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

机译:四氟对苯二甲酸的优化合成:用于新型配位聚合物和金属-有机骨架的通用连接配体

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摘要

Pure 2,3,5,6-tetrafluoroterephthalic acid (H2tfBDC) 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 (P1̅, Z = 1). Recrystallization from water/acetone leads to single crystals of H2tfBDC·2H2O (>2, P21/c, Z = 2), where an extensive hydrogen bonding network is found. By reacting H2tfBDC with an aqueous ammonia solution, single crystals of (NH4)2tfBDC (>3, C2/m, Z = 2) are obtained. >3 is thermally stable up to 250 °C and shows an enhanced solubility in water compared to H2tfBDC. Monosubstituted 2,3,5,6-tetrafluorobenzoic acid (H2tfBC, >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.
机译:通过使1,2,4,5-四氟苯与过量的(> 2当量)正丁基锂在四氢呋喃(THF)中反应以高收率(95%)获得纯的2,3,5,6-四氟对苯二甲酸(H2tfBDC) ),然后用CO2进行碳酸化,无需进行任何广泛的纯化程序。 H2tfBDC(> 1 )的单晶X射线结构分析证实了氘代样品(P 1 < mo>̅ ,Z = 1)。从水/丙酮中重结晶会生成H2tfBDC·2H2O单晶(> 2 ,P21 / c,Z = 2),在其中发现了广泛的氢键网络。通过使H2tfBDC与氨水溶液反应,获得(NH4)2tfBDC(> 3 ,C2 / m,Z = 2)的单晶。 > 3 在高达250°C的温度下具有热稳定性,并且与H2tfBDC相比,在水中的溶解度有所提高。单取代的2,3,5,6-四氟苯甲酸(H2tfBC,> 4)是通过使1,2,4,5-四氟苯与化学计量的(1当量)正丁基锂在THF中反应而获得的。其晶体结构(Fdd2,Z = 16)显示出二聚体单元作为特征结构特征。

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