New multi-ferrocenyl- and multi-ferricenyl- materials via coordination-driven self-assembly and via charge-driven electro-crystallization.
New multi-ferrocenyl- and multi-ferricenyl- materials via coordination-driven self-assembly and via charge-driven electro-crystallization.
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DOI：
10.1021/ic401803p
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发表时间：
2013-10
影响因子：
4.6
通讯作者：
Hakikulla H. Shah;Rayya A. Al-Balushi;Mohammed K. Al-Suti;Muhammad S. Khan;C. H. Woodall;A. Sudlow;P. Raithby;G. Kociok‐Köhn;K. Molloy;F. Marken
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文献类型：
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作者：
Hakikulla H. Shah;Rayya A. Al-Balushi;Mohammed K. Al-Suti;Muhammad S. Khan;C. H. Woodall;A. Sudlow;P. Raithby;G. Kociok‐Köhn;K. Molloy;F. Marken
二茂铁乙炔基吡啶(L)(2)与卤化铜铜(X=I(-)、Br2(-)、Cl2(-))反应，合成了三种新的四茂铁乙炔基吡啶铜配合物，L4(CuI)4(3)，L4(CuBr2)2(4)和L4(CuCl2)(5)。用光谱方法对配体2和配合物3-5进行了表征。2-4的结构经单晶X-射线单晶衍射学确证。2通过C-H··N氢键在结晶态形成二聚体。4和5是二聚体，3是四聚体，在所有情况下都通过铜-X··铜桥联作用连接。在二氯乙烷中的循环伏安显示了化学可逆的多二茂铁氧化信号，并证明了产物的电结晶。用电沉积的方法将氧化产物分离到铂电极上，并用扫描电子显微镜对氧化产物进行了观察，证实了氧化产物晶型的自发形成，具有独特的形貌。能量色散X射线元素分析表明，电晶化产物3、4和5分别存在P：Fe为1：1、0.5：1和1：1的六氟磷酸盐(反离子)，建议电晶化产物为[3](4+)(PF6(-))4、[4](2+)(PF6(-))2和[5](4+)(PF6(-))4。
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.