Zhao Zhan-Hua, Han Bao-Liang, Su Hai-Feng, Guo Qi-Lin, Wang Wen-Xin, Zhuo Jing-Qiu, Guo Yong-Nan, Liu Jia-Long, Luo Geng-Geng, Cui Ping, Sun Di
College of Materials Science and Engineering, Huaqiao University, Xiamen, PR China.
Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Jinan, PR China.
Nat Commun. 2024 Oct 30;15(1):9401. doi: 10.1038/s41467-024-53640-4.
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 Cu, 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 (PF), 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.
将多种成分通过氢键组装成类似于病毒衣壳的定义明确的二十面体胶囊一直难以实现。与此同时，构建没有任何配位共价键连接的坚固的类沸石簇基超分子框架（CSF）仍然具有挑战性。在此，我们报道了一种基于簇的伪二十面体氢键胶囊Cu，它是由精心设计的组成铜簇和阴离子的自组装而弯曲的。固态下二十面体的自发形成利用了阳离子簇和阴离子（PF）之间48个电荷辅助的CH···F氢键，并且对簇上的表面保护配体高度敏感，微小的结构修饰会抑制其形成。最令人兴奋的是，通过将所得二十面体的边共享构建了一种扩展的三周期坚固类沸石CSF。CSF的垂直通道具有不寻常的3D正交双螺旋模式。CSF材料不仅在脱溶剂相中保持其单晶特性，而且还表现出优异的化学和热稳定性以及长寿命的磷光发射。
