Qi Yanfei, Li Yangguang, Qin Chao, Wang Enbo, Jin Hua, Xiao Dongrong, Wang Xinglong, Chang Song
Key Laboratory of Polyoxometalates Science of Ministry of Education, Department of Chemistry, Northeast Normal University, Changchun, Jinlin, People's Republic of China.
Inorg Chem. 2007 Apr 16;46(8):3217-30. doi: 10.1021/ic062338l. Epub 2007 Mar 20.
A series of novel organic-inorganic assemblies, [Zn(Meen)2]2[(4,4'-bipy)Zn2As8V12O40(H2O)] (1), [Zn(en)2(H2O)][Zn(en)2(4,4'-bipy)Zn2As8V12O40(H2O)].3H2O (2), [[Zn(en)3]2[Zn2As8V12O40(H2O)]].4H2O.0.25bipy (3) and [Zn2(en)5][[Zn(en)2][(bpe)HZn2As8V12O40(H2O)]2].7H2O (4) [en = ethylenediamine, Meen = 1,2-diaminopropane, 4,4'-bipy = 4,4'-bipyridine, and bpe = 1,2-bis(4-pyridyl)ethane] constructed from organically modified Zn-substituted polyoxovanadates and zinc organoamine subunits have been synthesized. Each anion cluster of compound 1 is directly linked by the 4,4'-bipy ligand into a one-dimensional (1D) straight chain. The secondary metal complex [Zn(Meen)2]2+ acts as an isolated countercation. The 1D chain structure of 2 is similar to that of 1 but sinuate because of the secondary metal complex [Zn(en)2]2+ decorated on the anion cluster. The en ligands covalently bonding to the surface anion of 3 not only support the secondary metal complex [Zn(en)2]2+ but also coordinate to another anion through the secondary metal complex [Zn(en)2]2+ bridge to form an "eight-shaped" chiral helix. The unprecedented 2D layer of compound 4 with large nanosized inner rectangular cavities [33.669(6) x 14.720(8) A] is successfully achieved through the anion clusters polymerized first into chains by flexible organic ligands and then secondary metal complexes bridged between the chains. The different coordination abilities and geometries of the bidentate organodiamine ligands used in the four-reaction systems play important roles in the formation of the final structures: from straight chains to sinuate chains, to helical chiral chains, and finally to a 2D layer with helices.
已合成了一系列由有机修饰的锌取代多钒酸盐和锌有机胺亚基构建的新型有机 - 无机组装体，即[Zn(Meen)₂]₂[(4,4'-联吡啶)Zn₂As₈V₁₂O₄₀(H₂O)] (1)、[Zn(en)₂(H₂O)][Zn(en)₂(4,4'-联吡啶)Zn₂As₈V₁₂O₄₀(H₂O)].3H₂O (2)、[[Zn(en)₃]₂[Zn₂As₈V₁₂O₄₀(H₂O)]].4H₂O.0.25联吡啶 (3) 和 [Zn₂(en)₅][[Zn(en)₂][(bpe)HZn₂As₈V₁₂O₄₀(H₂O)]₂].7H₂O (4) [en = 乙二胺，Meen = 1,2 - 二氨基丙烷，4,4'-联吡啶 = 4,4'-联吡啶，bpe = 1,2 - 双(4 - 吡啶基)乙烷]。化合物1的每个阴离子簇通过4,4'-联吡啶配体直接连接成一维（1D）直链。二级金属配合物[Zn(Meen)₂]²⁺作为孤立的抗衡阳离子。化合物2的1D链结构与化合物1相似，但由于修饰在阴离子簇上的二级金属配合物[Zn(en)₂]²⁺而呈正弦状。与化合物3的表面阴离子共价键合的en配体不仅支撑二级金属配合物[Zn(en)₂]²⁺，还通过二级金属配合物[Zn(en)₂]²⁺桥与另一个阴离子配位形成“8字形”手性螺旋。化合物4通过阴离子簇首先由柔性有机配体聚合成链，然后由二级金属配合物在链之间桥连，成功实现了具有大尺寸纳米内矩形腔[33.669(6)×14.720(8) Å]的前所未有的二维层。四反应体系中使用的双齿有机二胺配体的不同配位能力和几何形状在最终结构的形成中起重要作用：从直链到正弦链，再到螺旋手性链，最后到具有螺旋结构的二维层。
