New Multi-Ferrocenyl- and Multi-Ferricenyl- Materials via Coordination-Driven Self-Assembly and via Charge-Driven Electro-Crystallization

详细信息    查看全文

• 作者：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-K枚hn ; Kieran C. Molloy ; Frank Marken
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：October 21, 2013
• 年：2013
• 卷：52
• 期：20
• 页码：12012-12022
• 全文大小：525K
• 年卷期：v.52,no.20(October 21, 2013)
• ISSN：1520-510X

文摘

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^{鈥?/sup>, Br鈥?/sup>, Cl鈥?/sup>).The ligand 2 and the complexes 3鈥?b>5 have been fully characterized by spectroscopic methods. The structures of 2鈥?b>4 have been confirmed by single-crystal X-ray crystallography. 2 forms a dimer in the crystalline-state through C鈥揌路路N hydrogen bonds. 4 and 5 are dimers and 3 a tetramer, in all cases linked through Cu鈥揦路路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鈥?/sup>)₄, [4]2+(PF₆鈥?/sup>)₂, and [5]4+(PF₆鈥?/sup>)₄ for the electro-crystallized products.}