Mediating Order and Modulating Porosity by Controlled Hydrolysis in a Phosphonate Monoester Metal-Organic Framework

A crystalline and permanently porous copper phosphonate monoester framework has been synthesized from a tetraaryl trigonal phosphonate monoester linker. This material has a surface area over 1000 m(2) g(-1), as measured by N-2 sorption, the highest reported for a phosphonate-based metalorganic framework (MOF). The monoesters result in hydrophobic pore surfaces that give a low heat of adsorption for CO2 and low calculated selectivity for CO2 over N-2 and CH4 in binary mixtures. By careful manipulation of synthetic conditions, it is possible to selectively remove some of the monoesters lining the pore to form a hydrogen phosphonate while giving an isomorphous structure. This increases the affinity of the framework for CO2 giving higher ambient uptake, higher heat of adsorption, and much higher calculated selectivity for CO2 over both N-2 and CH4. Formation of the acid groups is noteworthy as complexation with the parent acid gives a different structure.