Wang San-Tai, Zhang Shu-Hua, Fang Wei-Hui, Zhang Jian
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.
College of Chemistry, Guilin University of Technology, Guilin, Guangxi 541004, China.
Inorg Chem. 2020 Sep 21;59(18):13760-13766. doi: 10.1021/acs.inorgchem.0c02119. Epub 2020 Sep 4.
Present herein is a stepwise assembly method toward aluminum-lanthanide-based (Al-Ln) compounds. From the perspective of charge balance, polyanions are necessary to bind with Ln ions. However, the synthesis of polyanions aluminum compounds remains quite challenging. Herein, two Al polyanions [Al(L)(Cat)]·4Hdma (AlOC-13, HL= 2,3-dihydroxybenzoic acid, Cat = catechol, and dma = dimethylamine) and [Al(L)(HL)(DMF)]·4Hdma·0.5DMF·0.5HO (AlOC-14, DMF = ,-dimethylformamide) were successfully obtained under solvothermal conditions. Catechol and Hdma were generated from the in situ decarboxylation of HL ligand and decomposition of DMF, respectively. AlOC-13 is qualified for further coordination assembly for the available vacancy coordination sites, good water solubility, and scale-up synthesis. The assembly of Al polyanions with equivalent Ln ions afforded a series of zigzag chain structures [LnAl(L)(Cat)(DMF)(HO)]·Hdma (Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) (AlOC-13-Ln). Moreover, the magnetic behavior and photoluminescence of the series of AlOC-13-Ln were also studied. AlOC-13-Dy shows obvious antiferromagnetic behavior, while AlOC-13-Tb exhibits excellent green characteristic luminescence. This study not only paves the way toward anionic aluminum clusters but also reveals their potential application in water treatment of cationic metal ions capture.
本文介绍了一种基于铝镧（Al-Ln）化合物的逐步组装方法。从电荷平衡的角度来看，多阴离子对于与Ln离子结合是必要的。然而，多阴离子铝化合物的合成仍然颇具挑战性。在此，在溶剂热条件下成功获得了两种铝多阴离子[Al(L)(Cat)]·4Hdma（AlOC-13，HL = 2,3-二羟基苯甲酸，Cat = 儿茶酚，dma = 二甲胺）和[Al(L)(HL)(DMF)]·4Hdma·0.5DMF·0.5H₂O（AlOC-14，DMF = N,N-二甲基甲酰胺）。儿茶酚和Hdma分别由HL配体的原位脱羧和DMF的分解产生。AlOC-13因其可用的空位配位点、良好的水溶性和放大合成能力而有资格进行进一步的配位组装。铝多阴离子与等量的Ln离子组装得到了一系列之字形链结构[LnAl(L)(Cat)(DMF)(H₂O)]·Hdma（Ln = Sm、Eu、Gd、Tb、Dy、Ho、Er、Yb）（AlOC-13-Ln）。此外，还研究了该系列AlOC-13-Ln的磁行为和光致发光。AlOC-13-Dy表现出明显的反铁磁行为，而AlOC-13-Tb表现出优异的绿色特征发光。这项研究不仅为阴离子铝簇开辟了道路，还揭示了它们在捕获阳离子金属离子的水处理中的潜在应用。
