Rare‐Earth‐Guided Hierarchical Assembly of Teddy‐Bear‐Like Giant Nickel‐Tungstate Polyoxometalates
Abstract
ABSTRACT The controlled assembly of giant polyoxometalates (POMs) remains a significant challenge in inorganic chemistry. Herein, we demonstrate that rare‐earth ions can direct distinct structural outcomes in nickel‐substituted tungstate systems. Hydrothermal reaction of the flexible precursor [B‐ α ‐SbW 9 O 33 ] with KH 2 PO 4 , Er 2 O 3 , and NiCl 2 yielded a giant all‐inorganic cluster {W 88 Ni 39 } (1) , adopting an unprecedented “Teddy‐Bear”‐like architecture. Under identical conditions, omission of Er 2 O 3 (or replacement with Dy 2 O 3 ) afforded the smaller cluster {W 55 Ni 17 } (2) , corresponding to the “head” of the “Teddy‐Bear”. Notably, Dy 2 O 3 improves the crystallization yield of {W 55 Ni 17 } relative to the rare‐earth‐free reaction. Remarkably, replacing Er 2 O 3 with Gd 2 O 3 afforded a giant tetramer {W 140 Gd 10 Ni 48 } (3) , whose monomer is analogous to the [W 33 Ni 21 ] “Teddy‐Bear body” motif in {W 88 Ni 39 } . These clusters rank among the largest discrete tungsten‐based POM assemblies known. Importantly, the crystallization of {W 88 Ni 39 } and {W 140 Gd 10 Ni 48 } enables an efficient organic‐free separation of the rare‐earth oxides Er 2 O 3 and Gd 2 O 3 with a separation factor of 360.37, revealing a new strategy based on structure‐directed hierarchical assembly for selective crystallization in rare‐earth‐mediated POM systems.
Article Details
Authors (8)
Shu‐Rong Li
Department of Chemistry College of Chemistry and Chemical Engineering and State Key Laboratory of Physical Chemistry of Solid Surfaces Xiamen University Xiamen China
Shi‐Yi Wang
Department of Chemistry College of Chemistry and Chemical Engineering and State Key Laboratory of Physical Chemistry of Solid Surfaces Xiamen University Xiamen China
Han Xu
Ming‐Qiang Qi
Department of Chemistry College of Chemistry and Chemical Engineering and State Key Laboratory of Physical Chemistry of Solid Surfaces Xiamen University Xiamen China
Hai‐Feng Su
Department of Chemistry College of Chemistry and Chemical Engineering and State Key Laboratory of Physical Chemistry of Solid Surfaces Xiamen University Xiamen China
La‐Sheng Long
State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry College of Chemistry and Chemical Engineering Xiamen University Xiamen China
Lan‐Sun Zheng
State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry College of Chemistry and Chemical Engineering Xiamen University Xiamen China
Xiang‐Jian Kong
Department of Chemistry College of Chemistry and Chemical Engineering and State Key Laboratory of Physical Chemistry of Solid Surfaces Xiamen University Xiamen China