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-Kohn, Kieran C. Molloy, Frank Marken

Research output: Contribution to journalArticle

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Abstract

Three new tetra-ferrocenylethynylpyridinyl copper complexes, L4(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
Early online date9 Oct 2013
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

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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-Kohn, Gabriele; Molloy, Kieran C.; Marken, Frank.

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

Research output: Contribution to journalArticle

Shah, Hakikulla H. ; Al-balushi, Rayya A. ; Al-suti, Mohammed K. ; Khan, Muhammad S. ; Woodall, Christopher H. ; Sudlow, Anna L. ; Raithby, Paul R. ; Kociok-Kohn, 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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abstract = "Three new tetra-ferrocenylethynylpyridinyl copper complexes, L4(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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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-Kohn, Gabriele

AU - Molloy, Kieran C.

AU - Marken, Frank

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N2 - Three new tetra-ferrocenylethynylpyridinyl copper complexes, L4(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.

AB - Three new tetra-ferrocenylethynylpyridinyl copper complexes, L4(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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