Assemblies of a new flexible multicarboxylate ligand and d10 metal centers toward the construction of homochiral helical coordination polymers: structures, luminescence, and NLO-active properties.
Assemblies of a new flexible multicarboxylate ligand and d10 metal centers toward the construction of homochiral helical coordination polymers: structures, luminescence, and NLO-active properties.
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DOI：
10.1021/ic051502m
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发表时间：
2006-01
影响因子：
4.6
通讯作者：
Shuangquan Zang;Yang Su;Yi-zhi Li;Z. Ni;Q. Meng
中科院分区：
文献类型：
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作者：
Shuangquan Zang;Yang Su;Yi-zhi Li;Z. Ni;Q. Meng
在 4,4'-联吡啶 (bpy) 存在下，2,2',3,3'-氧二邻苯二甲酸 (2,2',3,3'-H(4)ODPA) 的新型柔性多羧酸盐配体与 M(NO(3))(2).xH(2)O (M = Zn, x = 6; M = Cd, x = 4) 之间的水（溶剂）热反应提供了两个新型纯手性螺旋配位聚合物[[Zn(2)(2,2',3,3'-ODPA)(bpy)(H(2)O)(3)].(H(2)O)(2)为1和[Cd(2)(2,2',3,3'-ODPA)(bpy)(H(2)O)(3)].(H(2)O)(2)为2]。虽然化学式几乎相同，但它们具有不同的空间基团（1为P2(1)2(1)2(1)，2为P2(1)）和2,2',3,3'-ODPA配体不同的桥接模式。 1和2中都发现了两种同手性螺旋（右旋），每种螺旋仅区分一种晶体学非等价金属原子。 1具有二维金属有机骨架，可以看作两个平行的纯手性Zn1和Zn2螺旋的统一体，其中节点是醚氧原子。相比之下，2 具有 3D 金属有机骨架，在二维上由两个部分重叠的纯手性 Cd1 和 Cd2 螺旋组成。此外，金属-ODPA螺旋在二维1和2上都给出了2D手性人字形结构基序，bpy的第二个配体进一步增强了该结构基序。 1和2的散装物料均具有良好的二次谐波产生活性，约为尿素的1和0.8倍。
Hydro(solvo)thermal reactions between a new flexible multicarboxylate ligand of 2,2',3,3'-oxydiphthalic acid (2,2',3,3'-H(4)ODPA) and M(NO(3))(2).xH(2)O (M = Zn, x = 6; M = Cd, x = 4) in the presence of 4,4'-bipyridine (bpy) afford two novel homochiral helical coordination polymers [[Zn(2)(2,2',3,3'-ODPA)(bpy)(H(2)O)(3)].(H(2)O)(2) for 1 and [Cd(2)(2,2',3,3'-ODPA)(bpy)(H(2)O)(3)].(H(2)O)(2) for 2]. Though having almost the same chemical formula, they have different space groups (P2(1)2(1)2(1) for 1 and P2(1) for 2) and different bridging modes of the 2,2',3,3'-ODPA ligand. Two kinds of homochiral helices (right-handed) are found in both 1 and 2, each of which discriminates only one kind of crystallographical nonequivalent metal atom. 1 has a 2D metal-organic framework and can be seen as the unity of two parallel homochiral Zn1 and Zn2 helices, in which the nodes are etheric oxygen atoms. In contrast, 2 has a 3D metal-organic framework and consists of two partially overlapped homochiral Cd1 and Cd2 helices in the two dimensions. Moreover, metal-ODPA helices give a 2D chiral herringbone structural motif in both 1 and 2 in the two dimensions, which are further strengthened by the second ligand of bpy. Bulk materials for 1 and 2 all have good second-harmonic generation activity, approximately 1 and 0.8 times that of urea.