Chen Bin, Holstein Julian J, Platzek André, Schneider Laura, Wu Kai, Clever Guido H
Department of Chemistry and Chemical Biology, TU Dortmund University Otto-Hahn Straße 6 44227 Dortmund Germany
State Key Laboratory of Radiation Medicine and Protection, School for Radiological and Interdisciplinary Sciences (RAD-X), Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, Soochow University Suzhou 215123 China.
Chem Sci. 2022 Jan 17;13(6):1829-1834. doi: 10.1039/d1sc06931d. eCollection 2022 Feb 9.
Recently developed self-assembly strategies allow to rationally reduce the symmetry of metallosupramolecular architectures. In addition, the combination of multiple ligand types without creating compound mixtures has become possible. Among several approaches to realize non-statistical heteroleptic assembly, Coordination Sphere Engineering (CSE) makes use of secondary repulsive or attractive interactions in direct vicinity of the metal nodes. Previously, we used steric congestion to turn dinuclear [PdL] cages with fourfold symmetry into [PdLX] (X = solvent, halide) bowl structures. Here, we introduce a new subtype of this strategy based on balancing hydrogen bonding and repulsive interactions between ligands carrying quinoline (L) and 1,8-naphthyridine (L) donors to generate -[PdL] and [PdLL'] cages, assisted by templation of encapsulated fullerenes. Combined with steric congestion caused by acridine (L) donors, we further report the first example of a heteroleptic [PdLL'X] bowl. Formation, structure and fullerene binding ability of these metallo-supramolecular hosts were studied by NMR, mass spectrometry and single crystal X-ray diffraction.
最近开发的自组装策略能够合理地降低金属超分子结构的对称性。此外，在不产生化合物混合物的情况下组合多种配体类型已成为可能。在实现非统计性杂配体组装的几种方法中，配位球工程（CSE）利用金属节点紧邻区域的二级排斥或吸引相互作用。此前，我们利用空间拥挤将具有四重对称性的双核[PdL]笼转变为[PdLX]（X = 溶剂、卤化物）碗状结构。在此，我们基于平衡携带喹啉（L）和1,8 - 萘啶（L）供体的配体之间的氢键和排斥相互作用，引入这种策略的一种新亚型，以生成 - [PdL]和[PdLL']笼，并借助封装富勒烯的模板作用。结合吖啶（L）供体引起的空间拥挤，我们进一步报道了杂配体[PdLL'X]碗的首个实例。通过核磁共振、质谱和单晶X射线衍射研究了这些金属超分子主体的形成、结构和富勒烯结合能力。
