Inclusion and reactivity of main group radicals in the porous framework MIL-53(Al)

Inclusion of the dithiadiazolyl and diselenadiazolyl radicals PhCNEEN (E = S, Se) into the porous framework, Al(bdc)(OH) [MIL-53(Al); bdc = 1,4-benzenedicarboxylate] was achieved by vacuum sublimation. PXRD studies reveal the inclusion complexes adopt the orthorhombic space group Imma. Variable temperature PXRD studies coupled with thermal analysis reveal that for PhCNSSN@MIL-53(Al), radical elimination from the pores at elevated temperatures is accompanied by an opening of the pore channels. Radicals can also be extracted from the framework using an appropriate solvent. Oxidation of the radical guest within the host framework has been achieved with Cl2 or Br2 and led to complete radical oxidation (based on EPR studies) whereas the milder oxidant I2 leads to incomplete oxidation.NTS thanks Dr J. Auld for HRMS measurements, as well as Dr K. Pringouri and L. Watanabe for CHN data. JMR would like to thank NSERC for an operating grant (RGPIN-2015-245402) and CFI and ORF for infrastructure grants. AA and JC acknowledge support from grant PGC-2018-099024-B100 from the Ministry of Science, Innovation and Universities of Spain and the European Regional Development Fund. Additional support from Diputacion General de Aragon (DGA-M4) is also acknowledged.Peer reviewe