Lu Tian-Qi, Xu Han, Cheng Lan-Tao, Wang Xue-Tao, Chen Cheng, Cao Lingyun, Zhuang Gui-Lin, Zheng Jun, Zheng Xiu-Ying
Institutes of Physical Science and Information Technology, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Anhui University, Hefei 230601, China.
State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, iChEM, College of Chemistry and Chemical Engineering, Xiamen University, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen 361005, China.
Inorg Chem. 2022 Jun 13;61(23):8861-8869. doi: 10.1021/acs.inorgchem.2c00898. Epub 2022 Jun 2.
A family of nanoclusters, [Ln(EDTA)(OAc)(CO)(μ-OH)(μ-OH)(HO)]·OAc·HO ( ≈ 50, Ln = Sm for ; ≈ 70, Ln = Eu for ) and [Gd(EDTA)(OAc)(CO)(CO)(μ-OH)(μ-OH)(HO)]·(HO) ( ≈ 70 for ; HEDTA = ethylene diamine tetraacetic acid), was prepared through the assembly of repeating subunits under the action of an anion template. The analysis of the structures showed that compounds and containing 33 Ln ions were isostructural, which were constructed by three kinds of subunits in the presence of CO as an anion template, while compound had a slightly different structure. Compound containing 32 Gd ions was formed by three types of subunits in the presence of CO and CO as a mixed anion template. The CO anions came from the slow fixation of CO in the air. Meanwhile, one kind of high-nuclearity lanthanide clusters showed high chemical stability. The quantum Monte Carlo (QMC) calculation suggested that weak antiferromagnetic interactions were dominant between Gd ions in . Magnetocaloric studies showed that compound had a large entropy change of 43.0 J kg K at 2 K and 7 T. Surprisingly, compound showed excellent recognition and detection effects for permanganate in aqueous solvents based on the fluorescence quenching phenomenon.
通过在阴离子模板作用下重复亚基的组装，制备了一族纳米团簇，即[Ln(EDTA)(OAc)(CO)(μ-OH)(μ-OH)(HO)]·OAc·HO（≈50，Ln = Sm时为 ；≈70，Ln = Eu时为 ）和[Gd(EDTA)(OAc)(CO)(CO)(μ-OH)(μ-OH)(HO)]·(HO)（≈70， ；HEDTA = 乙二胺四乙酸）。结构分析表明，含有33个Ln离子的化合物 和 是同构的，它们是在CO作为阴离子模板存在的情况下由三种亚基构建而成的，而化合物 的结构略有不同。含有32个Gd离子的化合物 是在CO和CO作为混合阴离子模板存在的情况下由三种类型的亚基形成的。CO阴离子来自空气中CO的缓慢固定。同时，一种高核镧系团簇表现出高化学稳定性。量子蒙特卡罗（QMC）计算表明， 中Gd离子之间以弱反铁磁相互作用为主。磁热研究表明，化合物 在2 K和7 T时具有43.0 J kg K的大熵变。令人惊讶的是，基于荧光猝灭现象，化合物 对水溶液中的高锰酸盐表现出优异的识别和检测效果。
