Two mesoporous anionic metal-organic frameworks for selective and efficient adsorption of a cationic organic dye

Anionic metal-organic frameworks (MOFs) are beginning to have a great impact in the field of absorption and separation of ionic organic molecules due to the enhanced electrostatic interactions between their anionic frameworks and counter-ionic guests. Herein, the rational design and synthesis of two mesoporous anionic MOFs, [Zn₃(ITTC)₃](Me₂ NH₂)₃·3DMF·H₂O (1) and [Cd₂(ITTC)₃](Me₂NH₂)₅·2DMF (2), where H₃ITTC = 4,4',4''-(1H-imidazole-2,4,5-triyl) tribenzoic acid, is reported. Structural analysis revealed that both materials are anionic MOFs with a 2-fold interpenetrating three dimensional (3D) framework. The cross sectional area of the open one-dimensional rectangular channels is 31.7 Å × 15.6 Å for 1, of which the architecture is indicative of an unprecedented (3,3,4,5)-connection topology. For 2, the diameter of the open one-dimensional regular hexagonal channel is about 34.1 Å, decorated with uncoordinated carboxyl O atoms, and the framework exhibits a (3,4)-connected fcu network. Due to their anionic frameworks and bulky pore window sizes, both MOFs can be employed for absorbing and separating the cationic organic dye methylene blue (MB). The results reveal that both MOFs have better dye adsorption selectivity for MB, than for MO and SDI, because of charge and size-matching effects, enabling them to be potential candidates for use in environmental cleaning. By comparison, 2 presents superior selectivity and adsorptivity for cationic MB which depends on the presence of a basic functionalized pore surface.