An Aluminum-Based Metal-Organic Cage for Cesium Capture.

Abstract

Metal-organic cages are a class of supramolecular structures that often require the careful selection of organic linkers and metal nodes. Of this class, few examples of metal-organic cages exist where the nodes are composed of main group metals. Herein, we have prepared an aluminum-based metal-organic cage, H8[Al8(pdc)8(OAc)8O4] (Al-pdc-AA), using inexpensive and commercially available materials. The cage formation was achieved via solvothermal self-assembly of solvated aluminum and pyridine-dicarboxylic linkers in the presence of a capping agent, acetic acid. The obtained supramolecular structure was characterized by single-crystal X-ray diffraction (SCXRD), thermogravimetric analysis, and NMR spectroscopy. Based on crystal structure and computational analyses, the cage has a 3.7 Å diameter electron-rich cavity suitable for the binding of cations such as cesium (ionic radius of 1.69 Å). The host-guest interactions were probed with 1H and 133Cs NMR spectroscopy in DMSO, where at low concentrations, Cs+ binds to Al-pdc-AA in a 1:1 ratio. The binding site was identified from the crystal structure of CsH7[Al8(pdc)8(OAc)8O4] (Cs+⊂Al-pdc-AA), and a binding affinity of ∼106-107 M-1 was determined from NMR titration experiments. The Al-pdc-AA showed improved selectivity for cesium binding over alkali metal cations (Cs+ > Rb+ > K+ ≫ Na+ ∼ Li+). Collectively, the study reports a novel aluminum cage that can serve as a promising host for efficient and selective cesium removal.