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COMMUNICATION /chemcomm | ChemComm A novel metal–organic coordination polymer for selective adsorption of CO2 over CH4w Bin Mu, Feng Li and Krista S. Walton* Received (in Cambridge, UK) 6th November 2008, Accepted 25th February 2009 First published as an Advance Article on the web 30th March 2009 DOI: 10.1039/b819828d A unique two-dimensional interpenetrating network structure possessing unsaturated metal sites and uncoordinated carboxylic functional groups exhibits among the highest reported adsorption selectivities for CO2 over CH4. Porous coordination polymers or metal–organic frameworks (MOFs) have attracted great interest recently for potential applications in adsorption separations, gas storage, sensing, and catalysis.1 In contrast to conventional microporous materials, these organic–inorganic hybrids have the potential for synthesis using a rational design approach by ?exible control of the architecture and functional group.2 In materials such as those assembled from the paddle-wheel structure, as-synthesized MOFs have solvent molecules attached as ligands to the metal centers. Removal of these solvent ligands by thermal activation generates unsaturated metal centers (UMCs) or open metal sites. Thus, the metal atoms are exposed on the interior surfaces of the material and are open to direct approach by sorbate molecules. These exposed metal sites can be seen as analogous to entatic metal centers in bioinorganic chemistry, in which metal ions are forced into unusual coordination geometry like the iron in hemoglobin.3 Open metal sites greatly increase the ability of the material to selectively adsorb particular molecules. Consequently, the incorporation of UMCs into MOFs is a practical strategy for manipulating the adsorption behavior. There have been a number of reports in recent years of MOFs with UMCs.1c,4 Many of these materials possess 3D structures with channels or interconnected pores. The adsorption properties of a particular material will depend on thi