A framework for predicting surface areas in microporous coordination polymers.

A predictive tool termed the linker to metal cluster (LiMe) ratio is introduced as a method for understanding surface area in microporous coordination polymers (MCPs). Calibrated with geometric accessible surface area computations, the LiMe ratio uses molecular weight of building block components to indicate the maximum attainable surface area for a given linker and metal cluster combination. MOF-5 and HKUST-1 are used as prototypical structures to analyze MCPs with octahedral M(4)O(CO(2)R)(6) and paddlewheel M(2)(CO(2)R)(4) metal clusters. Insight into the effects of linker size, geometry, number of coordinating groups, and framework interpenetration is revealed through the LiMe ratio analysis of various MCPs. Experimental surface area deviation provides indication that a material may suffer from incomplete guest removal, structural collapse, or interpenetration. Because minimal data input are required, the LiMe ratio surface area analysis is suggested as a quick method for experimental verification as well as a guide for the design of new materials.