Metallophilic and Inter‐Ligand Interactions in Diargentous Compounds Bound by a Geometrically Flexible Macrocycle

作者：Qiuran Wang, Michael R. Gau, Brian C. Manor, Patrick J. Carroll, Neil C. Tomson · 发表于：European Journal of Inorganic Chemistry · 年份：2023 · DOI：10.1002/ejic.202300335 · 被引用次数：8 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Magnetism in coordination complexes、Crystallography and molecular interactions

Abstract A series of mono‐ and di‐nuclear Ag I complexes supported by a flexible macrocyclic ligand are reported. The geometric flexibility of the ligand was found to allow for a range of Ag−Ag interactions in the disilver complexes, depending on the identities of both the ancillary ligand and the counterion. Studies of the solution‐phase dynamic exchange processes for these latter complexes found rapid interconversion through a mechanism that retained the multi‐nuclearity. Quantum Theory of Atoms in Molecules (QTAIM) and Independent Gradient Model based on Hirshfeld partition (IGMH) analyses are used to evaluate the d 10 ‐d 10 interactions between silver centers in the various geometries observed for the solid‐state structures of these complexes, revealing nearly identical Ag−Ag interactions, regardless of the relative geometries of the Ag centers. Instead, a weak, but non‐negligible, inter‐ligand interaction between two isocyanide units may contribute to the folded‐ligand geometry observed in the solid state.