Cai Jing, Zheng Xiu-Ying, Xie Jing, Yan Zhi-Hao, Kong Xiang-Jian, Ren Yan-Ping, Long La-Sheng, Zheng Lan-Sun
Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, China.
Inorg Chem. 2017 Jul 17;56(14):8439-8445. doi: 10.1021/acs.inorgchem.7b01104. Epub 2017 Jun 26.
A series of heterometallic 3d-4f clusters, formulated as Na[Ln(HO)Ni(HO)(SbO)(SbWO)(NiWO)(WO)(CHCOO)]·(HO) [abbreviated as LnNi, where Ln = La (1), Pr (2), and Nd (3)], KNa[Ln(HO)Ni(HO)(SbWO)(WO)(CO)]·(HO) [abbreviated as LnNi, where Ln = La (4), Pr (5), and Nd (6)], and KNa[LnNi(μ-OH)(SbWO)(PWO)(CHCOO)]·(HO) [abbreviated as LnNi, where Ln = Dy (7) and Er (8)], were obtained through the reaction of the lacunary {SbWO} precursor with Ln(NO)·6HO and NiCl·6HO in a NaAc/HAc buffer in the presence of different anions. Single-crystal X-ray structure analysis revealed that compounds 1-3 possessed tetrameric architectures featuring three Keggin-type {SbWO} and one Anderson-type {NiWO} building blocks encapsulating one {SbO} cluster, three WO units, three Ln metal ions, and two Ni metal ions. Compounds 4-6 displayed cyclic trimeric aggregates of three {SbWO} units enveloping one CO-templated trinuclear [Ln(CO)] and one WO-templated [Ni(WO)] unit. Compounds 7 and 8 exhibited unique pentameric architectures that featured three 3d-4f cubane clusters of {LnNi(μ-OH)} capped by two {SbWO} and three {PWO} building blocks. Interestingly, the structural regulation of the heterometallic 3d-4f clusters in the polyoxometalate systems with trimers, tetramers, and pentamers was realized by introducing different anions.
通过缺位的{SbWO}前体与Ln(NO₃)₃·6H₂O和NiCl₂·6H₂O在NaAc/HAc缓冲液中、在不同阴离子存在下反应，得到了一系列异金属3d-4f簇合物，其化学式为Na[Ln(OH)Ni(OH)(SbO)(SbWO₄)(NiWO₄)(WO₄)(CH₃COO)]·(H₂O) [简称为LnNi，其中Ln = La (1)、Pr (2)和Nd (3)]、KNa[Ln(OH)Ni(OH)(SbWO₄)(WO₄)(CO₃)]·(H₂O) [简称为LnNi，其中Ln = La (4)、Pr (5)和Nd (6)]以及KNa[LnNi(μ-OH)(SbWO₄)(PWO₄)(CH₃COO)]·(H₂O) [简称为LnNi，其中Ln = Dy (7)和Er (8)]。单晶X射线结构分析表明，化合物1 - 3具有四聚体结构，其特征是三个Keggin型{SbWO₄}和一个Anderson型{NiWO₄}结构单元包裹着一个{SbO}簇、三个WO₄单元、三个Ln金属离子和两个Ni金属离子。化合物4 - 6展示出由三个{SbWO₄}单元组成的环状三聚体聚集体，包围着一个CO模板化的三核[Ln(CO₃)]和一个WO₄模板化的[Ni(WO₄)]单元。化合物7和8呈现出独特的五聚体结构，其特征是由两个{SbWO₄}和三个{PWO₄}结构单元封端的三个{LnNi(μ-OH)}的3d-4f立方烷簇。有趣的是，通过引入不同阴离子，在多金属氧酸盐体系中实现了异金属3d-4f簇合物三聚体、四聚体和五聚体的结构调控。
