Zhang Ying-Ying, Gao Wen-Xi, Lin Yue-Jian, Mi Li-Wei, Jin Guo-Xin
Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, State Key Laboratory of Molecular Engineering of Polymers, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Fudan University, Shanghai, 200433, P. R. China.
Center for Advanced Materials Research, Zhongyuan University of Technology, Zhengzhou, 451191, P. R. China.
Chemistry. 2017 Aug 16;23(46):11133-11140. doi: 10.1002/chem.201702244. Epub 2017 Aug 1.
Different types of multinuclear half-sandwich rhodium macrocycles and cages were designed and synthesized by using two similar multifunctional hydroxamate ligands (pyrazine-2-hydroxamic acid (NaHL ) and 4,4'-bipyridine-2-hydroxamic acid (KHL )) featuring one monodentate site and two pairs of chelating sites. The Rh -Pd heterometallic macrocycles were constructed by using the semi-open palladium(II) source [Pd(en)Cl ] with two free acceptor sites. However, only one kind of macrocycle was found when the shorter ligand L was used, while in for the larger ligand, various spectroscopic techniques demonstrated the coexistence of hexanuclear and octanuclear macrocycles in solution and the proportions of both components depended on concentration and temperature. The palladium salt Pd(NO ) , as a source of "naked" Pd , was introduced to assemble the cuboid-shaped cage composed of two types of metal ions and three types of organic ligands. In addition, two silver(I)-containing mixed-metal complexes bridged by pyrazine were obtained, in which two forms of decanuclear complex with C and C point symmetry cocrystallized-one is a polymeric structure and the other is a discrete cage. However, the third form, with D point symmetry, was found in the larger cage.
通过使用两种类似的多功能异羟肟酸配体（吡嗪 - 2 - 异羟肟酸（NaHL）和4,4'-联吡啶 - 2 - 异羟肟酸（KHL））设计并合成了不同类型的多核半夹心铑大环和笼状化合物，这些配体具有一个单齿位点和两对螯合位点。通过使用具有两个自由受体位点的半开放钯（II）源[Pd(en)Cl]构建了Rh - Pd异金属大环。然而，当使用较短的配体L时，仅发现了一种大环，而对于较大的配体，各种光谱技术表明溶液中六核和八核大环共存，且两种组分的比例取决于浓度和温度。引入钯盐Pd(NO₃)₂作为“裸”Pd²⁺的来源，以组装由两种金属离子和三种有机配体组成的长方体形笼状化合物。此外，还获得了两种由吡嗪桥连的含银（I）混合金属配合物，其中两种具有C₂和C₂点对称性的十核配合物形式共结晶——一种是聚合物结构，另一种是离散的笼状结构。然而，在较大的笼状结构中发现了具有D₂点对称性的第三种形式。
