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

Research output: Contribution to journalArticle

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

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Crystallization
Self assembly
self assembly
crystallization
Dimers
Oxidation
Copper
products
Ethylene Dichlorides
Crystalline materials
X ray crystallography
oxidation
Electrodeposition
Cyclic voltammetry
dimers
Hydrogen bonds
copper
Single crystals
Ligands
X rays

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

New multi-ferrocenyl- and multi-ferricenyl- materials via coordination-driven self-assembly and via charge-driven electro-crystallization. / Shah, Hakikulla H.; Al-Balushi, Rayya A.; Al-Suti, Mohammed K.; Khan, Muhammad S.; Woodall, Christopher H.; Sudlow, Anna L.; Raithby, Paul R.; Kociok-Köhn, Gabriele; Molloy, Kieran C.; Marken, Frank.

In: Inorganic Chemistry, Vol. 52, No. 20, 2013, p. 12012-12022.

Research output: Contribution to journalArticle

Shah, HH, Al-Balushi, RA, Al-Suti, MK, Khan, MS, Woodall, CH, Sudlow, AL, Raithby, PR, Kociok-Köhn, G, Molloy, KC & Marken, F 2013, 'New multi-ferrocenyl- and multi-ferricenyl- materials via coordination-driven self-assembly and via charge-driven electro-crystallization', Inorganic Chemistry, vol. 52, no. 20, pp. 12012-12022. https://doi.org/10.1021/ic401803p
Shah, Hakikulla H. ; Al-Balushi, Rayya A. ; Al-Suti, Mohammed K. ; Khan, Muhammad S. ; Woodall, Christopher H. ; Sudlow, Anna L. ; Raithby, Paul R. ; Kociok-Köhn, Gabriele ; Molloy, Kieran C. ; Marken, Frank. / New multi-ferrocenyl- and multi-ferricenyl- materials via coordination-driven self-assembly and via charge-driven electro-crystallization. In: Inorganic Chemistry. 2013 ; Vol. 52, No. 20. pp. 12012-12022.
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AU - Shah, Hakikulla H.

AU - Al-Balushi, Rayya A.

AU - Al-Suti, Mohammed K.

AU - Khan, Muhammad S.

AU - Woodall, Christopher H.

AU - Sudlow, Anna L.

AU - Raithby, Paul R.

AU - Kociok-Köhn, Gabriele

AU - Molloy, Kieran C.

AU - Marken, Frank

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AB - 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.

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