Buckling cluster-based H-bonded icosahedral capsules and their propagation to a robust zeolite-like supramolecular framework
Zhan-Hua Zhao, Bao‐Liang Han, Hai‐Feng Su, Qi-Lin Guo, Wenxin Wang, Jing-Qiu Zhuo, Y. C. Guo, Jia-Long Liu, Geng‐Geng Luo, Ping Cui, Di Sun
Abstract
Hydrogen-bonded assembly of multiple components into well-defined icosahedral capsules akin to virus capsids has been elusive. In parallel, constructing robust zeolitic-like cluster-based supramolecular frameworks (CSFs) without any coordination covalent bonding linkages remains challenging. Herein, we report a cluster-based pseudoicosahedral H-bonded capsule Cu60, which is buckled by the self-organization of judiciously designed constituent copper clusters and anions. The spontaneous formation of the icosahedron in the solid state takes advantage of 48 charge-assisted CH···F hydrogen bonds between cationic clusters and anions (PF6-), and is highly sensitive to the surface protective ligands on the clusters with minor structural modification inhibiting its formation. Most excitingly, an extended three-periodic robust zeolitic-like CSF, is constructed by edge-sharing the resultant icosahedrons. The perpendicular channels of the CSF feature unusual 3D orthogonal double-helical patterns. The CSF material not only keeps its single-crystal character in the desolvated phase, but also exhibits excellent chemical and thermal stabilities as well as long-lived phosphorescence emission. H-bonded assembly of multiple components into well-defined icosahedral capsules has been elusive, and constructing stable sophisticated cluster-based supramolecular frameworks without coordinative bonding linkages remains challenging. Here, the authors report a cluster-based icosahedral H-bonded capsule Cu60 and its self-propagation into a 3D robust zeolitic-like supramolecular framework.