Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi'an 710069, P. R. China.
Chem Asian J. 2010 Jul 5;5(7):1611-9. doi: 10.1002/asia.200900751.
This article systematically investigates the influence of the properties of inhomogeneous N-auxiliary ligands and pH value on the helical structures of complexes based on C(2)-symmetric ligand 1,3-adamantanedicarboxylic acid (H(2)ADC). Five kinds of neutral ligands (phen=1,10-phenanthroline, bipy=4,4'-bipyridine, bpa=1,2-bis(4-pyridyl)ethane, bpe=1,2-bis(4-pyridyl)ethane, and bpp=1,3-bis(4-pyridyl)propane) were selected, and a series of new Zn(II)/Co(II) dicarboxylates have been synthesized by slow diffusion, namely, Zn(phen)(ADC)(H(2)O).CH(3)OH (1), {[Zn(ADC)(bpe)].H(2)O}(n) (2), {[Zn(ADC)(bipy)].2H(2)O}(n) (3), {Zn(ADC)(bpa).5H(2)O}(n) (4), {Zn(ADC)(bpp).CH(3)OH}(n) (5), {[Zn(ADC)(bpp)]}(n) (6), {[Co(ADC)(bpp)(CH(3)OH)(H(2)O)].CH(3)OH2 H(2)O}(n) (7), and {[Co(ADC)(bpp)]}(n) (8). Single-crystal X-ray structural analysis shows that complex 1 forms a 0D dinuclear with closed-loop unit. The complex 2 is a 2D layer framework. Compounds 3 and 4 are isomorphous with a small discrepancy and present one-dimensional chainlike structures. It is interesting that the 2D organic-inorganic hybrid frameworks containing meso-helical chains have been observed. Compound 5 is a 2D interpenetrated network with (4,4) topology, in which homochiral left-handed helical chains are arranged in an ABAB sequence parallel to the plane defined by (a,c), and right-handed helical chains running along the a axis are also observed in the solid state, resulting in a meso-helical structure. Compounds 6, 7, and 8 crystallize in a chiral space group P212121. Highly dimensional 6 and 8 are essentially isostructural and present a threefold interpenetrated 3D diamondoid network containing three helical chains, whereas 7 exhibits a 2D grid layer with a left-handed helical chain. Furthermore, thermal stability, X-ray powder diffraction, and the luminescent properties of 1-6 are also discussed.
本文系统研究了非均相 N-辅助配体的性质和 pH 值对基于 C(2)对称配体 1,3-金刚烷二羧酸(H(2)ADC)的配合物螺旋结构的影响。选择了五种中性配体(苯=1,10-菲咯啉、联吡啶=bipy=4,4'-联吡啶、1,2-双(4-吡啶基)乙烷=bpa=1,2-双(4-吡啶基)乙烷、1,2-双(4-吡啶基)乙烷=bpe=1,2-双(4-吡啶基)乙烷、1,3-双(4-吡啶基)丙烷=bpp=1,3-双(4-吡啶基)丙烷)，通过缓慢扩散合成了一系列新的 Zn(II)/Co(II) 二羧酸酯，即Zn(phen)(ADC)(H(2)O).CH(3)OH (1)、{[Zn(ADC)(bpe)].H(2)O}(n) (2)、{[Zn(ADC)(bipy)].2H(2)O}(n) (3)、{Zn(ADC)(bpa).5H(2)O}(n) (4)、{Zn(ADC)(bpp).CH(3)OH}(n) (5)、{[Zn(ADC)(bpp)]}(n) (6)、{[Co(ADC)(bpp)(CH(3)OH)(H(2)O)].CH(3)OH2 H(2)O}(n) (7)和{[Co(ADC)(bpp)]}(n) (8)。单晶 X 射线结构分析表明，配合物 1 形成具有闭合环单元的 0D 双核。配合物 2 是二维层状结构。化合物 3 和 4 是同构的，略有差异，呈现一维链状结构。有趣的是，观察到了含有介孔螺旋链的二维有机-无机杂化骨架。化合物 5 是具有(4,4)拓扑的二维互穿网络，其中同手性的左手螺旋链以 ABAB 序列平行于(a,c)定义的平面排列，在固态中还观察到沿 a 轴的右手螺旋链，导致介孔螺旋结构。化合物 6、7 和 8 在手性空间群 P212121 中结晶。高维 6 和 8 在本质上是同构的，呈现出三重互穿的 3D 金刚石状网络，包含三个螺旋链，而 7 则表现出具有左手螺旋链的二维网格层。此外，还讨论了 1-6 的热稳定性、X 射线粉末衍射和发光性能。
