Polyoxometalate–Organic Hybrid “Calixarenes” as Supramolecular Hosts
Yuan Gao, Ji Feng Guo, Yuyan Lai, Jiaheng Lin, Junrui Liu, Jianming Ji, Panchao Yin, Wei Wang, Hongmei Zhao, Guanying Chen, Lei Wang, Xikui Fang
Abstract
Abstract Calixarenes are among the most useful and versatile macrocycles in supramolecular chemistry. The one thing that has not changed in the 80 years since their discovery, despite numerous derivatizations, is their fully organic, covalent scaffolds. Here, we report a new type of organic–inorganic hybrid “calixarenes” constructed by means of coordination‐driven assembly. Replacing acetate ligands on the {SiW 10 Cr 2 (OAc) 2 } clusters with 5‐hydroxyisophthalates allows these 95° inorganic building blocks to be linked into bowl‐shaped, hybrid “calix[ n ]arenes” ( n =3, 4). With a large concave cavity, the metal–organic calix[4]arene can accommodate nanometer‐sized polyoxoanions in an entropically driven process. The development of hybrid variants of calixarenes is expected to expand the scope of their physicochemical properties, guest/substrate binding, and applications on multiple fronts.