Abstract Three novel inorganic-organic hybrid nanomaterials [Mn(HL)4Cl2](PW12O40)2.4CH3OH.8H2O (1), [Ni(L)2]2(PW12O40).2HCl.4CH3OH.8H2O (2) and [Cd(HL)6](PW12O40)2.3CH3OH.8H2O (3) have been synthesized by a simple one-pot reaction of phosphotungestic acid (H3PW12O40 abbreviated as PW12) and 2-pyridinecarbaldehyde semicarbazone ligand (HL). The synthesized hybrid nanomaterials were characterized by FT˗IR, UV˗Vis, powder and single crystal X˗ray diffraction (XRD), SEM, EDX and TGA. The FT-IR, UV–Vis, PXRD and TG results of nanomaterials 1–3 confirm their successful synthesis. Compound 1 with a monoclinic P21/c space group exhibits a three-dimensional (3D) framework composed Keggin-type PW12 clusters and discrete octahedral trans-[Mn(HL)4Cl2]. In compound 2, a 3D network constructed from octahedral [Ni(L)2] and individual PW12 clusters in the triclinic P-1 space group. Compound 3 crystallizes in the triclinic P-1 space group and displays a complicated 3D network built by the Keggin PW12 POM clusters and discrete tetrahedral [Cd(HL)4]2+complex subunits. In counds 1 and 3, the HL semicarbazone act as a O(C O)-donor monodentate ligand, while in the compound 2 the deprotonated L semicarbazone functions as a Npy,N,O(C O)-donor tridentate ligand. The crystal components in 1–3 are connected through numerous weak N/C–H⋯O(POM) and N/C–H⋯Cl hydrogen bonds to construct the three-dimensional networks. In 1–3, the 3D supramolecular networks are maintained through electrostatic and/or hydrogen bonding interactions. For compounds 1–3, both the simulated and experimental X-ray powder diffraction patterns match each other, indicating good phase purity of our samples. Furthermore, the performance of 1–3 in the removal of cationic methylene blue (MB) dye and anionic methyl orang (MO) dye from aqueous solutions was investigated.

中文翻译：

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基于 keggin 型 12-钨磷酸盐和一些金属缩氨基脲复合物的新型混合纳米结构：合成、X 射线晶体结构和光谱研究

摘要 三种新型无机-有机杂化纳米材料 [Mn(HL)4Cl2](PW12O40)2.4CH3OH.8H2O (1), [Ni(L)2]2(PW12O40).2HCl.4CH3OH.8H2O (2) 和 [Cd( HL)6](PW12O40)2.3CH3OH.8H2O (3) 已通过磷钨酸（H3PW12O40 缩写为 PW12）和 2-吡啶甲醛缩氨基脲配体 (HL) 的简单一锅反应合成。合成的杂化纳米材料通过FT˗IR、UV˗Vis、粉末和单晶X˗射线衍射（XRD）、SEM、EDX和TGA表征。纳米材料 1-3 的 FT-IR、UV-Vis、PXRD 和 TG 结果证实了它们的成功合成。具有单斜 P21/c 空间群的化合物 1 表现出由 Keggin 型 PW12 簇和离散八面体反式 [Mn(HL)4Cl2] 组成的三维 (3D) 框架。在化合物 2 中，由八面体 [Ni(L)2] 和三斜 P-1 空间群中的单个 PW12 簇构建的 3D 网络。化合物 3 在三斜 P-1 空间群中结晶，并显示出由 Keggin PW12 POM 簇和离散四面体 [Cd(HL)4]2+复杂亚基构建的复杂 3D 网络。在化合物 1 和 3 中，HL 缩氨基脲作为 O(CO)-供体单齿配体，而在化合物 2 中，去质子化的 L 缩氨基脲作为 Npy,N,O(CO)-供体三齿配体。1-3中的晶体成分通过无数弱N/C-H⋯O(POM)和N/C-H⋯Cl氢键连接，构成三维网络。在 1-3 中，3D 超分子网络通过静电和/或氢键相互作用维持。对于化合物 1-3，模拟和实验 X 射线粉末衍射图相互匹配，表明我们的样品具有良好的相纯度。此外，研究了 1-3 从水溶液中去除阳离子亚甲蓝 (MB) 染料和阴离子甲基橙 (MO) 染料的性能。