Exposed Equatorial Positions of Metal Centers via Sequential Ligand Elimination and Installation in MOFs
- Texas A & M Univ., College Station, TX (United States)
- China Univ. of Petroleum (East China), Shandong (China)
- SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Texas A&M Univ. at Qatar, Doha (Qatar)
Here, 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.
- Research Organization:
- Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Fossil Energy (FE)
- Grant/Contract Number:
- A-0030; IIP-1632486; SC0001015; DGE-1252521; NPRP9-377-1-080; FE0026472
- OSTI ID:
- 1475583
- Journal Information:
- Journal of the American Chemical Society, Vol. 140, Issue 34; ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
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