Tunable Fullerene Affinity of Cages, Bowls and Rings Assembled by PdII Coordination Sphere Engineering
Tunable Fullerene Affinity of Cages, Bowls and Rings Assembled by PdII Coordination Sphere Engineering
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DOI：
10.1002/chem.201903317
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发表时间：
2019-10-24
影响因子：
4.3
通讯作者：
Clever, Guido H.
中科院分区：
文献类型：
--
作者：
Chen, Bin;Horiuchi, Shinnosuke;Clever, Guido H.
对于金属介导的主体化合物，以非统计方式降低对称性和引入多个官能团的策略的发展是一项具有挑战性的任务。我们表明，引入空间应力周围的协调环境的正方形平面的Pd-II阳离子和双单齿氮供体配体允许控制组装产品的大小和形状，从[Pd 2L 4]笼[Pd 2L 3]碗状结构[Pd 2L 2]环。因此，香蕉形配体骨架配备吡啶，两种不同的喹啉异构体和吖啶，后三个通过稠合苯环上的氢取代基引入空间拥挤。通过NMR光谱、质谱和单晶X-射线衍射研究了四种所得宿主对C-60和C-70富勒烯结合的不同行为，并与结构差异相关。发现基于吡啶、6-喹啉或3-喹啉供体的三个笼要么结合C-60、C-70，要么根本不结合富勒烯。
For metal-mediated host compounds, the development of strategies to reduce symmetry and introduce multiple functionalities in a non-statistical way is a challenging task. We show that the introduction of steric stress around the coordination environment of square-planar Pd-II cations and bis-monodentate nitrogen donor ligands allows to control the size and shape of the assembled product, from [Pd2L4] cages over [Pd2L3] bowl-shaped structures to [Pd2L2] rings. Therefore, banana-shaped ligand backbones were equipped with pyridines, two different quinoline isomers and acridine, the latter three introducing steric congestion through hydrogen substituents on annelated benzene rings. Differing behavior of the four resulting hosts towards the binding of C-60 and C-70 fullerenes was studied and related to structural differences by NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction. The three cages based on pyridine, 6-quinoline or 3-quinoline donors were found to either bind C-60, C-70 or no fullerene at all.