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超分子范式用于捕获和共沉淀金(III)配合物。

Supramolecular Paradigm for Capture and Co-Precipitation of Gold(III) Coordination Complexes.

机构信息

Department of Chemistry & Biochemistry, University of Notre Dame, 236 Nieuwland Science Hall, Notre Dame, IN, 46545, USA.

出版信息

Chemistry. 2021 Jan 7;27(2):751-757. doi: 10.1002/chem.202003680. Epub 2020 Nov 27.

Abstract

A new supramolecular paradigm is presented for reliable capture and co-precipitation of haloauric acids (HAuX ) from organic solvents or water. Two classes of acyclic organic compounds act as complementary receptors (tectons) by forming two sets of directional non-covalent interactions, (a) hydrogen bonding between amide (or amidinium) NH residues and the electronegative X ligands on the AuX , and (b) electrostatic stacking of the electron deficient Au center against the face of an aromatic surface. X-ray diffraction analysis of four co-crystal structures reveals the additional common feature of proton bridged carbonyls as a new and predictable supramolecular design element that creates one-dimensional polymers linked by very short hydrogen bonds (CO⋅⋅⋅OC distance <2.5 Å). Two other co-crystal structures show that the amidinium-π⋅⋅⋅XAu interaction will reliably engage AuX with high directionality. These acyclic compounds are very attractive as co-precipitation agents within new "green" gold recovery processes. They also have high potential as tectons for controlled self-assembly or co-crystal engineering of haloaurate composites. More generally, the supramolecular paradigm will facilitate the design of next-generation receptors or tectons with high affinity for precious metal square planar coordination complexes for use in advanced materials, nanotechnology, or medicine.

摘要

提出了一种新的超分子范例,用于从有机溶剂或水中可靠地捕获和共沉淀卤化金酸(HAuX)。两类非环有机化合物通过形成两组定向非共价相互作用充当互补受体(构筑块),(a)酰胺(或脒基)NH 残基与 AuX 上的电负性 X 配体之间的氢键,以及(b)电子缺Au 中心与芳香表面的面之间的静电堆积。四个共晶结构的 X 射线衍射分析揭示了质子桥接羰基作为新的和可预测的超分子设计元素的额外共同特征,该元素创建了通过非常短的氢键(CO⋅⋅⋅OC 距离<2.5 Å)连接的一维聚合物。另外两个共晶结构表明,脒基-π⋅⋅⋅XAu 相互作用将可靠地以高方向性结合 AuX。这些非环化合物作为新型“绿色”金回收工艺中的共沉淀剂非常有吸引力。它们也有可能作为构筑块用于卤化金酸盐复合材料的可控自组装或共晶工程。更一般地说,该超分子范例将有助于设计下一代受体或构筑块,这些受体或构筑块对贵金属四方平面配位配合物具有高亲和力,可用于先进材料、纳米技术或医学。

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