Zn[Htma][ddm]: An Interesting Three-Dimensional Chiral Nonlinear Optical-Active Zinc-Trimesate Framework
Zn[Htma][ddm]: An Interesting Three-Dimensional Chiral Nonlinear Optical-Active Zinc-Trimesate Framework
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Zn[Htma][ddm]：一种有趣的三维手性非线性光学活性苯均酸锌框架
DOI：
10.1021/cg901259e
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发表时间：
2010-02-01
影响因子：
3.8
通讯作者：
Dai, Jing-Cao
中科院分区：
文献类型：
--
作者：
Liu, Li;Huang, Shu-Ping;Dai, Jing-Cao
新型聚合物固体 Zn[Htma][ddm] (1)（tma = 均苯三酸，ddm = p,p'-二氨基二烯基甲烷）的三维 (3D) 手性螺旋骨架是通过二水合乙酸锌、H(3)tma 和 ddm 的水热反应制备的。 X射线单晶结构分析表明1(C22H18N2O6Zn)结晶于斜方P2(1)2(1)2(1)空间群，Z = 4(a = 5.4533(3)埃，b = 17.593(1)埃，c 20.542(1)埃，V = 1970.8(2)埃(3))。 1 中的四面体配位锌中心由具有 Delta 配置的刚性三角构造 tma 配体加上柔性 ddm 分子桥接，产生有趣的 3D 手性螺旋金刚石网络单一对映体，该对映体已被固态圆二色光谱证实。 1 在周围环境中在高达约 297 摄氏度的温度下保持稳定，并在 326 nm 激发后在 420 nm 处表现出强烈的荧光发射带以及带隙半导体特性。理论计算表明1是一种潜在的非线性光学活性材料。
The three-dimensional (3D) chiral helical framework of the new polymeric solid, Zn[Htma][ddm] (1) (tma = trimesate, ddm = p,p'-diamino-diplienyl-methane), has been prepared by the hydrothermal reaction of zinc acetate dihydrate, H(3)tma, and ddm. X-ray single-crystal structural analysis reveals that 1 (C22H18N2O6Zn) crystallizes in the orthorhombic P2(1)2(1)2(1) space group, Z = 4 (a = 5.4533(3) angstrom, b = 17.593(1) angstrom, c 20.542(1) angstrom, V = 1970.8(2) angstrom(3)). Tetrahedrally coordinated zinc centers in 1 bridged by the rigid trigonal tectonic tma ligands with Delta-configuration plus the flexible ddm molecules give rise to an interesting 3D chiral helical diamondoid network single enantiomer that has been confirmed by solid-state circular dichroism spectra. 1 is stable up to about 297 degrees C in the ambient environment and exhibits an intense fluorescent emission band at 420 nm upon excitation at 326 nm and the band gap semiconducing character. The theoretical calculations reveal that 1 is a potential nonlinear optical-active material.