Synthesis, Structure, Property, and Dinuclear Cu(II) Complexation of Tetraoxacalix[2]arene[2]phenanthrolines
Synthesis, Structure, Property, and Dinuclear Cu(II) Complexation of Tetraoxacalix[2]arene[2]phenanthrolines
复制标题
四恶萼[2]芳烃[2]菲咯啉的合成、结构、性质及双核Cu(II)络合
DOI：
10.1021/acs.inorgchem.8b02039
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发表时间：
2018
影响因子：
4.6
通讯作者：
Wang De-Xian
中科院分区：
文献类型：
--
作者：
Wang Xue-Yuan;Ao Yu-Fei;Wang Qi-Qang;Wang De-Xian
通过一系列二羟基芳烃和1，10-菲咯啉衍生物之间的一锅法，方便地合成了许多新型四氧杂杯[2]芳烃[2]菲咯啉7 - 11，其中含有菲咯啉和不同的芳香键。单晶衍射分析表明，所得到的大环具有不同的构象和空腔结构，这是由不同的芳香键调控。与芳族键的长度一致，两个菲咯啉部分之间的距离（dN-N）分别从6.92逐渐增加到13.30 μ m。这些大环化合物的物理化学性质进行了研究，通过光谱，CV，和DPV测量。由于邻菲咯啉部分的配位能力和可调的构象结构，大环主体可以与Cu 2+形成明显的双核配合物。典型地，具有短芳香键的7 b-2Cu（II）络合物给出O-桥连的双铜结构，而具有长芳香键的11b-2Cu（II）络合物具有两个离散的铜中心。用XPS、CV和DPV技术研究了配合物的光谱结构和氧化还原性质。因此，这项工作提供了一个平台，以获得具有明确结构的仿生含铜小分子模型。
A number of novel tetraoxacalix[2]arene[2]phenanthrolines7–11containing phenanthroline and diverse aromatic linkages were conveniently synthesized by a one-pot protocol between a series of dihydroxy arenes and 1,10-phenanthroline derivatives. Single-crystal diffraction analysis revealed that the resulting macrocycles possess diverse conformational and cavity structures which are regulated by the different aromatic linkages. In line with the length of the aromatic linkages, the distance between the two phenanthroline moieties (dN–N) gradually increases from 6.92 to 13.30 Å, respectively. The physicochemical properties of these macrocyclic compounds were investigated by spectroscopic, CV, and DPV measurements. Owing to the coordination ability of the phenanthroline moieties and the tunable conformational structure, the macrocyclic hosts can form distinct dinuclear complexation with Cu2+. Typically, with a short aromatic linkage the7b–2Cu(II) complex gives an O-bridged dicopper structure, while with long linkage the11b–2Cu(II) complex possesses two discrete copper centers. The spectroscopic structure and the redox property of the dicopper complexes were investigated by XPS, CV, and DPV techniques. This work hence provides a platform to access biomimetic copper-containing small-molecule models with well-defined structures.