Closo‐[B12H12]2− Derivatives with Polar Groups As Promising Building Blocks in Metal‐Organic Frameworks for Gas Separation

Abstract Engineering design of metal organic frameworks (MOFs) for gas separation applications is nowadays a thriving field of investigation. Based on the recent experimental studies of dodecaborate‐hybrid MOFs as potential materials to separate industry‐relevant gas mixtures, we herein present a systematic theoretical study on the derivatives of the closo ‐dodecaborate anion [B 12 H 12 ] 2− , which can serve as building blocks for MOFs. We discover that amino functionalization can impart a greater ability to selectively capture carbon dioxide from its mixtures with other gases such as nitrogen, ethylene and acetylene. The main advantage lies in the polarization effect induced by amino group, which favors the localization of the negative charges on the boron‐cluster anion and offers a nucleophilic anchoring site to accommodate the carbon atom in carbon dioxide. This work suggests an appealing strategy of polar functionalization to optimize the molecule discrimination ability via preferential adsorption.