Optimized Synthesis of Tetrafluoroterephthalic Acid: A Versatile Linking Ligand for the Construction of New Coordination Polymers and Metal-Organic Frameworks

Pure 2,3,5,6-tetrafluoroterephthalic acid (H(2)tfBDC) is obtained in high yields (95%) by reacting 1,2,4,5-tetrafluorobenzene with a surplus (>2 equiv) of n-butyllithium in tetrahydrofuran (THF) and subsequent carbonation with CO2 without any extensive purification procedure. A single crystal X-ray structure analysis of H2tfBDC (1) confirms former data obtained for a deuterated sample (P (1) over bar, Z = 1). Recrystallization from water/acetone leads to single crystals of H(2)tfBDC center dot 2H(2)O (2, P2(1)/c, Z. 2), where an extensive hydrogen bonding network is found. By reacting H2tfBDC with an aqueous ammonia solution, single crystals of (NH4)(2)tfBDC (3, C2/m, Z. 2) are obtained. 3 is thermally stable up to 250 degrees C and shows an enhanced solubility in water compared to H(2)tfBDC. Monosubstituted 2,3,5,6-tetrafluorobenzoic acid (H(2)tfBC, 4) is obtained by reacting 1,2,4,5-tetrafluorobenzene with stoichiometric amounts (1 equiv) of n-butyllithium in THF. Its crystal structure (Fdd2, Z = 16) shows dimeric units as characteristic structural feature.