Interpenetration Control in Thorium Metal-Organic Frameworks: Structural Complexity toward Iodine Adsorption

The rational design and synthesis of metal-organic frameworks with well-controlled interpenetration have been active research areas of inquiry, particularly for porosity-related applications. Herein, we extend the use of the ligand steric modulation strategy to initiate the first study of the interpenetration control of thorium-based MOFs. The approximate "hardness"of the Th4+ cation, which was conjugated with aromatic substitutions and delicately modified synthetic conditions, allows for the crystallization of single crystals of seven new Th-MOFs with five distinct topologies. Solvothermal reactions of Th(NO3)4 with the triphenyl H2TPDC ligand under variable conditions exclusively gave rise to an interpenetrated Th-MOF with a hex topology, namely Th-SINAP-16. Modifications of the ligand sterics with two pendant methyl groups to 2′,5′-Me2TPDC2- and 2,2″-Me2TPDC2- afforded two noninterpenetrated UiO-68-type Th-MOFs (Th-SINAP-17 and Th-SINAP-20, respectively) with record-high pore volumes (74.8% and 75.3%, respectively) among all the thorium MOFs. Moreover, another four Th-MOFs Th-SINAP-n (n = 18, 19, 21, and 22) with three different topologies were obtained by a simple synthetic modulation. Notably, Th-SINAP-16 and Th-SINAP-21 represent the second rare examples of interpenetrated Th-MOFs reported to date. These findings revealed the unprecedented structural complexity and synthetic accessibility of Th-MOFs among all tetravalent metal containing MOFs. Such features make Th-MOFs as an ideal platform to elucidate the structure-property relationship for various applications, e.g. iodine adsorption.