Fluorine extraction from organofluorine molecules to make fluorinated clusters in yttrium MOFs

Abstract

A new rare earth based two-dimensional coordination network and a three-dimensional metal–organic framework (MOF) have been synthesized using bicinchoninic acid (BCA) and yttrium(III) ions. Yttrium dimer nodes are formed in the absence of a modulator, resulting in a 2D layered coordination network (Y–BCA-2D). The presence of fluorinating agents, e.g., 2-fluorobenzoic acid (2-FBA), 2,6-difluorobenzoic acid (2,6-DFBA), and perfluorohexanoic acid (PFHxA) result in μ₃-F bridged metal hexaclusters (Y₆F₈) that form a three-dimensional MOF (Y–BCA-3D). It was found that Y³⁺ can break highly stable C–F bonds in aromatic and aliphatic fluorinated compounds. Single-crystal X-ray diffraction (SC-XRD) shows the presence of fluorine in the metal cluster which was confirmed by energy dispersive X-ray spectroscopy (EDS). High resolution X-ray photoelectron spectroscopy (XPS) and ¹⁹F Nuclear Magnetic Resonance (NMR) also verify the presence of metal–fluorine bonds in the cluster. The Y–BCA-3D MOF selectively adsorbs CO₂ but not N₂.