Yang Zeng-Xi, Liang Xue-Wei, Lin Dunmin, Zheng Qiaoji, Huo Yu
College of Chemistry and Materials Science, Sichuan Normal University, Chengdu 610066, P. R. China.
Inorg Chem. 2023 Jan 30;62(4):1466-1475. doi: 10.1021/acs.inorgchem.2c03561. Epub 2023 Jan 19.
Two series of lanthanoid (Ln)-containing polyoxometalates (POMs) {[Ln(ampH)(HO)(ampH)(PWO)]·21HO (Ln = Tb, = 0 (), Ln = Er, = 1 ()) and K[Ln(ampH)(HO)(SiWO)]·23HO (Ln = Tb (), Er ()) (ampH = (aminomethyl) phosphonic acid)} have been synthesized with tri-lacunary Keggin-type POMs containing different types of heteroatoms. Compounds and display neutral organic-inorganic hybrid POM molecules containing {Ln(ampH)} ({Ln}) cores sandwiched by two {PWO} units. By changing the heteroatoms from P to Si, the extended 2D networks of and were successfully isolated where the adjacent {Ln} clusters were connected by {SiWO} moieties. Luminescence performances and magnetic properties of have been systematically surveyed. The solid-state fluorescence spectra of display characteristic emissions of Ln components resulting from the 4f-4f transitions, and energy transfer from the POM segments to Ln centers in and has been observed based on the lifetime decay behaviors. Furthermore, all compounds can be utilized as electrocatalysts toward reduction of nitrite with high stability.
合成了两个系列含镧系元素（Ln）的多金属氧酸盐（POMs）{[Ln(ampH)(HO)(ampH)(PWO)]·21HO（Ln = Tb， = 0（），Ln = Er， = 1（））和K[Ln(ampH)(HO)(SiWO)]·23HO（Ln = Tb（），Er（））（ampH =（氨甲基）膦酸）}，它们是由含不同类型杂原子的三缺位Keggin型POMs合成的。化合物 和 展示了中性有机 - 无机杂化POM分子，其包含被两个{PWO}单元夹在中间的{Ln(ampH)}（{Ln}）核。通过将杂原子从P变为Si，成功分离出了 和 的二维扩展网络，其中相邻的{Ln}簇通过{SiWO}部分相连。对 的发光性能和磁性进行了系统研究。 的固态荧光光谱显示了由4f - 4f跃迁产生的Ln组分的特征发射，并且基于寿命衰减行为观察到了从POM片段到 和 中Ln中心的能量转移。此外，所有化合物都可作为高稳定性的亚硝酸盐还原电催化剂。
