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Directional Bonding in Decaniobate Inorganic Frameworks
Author(s) -
Martin Nicolas P.,
Nyman May
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202010902
Subject(s) - polyoxometalate , selectivity , alkali metal , ion exchange , solubility , inorganic chemistry , metal organic framework , chemistry , ion , ionic radius , metal , materials science , nanotechnology , chemical physics , crystallography , catalysis , organic chemistry , adsorption
Metal–oxo clusters offer an opportunity to assemble inorganic and metal–organic frameworks (MOFs) by a controlled building‐block approach, which led to the revolutionary discoveries of zeolites and MOFs. Polyoxometalate clusters are soluble in water, but more challenging to link into frameworks; the inert oxo‐caps that provide solubility are resistant to replacement or further connectivity. We demonstrate how the unique directional bonding and varying basicity of the decaniobate ([Nb 10 ]) oxo‐caps can be exploited to build 1D, 2D, and 3D inorganic frameworks. In nine structures, A + (A=Li, Na, K, Rb and Cs), AE 2+ (AE=Ca, Sr, Ba) and Mn 2+ demonstrate that the dimensionality of the obtained material is controlled by cation charge and size. Increased cation charge decreases selectivity for oxo‐site bonding, leading to higher dimensional linking. Larger cation radii also decreases bonding selectivity, yielding higher dimensional materials. Ion‐exchange studies of the A + ‐Nb 10 family shows exclusive selectivity for Cs + over other alkalis, which is important for radioactive Cs removal and sequestration.