Various Anderson-type polyoxometalate-based metal-organic complexes induced by diverse solvents: assembly, structures and selective adsorption for organic dyes.,Dalton Transactions

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Various Anderson-type polyoxometalate-based metal-organic complexes induced by diverse solvents: assembly, structures and selective adsorption for organic dyes.
Dalton Transactions ( IF 3.5 ) Pub Date : 2020-01-06 , DOI: 10.1039/c9dt04397g
Jia-Hui Li ₁ , Xiu-Li Wang ₁ , Ge Song ₁ , Hong-Yan Lin ₁ , Xiang Wang ₁ , Guo-Cheng Liu ₁

Affiliation

Six new Anderson-type polyoxometalate (POM)-based metal-organic complexes (MOCs), namely, {HCu(HPCAP)2[CrMo6(OH)6O18]}·2H2O (1), {Zn4(PCAP)2[CrMo6(OH)6O18]2(H2O)12}·4H2O (2), {Zn3(PCAP)2[CrMo6(OH)5O19](H2O)6}·6H2O (3), {Ni3(PCAP)2[NiMo6(OH)5O19](H2O)6}·8H2O (4), {Cu3(PCAP)2[AlMo6(OH)5O19](H2O)6}·6H2O (5), and {Co3(HPCAP)2[AlMo6(OH)6O18](H2O)10}[AlMo6(OH)6O18]·6H2O (6) (HPCAP = 3-(2-pyridinecarboxylic acid amido)pyridine), were constructed from diverse metal ions (CuII/ZnII/NiII/CoII), the HPCAP ligand and various Anderson-type POM anions under hydrothermal and solvothermal conditions and structurally characterized by single-crystal X-ray diffraction, IR spectroscopy, powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Crystal analysis shows that complex 1 has a 3D supramolecular structure based on the CrMo6 anions and the 1D metal-organic ribbon chains [Cu(HPCAP)2] via hydrogen bonds. Complex 2 is a 2D supramolecular layer composed of two kinds of dinuclear metal clusters of [Zn2(CrMo6)2] and [Zn2(PCAP)2]. Complexes 3-5 show similar 3D frameworks. In 3-5, [M1Mo6]3- (M1 = Cr for 3, Ni for 4, and Al for 5) anions are bridged by MII ions (M = Zn for 3, Ni for 4, and Cu for 5) to give a 1D M-M1Mo6 inorganic chain; the adjacent 1D inorganic chains are connected through two directions of [M2(PACP)2] rings to form a 3D framework. It should be noted that in complex 4, the NiMo6 anions are in situ generated from the NiII ion and Mo7O246- anions, which is rarely observed in POM-based MOCs. Complex 6 shows a 1D ladder-like supramolecular double chain, which is composed of 1D Co-AlMo6 inorganic chains, [Co2(HPCAP)2] dual-core rings and discrete AlMo6 polyanions interlinked by hydrogen bonding interactions. These structural diversities show that solvents play key roles in the construction of various architectures. All of the title complexes have excellent adsorption activities for the cationic dyes methylene blue (MB) and gentian violet (GV); in particular, complex 5 is capable of selectively adsorbing MB and GV from the mixtures of MB and MO and GV and MO, respectively. In addition, the electrochemical properties of complexes 1, 4, and 5 are also studied.

中文翻译：

由多种溶剂诱导的各种安德森型多金属氧酸盐基金属有机配合物：有机染料的组装，结构和选择性吸附。

晶体分析表明，配合物1具有基于CrMo6阴离子和1D金属-有机带状链[Cu（HPCAP）2]的3D超分子结构，并通过氢键形成。配合物2是由[Zn2（CrMo6）2]和[Zn2（PCAP）2]的两种双核金属簇组成的二维超分子层。配合物3-5显示了类似的3D框架。在3-5中，[M1Mo6] 3-（M1 = Cr为3，Ni为4，Al为5）阴离子与MII离子桥接（M = Zn为3，Ni为4，Cu为5）。一维M-M1Mo6无机链; 相邻的1D无机链通过[M2（PACP）2]环的两个方向连接，形成3D骨架。应当指出，在配合物4中，NiMo6阴离子是由NiII离子和Mo7O246-阴离子原位生成的，这在基于POM的MOC中很少见。配合物6显示一维阶梯状超分子双链，它由一维Co-AlMo6无机链，[Co2（HPCAP）2]双核环和通过氢键相互作用相互连接的离散AlMo6聚阴离子组成。这些结构多样性表明，溶剂在各种体系结构的构建中起着关键作用。所有的标题配合物对阳离子染料亚甲基蓝（MB）和龙胆紫（GV）均具有出色的吸附活性；特别地，配合物5能够分别从MB和MO以及GV和MO的混合物中选择性地吸附MB和GV。另外，还研究了配合物1、4和5的电化学性质。所有的标题配合物对阳离子染料亚甲基蓝（MB）和龙胆紫（GV）均具有出色的吸附活性；特别地，配合物5能够分别从MB和MO以及GV和MO的混合物中选择性地吸附MB和GV。另外，还研究了配合物1、4和5的电化学性质。所有的标题配合物对阳离子染料亚甲基蓝（MB）和龙胆紫（GV）均具有出色的吸附活性；特别地，配合物5能够分别从MB和MO以及GV和MO的混合物中选择性地吸附MB和GV。另外，还研究了配合物1、4和5的电化学性质。

更新日期：2020-01-06

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