State Key Laboratory of Molecular Engineering of Polymers, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Fudan University , Shanghai 200433, PR China.
J Am Chem Soc. 2015 Oct 28;137(42):13670-8. doi: 10.1021/jacs.5b08826. Epub 2015 Oct 15.
In modern coordination chemistry, supramolecular coordination complexes take advantage of ligand design to control the shapes and sizes of such architectures. Here we describe how to utilize starting building blocks and a multifunctional ligand to rationally design and synthesize different types of discrete assemblies. Using a hydroxamate ligand featuring two pair of chelating sites together with half-sandwich iridium and rhodium fragments, we were able to construct a series multinuclear organometallic macrocycles and cages through stepwise coordination-driven self-assembly. Experimental observations, supported by computational work, show that selective coordination modes were ascribed to the significant electronic density differences of the two chelating sites, (O,O') and (N,N'). The results underline the advantages of the discrimination between soft and hard binding sites, and suggest that hydroxamic acids can be used as a versatile class of facile multifunctional scaffold for the construction of novel two-dimensional and three-dimensional architectures.
在现代配位化学中，超分子配位配合物利用配体设计来控制这些结构的形状和大小。在这里，我们描述了如何利用起始构建块和多功能配体来合理设计和合成不同类型的离散组装体。使用具有两对螯合位点的偕羟肟酸配体和半夹心铱和铑片段，我们能够通过逐步配位驱动自组装构建一系列多核有机金属大环和笼。实验观察结果得到计算工作的支持，表明选择性配位模式归因于两个螯合位点（O,O'）和（N,N'）的显著电子密度差异。这些结果强调了区分软和硬结合位点的优势，并表明偕羟肟酸可以用作一类通用的多功能支架，用于构建新型二维和三维结构。
