摘要

The full separation of alkane isomers as a function of different degrees of branching remains a daunting challenge due to its stringent requirement with respect to pore dimensions of the adsorbents. In this work, we report a novel microporous coordination network built on calcium (II) and chloranilate. The compound has a flexible framework and exhibits temperature‐dependent adsorption behavior toward hexane isomers. At 30?°C, it accommodates substantial amounts of linear and monobranched hexanes but fully excludes their dibranched isomer, and at elevated temperatures such as 150?°C, it acts as a splitter for linear and branched alkanes. Its capability of efficient discrimination of hexane isomers as a function of branching is verified by experimental breakthrough measurements. Ab initio calculations have uncovered the underlying selective size‐exclusion separation mechanism.(#br)A novel calcium‐based metal–organic framework shows temperature‐ and adsorbate‐dependent adsorption of hexane isomers with different branching, leading to temperature‐programmed separation of the isomers as a function of different degrees of branching.