New Multi-Ferrocenyl- and Multi-Ferricenyl- Materials via Coordination-Driven Self-Assembly and via Charge-Driven Electro-Crystallization
Autor: | Hakikulla H. Shah, Frank Marken, Gabriele Kociok-Köhn, Paul R. Raithby, Kieran C. Molloy, Christopher H. Woodall, Anna L. Sudlow, Mohammed K. Al-Suti, Muhammad S. Khan, Rayya A. Al-Balushi |
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Rok vydání: | 2013 |
Předmět: | |
Zdroj: | Inorganic Chemistry. 52:12012-12022 |
ISSN: | 1520-510X 0020-1669 |
Popis: | 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. |
Databáze: | OpenAIRE |
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