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Two-dimensional Cd3-based metal–organic frameworks with halogen bonding sites for the uptake of I2

Zhi-Hao Zhang,Jia-Lu Ge,Yan Li,Qing Li,Pin-Pin Ma,Xiao-Yan Tang,Wen-Hua Zhang,David J. Young

Developing porous materials for the efficient capture of I2 is relevant to the sequestration and storage of radioactive iodine towards clean nuclear energy. In this work, three topologically identical two-dimensional (2D) metal–organic frameworks (MOFs) [Cd3(BTB)2(Pz)4]·xSol. (2), [Cd3(BTB)2(3-PyCN)2(H2O)2]·xSol. (3), and [Cd3(BTB)2(4-PyCN)4]·xSol. (4) have been prepared by ligand exchange with [Cd3(BTB)2(DEF)4]·2(DEF)0.5 (1) via single-crystal to single-crystal transformations (H3BTB = benzene-1,3,5-tribenzoic acid; DEF = diethylformamide; Pz = pyrazine; 3-PyCN = 3-cyanopyridine; 4-PyCN = 4-cyanopyridine; xSol. = guest solvates). MOFs 1–4 feature linear Cd3 cluster secondary building units (SBUs) interconnected by BTB ligands, with each Cd3 unit also associated with four terminally bonded ligands bearing halogen bonding sites, viz. N(DEF) for 1, N(Pz) for 2, –CN(3-PyCN) for 3, and –CN(4-PyCN) for 4. MOFs 1–4 adsorbed I2 in the sequence 2 > 3 > 4 > 1 with a maximum uptake of 54.1 mg g−1 for 2.