (counterion) with the P:Fe ratio of 1:1, 0.5:1, and 1:1 for the electrocrystallized products 3, 4, and 5, respectively, suggesting the formulas [3]4+(PF6 -)4, [4]2+(PF6 -) 2, and [5]4+(PF6 -)4 for the electro-crystallized products.

Original languageEnglish
Pages (from-to)12012-12022
Number of pages11
JournalInorganic Chemistry
Volume52
Issue number20
DOIs
Publication statusPublished - 2013

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

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    Shah, H. H., Al-Balushi, R. A., Al-Suti, M. K., Khan, M. S., Woodall, C. H., Sudlow, A. L., Raithby, P. R., Kociok-Köhn, G., Molloy, K. C., & Marken, F. (2013). New multi-ferrocenyl- and multi-ferricenyl- materials via coordination-driven self-assembly and via charge-driven electro-crystallization. Inorganic Chemistry, 52(20), 12012-12022. https://doi.org/10.1021/ic401803p