College of Chemistry, Beijing Normal University, Beijing, P R China.
Dalton Trans. 2012 Mar 7;41(9):2639-47. doi: 10.1039/c2dt11532h. Epub 2012 Jan 6.
Hydro- and solvo-thermal reactions of d-block metal ions (Mn(2+), Co(2+), Zn(2+) and Cd(2+)) with monosodium 2-sulfoterephthalate (NaH(2)stp) form six 3D coordination polymers featuring cluster core M(4)(μ(3)-OH)(2) in common: [M(2)(μ(3)-OH)(stp)(H(2)O)] (M = Co (1), Mn (2) and Zn (3)), [Zn(2)(μ(3)-OH)(stp)(H(2)O)(2)] (4), [Zn(4)(μ(3)-OH)(2)(stp)(2)(bpy)(2)(H(2)O)]·3.5H(2)O (5) and [Cd(2)(μ(3)-OH)(stp) (bpp)(2)]·H(2)O (6) (stp = 2-sulfoterephthalate, bpy = 4,4'-bipyridine and bpp = 1,3-di(4-pyridyl)propane). All these coordination polymers were characterized by single crystal X-ray diffraction, IR spectroscopy, thermogravimetric and elemental analysis. Complexes 1-3 are isostructural coordination polymers with 3D frameworks based on the chair-like Zn(4)(μ(3)-OH)(2) core and the quintuple helixes. In complex 4, there exist double helixes in the 3D framework based on the chair-like cluster cores. Complex 5 possesses a 2-fold interpenetration structure constructed from boat-like cluster core and the bridging ligands stp and bpy. For complex 6, the chair-like cluster cores and stp ligands form a 2D (4,4) network which is further pillared by bpp linkers to a 3D architecture. Magnetic studies indicate that complex 1 exhibits magnetic ordering below 4.9 K with spin canting, and complex 2 shows weak antiferromagnetic coupling between the Mn(II) ions with g = 2.02, J(wb) = -2.88 cm(-1), J(bb) = -0.37 cm(-1). The fluorescence studies show that the emissions of complexes 3-6 are attributed to the ligand π-π* transition.
D 块金属离子（Mn(2+)、Co(2+)、Zn(2+)和 Cd(2+)）与单酸钠 2-磺基对苯二甲酸（NaH(2)stp）的水热和溶剂热反应形成了六个具有共同的簇核M(4)(μ(3)-OH)(2)的 3D 配位聚合物：[M(2)(μ(3)-OH)(stp)(H(2)O)]（M = Co（1），Mn（2）和 Zn（3）），[Zn(2)(μ(3)-OH)(stp)(H(2)O)(2)]（4），[Zn(4)(μ(3)-OH)(2)(stp)(2)(bpy)(2)(H(2)O)]·3.5H(2)O（5）和[Cd(2)(μ(3)-OH)(stp)(bpp)(2)]·H(2)O（6）（stp = 2-磺基对苯二甲酸，bpy = 4,4'-联吡啶，bpp = 1,3-二（4-吡啶基）丙烷）。所有这些配位聚合物都通过单晶 X 射线衍射、红外光谱、热重分析和元素分析进行了表征。配合物 1-3 是具有基于椅式Zn(4)(μ(3)-OH)(2)核和五重螺旋的 3D 骨架的等结构配位聚合物。在配合物 4 中，在基于椅式簇核的 3D 骨架中存在双螺旋。配合物 5 具有由船式簇核和桥连配体 stp 和 bpy 构建的 2 倍互穿结构。对于配合物 6，椅式簇核和 stp 配体形成二维（4,4）网络，该网络进一步由 bpp 连接体支柱化形成 3D 结构。磁性研究表明，配合物 1 在 4.9 K 以下表现出磁有序，自旋倾斜，配合物 2 显示 Mn(II)离子之间的弱反铁磁耦合，g = 2.02，J(wb) = -2.88 cm(-1)，J(bb) = -0.37 cm(-1)。荧光研究表明，配合物 3-6 的发射归因于配体的π-π*跃迁。
