Orthogonalization of Polyaryl Linkers as a Route to More Porous Phosphonate Metal-Organic Frameworks

The coordinative pliancy of the phosphonate functional group means that metal-phosphonate materials often self-assemble as well-packed structures with minimal porosity, as efficient inter-ligand packing is enabled. Here, we report a multistep synthesis of a novel aryl-phosphonate linker with an orthogonalized ligand core, 1,3,5-tris(4'-phosphonophenyl)-2,4,6-trimethylbenzene (H₆ L2) designed to form more open structures. A series of crystalline metal-phosphonate frameworks (CALF-35 to -39) have been assembled by coordinating to divalent metals (Ba, Sr, Ca, Mg, Zn). H₆ L2 is unable to pack efficiently and, as a consequence, yields several distinct microporous structures. The resulting structures are discussed in detail, with a focus on the solid-state packing of the sterically rigidified linker. Combined with larger cations (Sr, and Ba), H₆ L2 packs in a parallel-offset manner, yielding isomorphous and microporous metal-organic frameworks (CALF-35 (Sr), and (Ba)). When coordinated to smaller metals (Ca, Mg, Zn), H₆ L2 forms four new structures. Two Ca MOFs of different stoichiometry, (CALF-36 and 37) and a Mg MOF CALF-38 show narrow pores and have high selectivities for CO₂ over N₂ and CH₄ . Finally, in CALF-39 (Zn), H₆ L2 linkers pack in a herringbone fashion, resulting in a material with 10.9×10.1 Ų square channels. The stability of all structures was tested, and the most porous structure, CALF-39 (Zn), was found to retain its structure and gas adsorption after immersion in water over pH 3-11.