Kim Heechan, Shin Juhwan, Kim Seyong, Lee Dongwhan
Department of Chemistry, Seoul National University 1 Gwanak-ro, Gwanak-gu Seoul 08826 Korea
Chem Sci. 2023 Mar 1;14(12):3265-3269. doi: 10.1039/d3sc00851g. eCollection 2023 Mar 22.
Uneven allocation of resources creates frustration, tension, and conflicts. Confronted with an apparent mismatch between the number of donor atoms and the number of metal atoms to be supported, helically twisted ligands cleverly come up with a sustainable symbiotic solution. As an example, we present a tricopper metallohelicate exhibiting screw motions for intramolecular site exchange. A combination of X-ray crystallographic and solution NMR spectroscopic studies revealed thermo-neutral site exchange of three metal centres hopping back and forth inside the helical cavity lined by a spiral staircase-like arrangement of ligand donor atoms. This hitherto unknown is a superimposition of translational and rotational movements of molecular actuation, taking the shortest path with an extraordinarily low energy barrier without compromising the overall structural integrity of the metal-ligand assembly.
资源分配不均会引发挫败感、紧张局势和冲突。面对供体原子数量与待配位金属原子数量之间明显的不匹配，螺旋扭曲配体巧妙地提出了一种可持续的共生解决方案。例如，我们展示了一种三铜金属螺旋体，其表现出用于分子内位点交换的螺旋运动。X射线晶体学和溶液核磁共振光谱研究相结合，揭示了三个金属中心在由配体供体原子的螺旋楼梯状排列所围成的螺旋腔内来回跳跃的热中性位点交换。这种前所未知的现象是分子驱动的平移和旋转运动的叠加，它以最短的路径、极低的能垒进行，同时又不损害金属-配体组装体的整体结构完整性。
