para-Benzene disulfonic acid and its tetrachloro and tetrafluoro derivatives--studies towards polyhalogenated metal-organic-frameworks with sulfo analogues of terephthalic acid.
para-Benzene disulfonic acid and its tetrachloro and tetrafluoro derivatives--studies towards polyhalogenated metal-organic-frameworks with sulfo analogues of terephthalic acid.
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DOI：
10.1039/c0dt01223h
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发表时间：
2011-03
影响因子：
4
通讯作者：
Thomas W. T. Muesmann;Christina Zitzer;Andrea Mietrach;T. Klüner;J. Christoffers;M. Wickleder
中科院分区：
文献类型：
--
作者：
Thomas W. T. Muesmann;Christina Zitzer;Andrea Mietrach;T. Klüner;J. Christoffers;M. Wickleder
我们开发了制备对苯二磺酸(H(2)BDS)及其四氯(H(2)BDSCl(4))和四氟(H(2)BDSF(4))衍生物的便捷合成路线。这些酸与DMF中的硝酸锌反应生成[Zn(BDS)(DMF)(2)]单晶（三斜晶系，P̄1[组合宏基]，Z=2，a=976.62(4)，b=986.85(4)，c=1014.40(4)，α=69.106(2)°， β=68.746(2)°, γ=86.295(2)°, wR(2)=0.0627), [Zn(BDSCl(4))(DMF)(4)] (三斜晶系, P ̄1[组合宏子], Z=1, a=831.5(1), b=905.2(1), c=989.6(1), α=90.44(2)°、β=91.41(2)°、γ=106.72(2)°、wR(2)=0.0635)和[Zn(BDSF(4))(DMF)(4)]（单斜晶系，P2(1)/c，Z=2，a=889.01(3)，b=968.91(3)， c=1633.07(5)pm，β=106.524(2)°，wR(2)=0.0948)。虽然 [Zn(BDS)(DMF)(2)] 呈现层状结构，但二磺酸盐连接基将锌离子连接成 [Zn(BDSCl(4))(DMF)(4)] 和 [Zn(BDSF(4))(DMF)(4)] 晶体结构中的链。热分析研究表明，化合物的去溶剂化发生在 100 至 200 °C 的温度范围内。无溶剂磺酸盐表现出非常高的稳定性，[Zn(BDS)(DMF)(2)] 在高达近 600 °C 的温度下保持稳定。卤代酸还用于从水溶液和作为铜源的 Cu(2)(OH)(2)(CO(3))（孔雀石）制备铜盐。 [Cu(H(2)O)(6)](BDSF(4))的晶体结构（三斜晶系，P̄1[结合宏晶]，Z=1，a=510.45(2)，b=744.68(3)，c=1077.77(4) pm，α=85.627 (2)°，β=77.449 (2)°， γ=76.015 (2)°) 表现出复杂的阳离子和不配位的磺酸根阴离子，而 [Cu(BDSCl(4))(H(2)O)(4)] （斜方晶系，Pnma，Z=4，a=721.27(2)，b=2147.81(6)，c=979.42(3) pm）中的 Cu(2+) 离子是 与晶体结构中的无限链相连。 [Cu(BDSCl(4))(H(2)O)(4)] 最有趣的结构特征是二磺酸双阴离子的平面性显着偏离。理论研究表明，在磺酸基发生顺式配位的情况下，由于空间位阻，船构象是有利的。还通过 DTA/TG 测量和 X 射线粉末衍射研究了铜化合物的热行为。
We developed convenient synthetic routes for the preparation of para-benzene disulfonic acid (H(2)BDS) and its tetrachloro (H(2)BDSCl(4)) and tetrafluoro (H(2)BDSF(4)) derivatives. The reaction of these acids with zinc nitrate in DMF led to single crystals of [Zn(BDS)(DMF)(2)] (triclinic, P ̄1[combining macron], Z=2, a=976.62(4), b=986.85(4), c=1014.40(4), α=69.106(2)°, β=68.746(2)°, γ=86.295(2)°, wR(2)=0.0627), [Zn(BDSCl(4))(DMF)(4)] (triclinic, P ̄1[combining macron], Z=1, a=831.5(1), b=905.2(1), c=989.6(1), α=90.44(2)°, β=91.41 (2)°, γ=106.72(2)°, wR(2)=0.0635), and [Zn(BDSF(4))(DMF)(4)] (monoclinic, P2(1)/c, Z=2, a=889.01(3), b=968.91(3), c=1633.07(5) pm, β=106.524(2)°, wR(2)=0.0948). While [Zn(BDS)(DMF)(2)] exhibits a layer structure, the disulfonate linkers connect the zinc ions into chains in the crystal structures of [Zn(BDSCl(4))(DMF)(4)] and [Zn(BDSF(4))(DMF)(4)]. Thermoanalytical investigations revealed that desolvation of the compounds occurs in a temperature range between 100 and 200 °C. The solvent free sulfonates show remarkably high stabilities, [Zn(BDS)(DMF)(2)] is stable up to nearly 600 °C. The halogenated acids were also used to prepare copper salts from aqueous solutions and Cu(2)(OH)(2)(CO(3)) (malachite) as a copper source. The crystal structure of [Cu(H(2)O)(6)](BDSF(4)) (triclinic, P ̄1[combining macron], Z=1, a=510.45(2), b=744.68(3), c=1077.77(4) pm, α=85.627 (2)°, β=77.449 (2)°, γ=76.015 (2)°) exhibits complex cations and uncoordinated sulfonate anions, while in [Cu(BDSCl(4))(H(2)O)(4)] (orthorhombic, Pnma, Z=4, a=721.27(2), b=2147.81(6), c=979.42(3) pm) the Cu(2+) ions are linked to infinite chains in the crystal structure. The most interesting structural feature of [Cu(BDSCl(4))(H(2)O)(4)] is the significant deviation from planarity of the disulfonate dianion. Theoretical investigations revealed that a boat conformation is favoured due to steric hindrance in cases where a syn coordination of the sulfonate groups occurs. The thermal behaviour of the copper compounds was also investigated by DTA/TG measurements and X-ray powder diffraction.