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Exposed Equatorial Positions of Metal Centers via Sequential Ligand Elimination and Installation in MOFs
- Yuan, Shuai, Zhang, Peng, Zhang, Liangliang, Garcia-Esparza, Angel T., Sokaras, Dimosthenis, Qin, Jun-Sheng, Feng, Liang, Day, Gregory S., Chen, Wenmiao, Drake, Hannah F., Elumalai, Palani, Madrahimov, Sherzod T., Sun, Daofeng, Zhou, Hong-Cai
- Journal of the American Chemical Society 2018 v.140 no.34 pp. 10814-10819
- catalysts, catalytic activity, cobalt, coordination polymers, copper, dimerization, ethylene, iron, ligands, manganese, metal ions, moieties, nickel, palladium
- Metal–organic frameworks (MOFs) provide highly designable platforms to construct complex coordination architectures for targeted applications. Herein, we demonstrate that trans-coordinated metal centers with exposed equatorial positions can be placed in a MOF matrix. A Zr-based MOF, namely, PCN-160, was initially synthesized as a scaffold structure. Postsynthetic linker labilization was subsequently implemented to partially remove the original dicarboxylate linkers and incorporate pyridinecarboxylates. A pair of neighboring pyridyl groups was arranged at proper proximity within the framework to form trans-binding sites that accommodate different metal cations including Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, and Pd²⁺. Furthermore, the trans-coordinated Ni²⁺ sites in porous frameworks can be readily accessed by substrates along the equatorial plane, facilitating the catalysis as manifested by the superior activity in ethylene dimerization over that observed for a cis-chelated catalyst.