Department of Chemistry and Biochemistry , University of Notre Dame , 236 Nieuwland Science Hall, Notre Dame , Indiana 46556 , United States.
J Am Chem Soc. 2018 Jun 6;140(22):6810-6813. doi: 10.1021/jacs.8b04155. Epub 2018 May 29.
Two macrocyclic tetralactam receptors are shown to selectively encapsulate anionic, square-planar chloride and bromide coordination complexes of gold(III), platinum(II), and palladium(II). Both receptors have a preorganized structure that is complementary to its precious metal guest. The receptors do not directly ligate the guest metal center but instead provide an array of arene π-electron donors that interact with the electropositive metal and hydrogen-bond donors that interact with the outer electronegative ligands. This unique mode of supramolecular recognition is illustrated by six X-ray crystal structures showing receptor encapsulation of AuCl, AuBr, PtCl, or PdCl. In organic solution, the 1:1 association constants correlate with specific supramolecular features identified in the solid state. Technical applications using these receptors are envisioned in a wide range of fields that involve precious metals, including mining, recycling, catalysis, nanoscience, and medicine.
两种大环四元环受体被证明可以选择性地包裹带负电荷的、平面正方形的金(III)、铂(II)和钯(II)的卤化物配位化合物。这两个受体都有一个预先组织好的结构,与它们的贵金属客体互补。受体不会直接连接客体金属中心,而是提供一系列的芳烃π-电子供体,与正电性金属相互作用,以及氢键供体,与外部的电负性配体相互作用。这种独特的超分子识别模式通过六个 X 射线晶体结构得到了说明,这些结构显示了受体对 AuCl、AuBr、PtCl 或 PdCl 的包合。在有机溶液中,1:1 的缔合常数与在固态中确定的特定超分子特征相关。预计这些受体在包括采矿、回收、催化、纳米科学和医学在内的广泛涉及贵金属的领域中具有技术应用。