Department of Chemistry, Università degli Studi di Torino, Via Pietro Giuria 7, 10125, Torino, Italy.
Department of Chemistry, Universitat de les Illes Balears, Crta de Valldemossa km 7.5, 07122, Palma de Mallorca, Spain.
Chempluschem. 2023 May;88(5):e202300052. doi: 10.1002/cplu.202300052.
The relevance of hydrogen-bonding, π-π stacking and aurophilic interactions in the solid-state of two new heterobimetallic (Au -Mn ) complexes is analyzed in this manuscript. They are discrete complexes of formulae [Mn(bipy) (H O){Au(CN) }][Au(CN) ] and [Mn(dmbipy) {Au(CN) }] ⋅ H O, (bipy=2,2'-bipyridine and dmbipy=5,5'-dimethyl-2,2'-bipyridine), which are based on dicyanidoaurate(I) groups and 2,2'-bipyridyl-like co-ligands. They have been synthesized in good yields and X-ray characterized. In both compounds, aurophilic, OH⋅⋅⋅N hydrogen bonding and π-π interactions governed the supramolecular assemblies in the solid state. These contacts with special emphasis on the aurophilic interactions have been studied using density functional theory calculations and characterized using the quantum theory of atoms-in-molecules and the noncovalent interaction plot. The aurophilic contacts have been also rationalized from an orbital point of view using the natural bond orbital methodology, evidencing stabilization energies up to 5.7 kcal/mol. Moreover, the interaction energies have been decomposed using the Kitaura-Morokuma energy decomposition analysis, confirming the importance of electrostatic and orbital effects.
本文分析了两个新型杂金属（Au-Mn）配合物在固态中氢键、π-π 堆积和金键相互作用的相关性。它们是化学式为[Mn(bipy)(H2O){Au(CN)4}][Au(CN)4]和[Mn(dmbipy){Au(CN)4}]·H2O 的离散配合物，（bipy=2,2'-联吡啶，dmbipy=5,5'-二甲基-2,2'-联吡啶），它们基于一价金氰化物基团和 2,2'-联吡啶类似的共配体。这些配合物以较高的产率合成并通过 X 射线进行了表征。在这两种化合物中，金键、OH···N 氢键和 π-π 相互作用控制了固态中的超分子组装。使用密度泛函理论计算和原子在分子中的量子理论和非共价相互作用图对这些具有特殊重点的金键相互作用进行了研究。使用自然键轨道方法从轨道角度合理化了金键接触，证明了高达 5.7 kcal/mol 的稳定能。此外，使用 Kitaura-Morokuma 能量分解分析对相互作用能进行了分解，证实了静电和轨道效应的重要性。
