Iodine‐Chemisorption, Interpenetration and Polycatenation: Cationic MOFs and CPs from Group 13 Metal Halides and Di‐Pyridyl‐Linkers

Eight cationic, two‐dimensional metal‐organic frameworks (MOFs) were synthesized in reactions of the group 13 metal halides AlBr(3), AlI(3), GaBr(3), InBr(3) and InI(3) with the dipyridyl ligands 1,2‐di(4‐pyridyl)ethylene (bpe), 1,2‐di(4‐pyridyl)ethane (bpa) and 4,4’‐bipyridine (bipy). Seven of them follow the general formula (2) (∞)[MX(2)(L)(2)]A, M=Al, In, X=Br, I, A(−)=[MX(4)](−), I(−), I(3) (−), L=bipy, bpa, bpe. Thereby, the porosity of the cationic frameworks can be utilized to take up the heavy molecule iodine in gas‐phase chemisorption vital for the capture of iodine radioisotopes. This is achieved by switching between I(−) and the polyiodide I(3) (−) in the cavities at room temperature, including single‐crystal‐to‐single‐crystal transformation. The MOFs are 2D networks that exhibit (4,4)‐topology in general or (6,3)‐topology for (2) (∞)[(GaBr(2))(2)(bpa)(5)][GaBr(4)](2)⋅bpa. The two‐dimensional networks can either be arranged to an inclined interpenetration of the cationic two‐dimensional networks, or to stacked networks without interpenetration. Interpenetration is accompanied by polycatenation. Due to the cationic character, the MOFs require the counter ions [MX(4)](−), I(−) or I(3) (−) counter ions in their pores. Whereas the [MX(4)](−), ions are immobile, iodide allows for chemisorption. Furthermore, eight additional coordination polymers and complexes were identified and isolated that elaborate the reaction space of the herein reported syntheses.