Metal-organic frameworks (MOFs) are porous crystalline materials constructed from organic linkers and metal ions (or clusters). Advances in MOFs applications include gas storage and separation, drug delivery, sensors, water capture, and catalysis, depends in part on new structures. We recently discovered a new methodology for the preparation of fluoro-bridged rare earth (RE) clusters.1 In this presentation a new series of RE MOFs synthesized using bicinchoninic acid (BCA) and lanthanides (RE= Y, Eu, Gd, Tb, Dy, Ho, and Yb) will be discussed. The formation and role of fluoro-bridged rigid metal clusters will also be discussed. Two-dimensional MOFs based on RE dimer nodes are formed in the absence of organo-fluorine molecule. In contrast the addition of 2-fluorobenzoic acid (2-fba), 2,6-difluorobenzoic acid (2,6-dfba), or other fluoro-organic compounds results in μ3-F bridged hexaclusters (Figure 1a) and the porous 3D MOFs shown in Figure 1b. The presence of fluorine was verified by XRD, EDS and XPS analysis. Prilimnary data shows these MOFs are selective for CO2. The Eu-MOFs are fluorescent, their fluorescence can be tuned using mixed metals for thermo or host-guest based sensing applications. This study will also help to explore how presence of μ3-F bridging could increase the fluorescence intensity in hexacluster MOFs.

Formation and importance of fluoro-bridging in rare earth metal-organic frameworks

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