A Strategy for the Construction of Triply Interlocked Organometallic Cages by Rational Design of Poly-NHC Precursors,Journal of the American Chemical Society

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A Strategy for the Construction of Triply Interlocked Organometallic Cages by Rational Design of Poly-NHC Precursors
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-07-09 , DOI: 10.1021/jacs.0c06470
Ya-Wen Zhang ₁ , Sha Bai ₁ , Yao-Yu Wang ₁ , Ying-Feng Han ₁

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Three-dimensional (3D) triply interlocked catenanes are a family of chemical topologies that consist of two identical, mechanically interlocked coordination cage components with intriguingly complex structures. Although only a few successful constructions of 3D interlocked catenanes have been achieved to date via metal-mediated assembly, these complex structures have thus far only been targeted by metal-nitrogen/oxygen coordination techniques. Here, taking advantage of rational ligand design, we report the efficient construction of a series of 3D triply interlocked [2]catenanes of the formula [Ag3L2]2, wherein the metal ions exclusively form bonds to N-heterocyclic carbene (NHC) units, and their subsequent transmetalation to the corresponding [Au3L2]2 gold analogues. The formation and transmetalation reactions proceed under mild conditions and are generally applicable. A series of characterization techniques were applied to confirm the formation and structure of the desired 3D triply interlocked architectures: multinuclear NMR spectroscopy, ESI-MS, and single-crystal X-ray diffraction analysis. The solid-state structure of [Ag3(1a)2]2(PF6)6 unambiguously confirms the existence of a 3D catenane that consists of two identical, mechanically interlocked trinuclear hexacarbene cage components. The interlocking of two 3D cages into a [2]catenane is driven by the efficient π•••π stacking of triazine-triazine stacks with cooperative interactions between imidazo[1,5-a]pyridine subunits. Notably, the triply interlocked organometallic cages exhibit good stability toward various organic solvents, concentrations, temperatures, and no disassembly occurred in the presence of coronene or pyrene. The future construction of mechanically interlocked architectures using metal-carbene bonds rather than metal-nitrogen bonds may provide assemblies with interesting properties for as-yet-unimagined applications in fields such as sensors and molecular electrical conductors.

中文翻译：

通过合理设计多 NHC 前驱体构建三重联锁有机金属笼的策略

三维 (3D) 三重联锁链是一个化学拓扑家族，由两个相同的、机械联锁的配位笼组件组成，具有有趣的复杂结构。尽管迄今为止仅通过金属介导的组装成功构建了少数 3D 互锁链，但迄今为止，这些复杂的结构仅被金属-氮/氧配位技术作为目标。在这里，利用合理的配体设计，我们报告了一系列式 [Ag3L2]2 的 3D 三重联锁 [2] 链的有效构建，其中金属离子仅与 N-杂环卡宾 (NHC) 单元形成键，并随后将它们金属转移为相应的 [Au3L2]2 金类似物。形成和金属转移反应在温和的条件下进行并且普遍适用。应用了一系列表征技术来确认所需 3D 三重联锁架构的形成和结构：多核 NMR 光谱、ESI-MS 和单晶 X 射线衍射分析。[Ag3(1a)2]2(PF6)6 的固态结构明确证实了 3D 链烷的存在，该链烷由两个相同的、机械互锁的三核六碳烯笼组件组成。两个 3D 笼互锁成 [2] 链是由三嗪-三嗪堆栈的有效 π•••π 堆积以及咪唑并 [1,5-a] 吡啶亚基之间的协同相互作用驱动的。值得注意的是，三重互锁的有机金属笼对各种有机溶剂、浓度、温度，并且在晕苯或芘存在下不会发生分解。使用金属-卡宾键而不是金属-氮键的机械互锁结构的未来构造可能为组件提供有趣的特性，用于传感器和分子电导体等领域中尚未想象的应用。

更新日期：2020-07-09

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