Liu Jian-Cai, Zhao Jun-Wei, Song Yu-Fei
State Key Laboratory of Chemical Resource Engineering, Beijing Advanced Innovation Center for Soft Matter Science and Engineering , Beijing University of Chemical Technology , Beijing 100029 , People's Republic of China.
Henan Key Laboratory of Polyoxometalate Chemistry, College of Chemistry and Chemical Engineering , Henan University , Kaifeng , Henan 475004 , People's Republic of China.
Inorg Chem. 2019 Aug 5;58(15):9706-9712. doi: 10.1021/acs.inorgchem.9b00618. Epub 2019 Jul 18.
A family of inorganic-organic hybrid one-dimensional (1-D) chain iron-lanthanide (Ln) heterometal encapsulated tungstotellurates [HN(CH)]KNa[Ln(Ac)(HO)Fe(Hpdca)(B-β-TeWO)][Ln(HO)Fe(Hpdca)(B-β-TeWO)]·50HO [Ln = Eu (), Tb (), Dy (), Er (), HAc = acetate acid, Hpdca = 2,5-pyridinedicarboxylic acid] were prepared using a facile "one-pot" reaction. The molecular structures of - consist of an intriguing organic-ligand-connecting Fe-Ln heterometal inserted tetrameric unit [Ln(Ac)(HO)Fe(Hpdca)(B-β-TeWO)][Ln(HO)Fe(Hpdca)(B-β-TeWO)]. Appealingly, the tetrameric unit is composed of two sandwich-type subunits [Ln(Ac)(HO)Fe(Hpdca)(B-β-TeWO)] and [Ln(HO)Fe(Hpdca)(B-β-TeWO)], in which each sandwich-type subunit can be regarded as a derivative of two Ln-organic complexes substituting two external Fe ions in the classic Krebs-type [Fe(HO)(β-TeWO)] fragment. Furthermore, adjacent tetrameric units are interconnected into a 1-D chain arrangement by Hpdca bridges. - represent the first examples of Fe-Ln heterometal encapsulated tungstotellurates. Comprehensive magnetic measurements of imply the possible single-molecule magnet properties in with an estimated relaxation time τ ≈ 6.06 × 10 s at = 0 Oe and τ ≈ 6.97 × 10 s at = 1500 Oe. In addition, the solid-state photoluminescence spectra of and at room temperature exhibit the typical f-f transitions of Ln cations. The Commission International d'Eclairage (CIE) color coordinates of (0.540 24, 0.442 44) for and (0.428 71, 0.428 30) for along with the correlated color temperatures of 1995 and 3278 K, dominant wavelengths of 586 and 578 nm, and color purities of 95.09% and 57.27% for and are obtained.
通过简便的“一锅法”反应制备了一系列无机-有机杂化一维（1-D）链状铁-镧系元素（Ln）异金属封装的钨碲酸盐[HN(CH)]KNa[Ln(Ac)(HO)Fe(Hpdca)(B-β-TeWO)][Ln(HO)Fe(Hpdca)(B-β-TeWO)]·50HO [Ln = Eu （），Tb （），Dy （），Er （），HAc = 乙酸，Hpdca = 2,5-吡啶二甲酸]。-的分子结构由一个有趣的有机配体连接的Fe-Ln异金属插入四聚体单元[Ln(Ac)(HO)Fe(Hpdca)(B-β-TeWO)][Ln(HO)Fe(Hpdca)(B-β-TeWO)]组成。吸引人的是，四聚体单元由两个三明治型亚单元[Ln(Ac)(HO)Fe(Hpdca)(B-β-TeWO)]和[Ln(HO)Fe(Hpdca)(B-β-TeWO)]组成，其中每个三明治型亚单元可视为两个Ln-有机配合物取代经典克雷布斯型[Fe(HO)(β-TeWO)]片段中两个外部Fe离子的衍生物。此外，相邻的四聚体单元通过Hpdca桥相互连接成一维链状排列。-代表了Fe-Ln异金属封装钨碲酸盐的首个实例。对-的综合磁性测量表明，在 = 0 Oe时，-可能具有单分子磁体性质，估计弛豫时间τ≈6.06×10 s，在 = 1500 Oe时，τ≈6.97×10 s。此外，-和-在室温下的固态光致发光光谱显示出Ln阳离子典型的f-f跃迁。得到了-的CIE色坐标（0.540 24，0.442 44）和-的（0.428 71，0.428 30），以及1995和3278 K的相关色温、586和578 nm的主波长，-和-的色纯度分别为95.09%和57.27%。
