Design Strategy for the Controlled Generation of Cationic Frameworks and Ensuing Anion-Exchange Capabilities.

Abstract

Cationic frameworks are an emerging class of exceptional solid adsorbents capable of encapsulating highly toxic and persistent anionic pollutants. The controlled generation of cationic frameworks, however, lags behind the abundant design strategies devised to control the structures and topologies of neutral frameworks. In this regard, we report a rational approach that allows the conversion of the synthetic approach toward constructing a neutral framework into one allowing for the synthesis of a cationic one without incurring any changes to the overall topology or the selected metal ion. We demonstrate that the replacement of a functional group on an organic linker that promotes a similar coordination mode, but bearing one less negative charge, can yield the systematic generation of cationic frameworks. Moreover, we confirm the cationic nature of the metal-organic frameworks through preliminary anion-exchange experiments and propose a method to retain permanent porosity in cationic frameworks through the use of strongly binding anions. Altogether, these results show great promise for the construction of tunable nanoporous frameworks capable of carrying out anion-exchange processes.