ABSTRACT: Eight cationic, two-dimensional metal-organic frameworks (MOFs) were synthesized in reactions of the group 13 metal halides AlBr3 , AlI3 , GaBr3 , InBr3 and InI3 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 ∞ [MX2 (L)2 ]A, M=Al, In, X=Br, I, A- =[MX4 ]- , I- , I3 - , 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 I3 - 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 ∞ [(GaBr2 )2 (bpa)5 ][GaBr4 ]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 [MX4 ]- , I- or I3 - counter ions in their pores. Whereas the [MX4 ]- , 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.
