The Role of Modulators in Controlling Layer Spacings in a Tritopic Linker Based Zirconium 2D Microporous Coordination Polymer

A 2D zirconium-based microporous coordination polymer derived from the tritopic linker 1,3,5-(4-carboxylphenyl)benzene, UMCM-309a, has been synthesized. This noninterpenetrated material possesses a Zr6(μ3-O)4(μ3-OH)4(RCO2)6(OH)6(H2O)6 cluster with six hexagonal-planar-coordinated linkers. UMCM-309a is stable in an aqueous HCl solution for over 4 months. The use of different monocarboxylates as modulators leads to similar 2D structures with different layer spacings; moreover, removal of the modulator yields the parent UMCM-309a.