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 tem...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2019, Vol.48 (43), p.16312-16321
Main Authors: Stephaniuk, Nadia T, Haskings, Erika M, Arauzo, Ana, Campo, Javier, Rawson, Jeremy M
Format: Article
Language:English
Subjects:
High temperature
Inclusion complexes
Oxidation
Radicals
Sublimation
Thermal analysis
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Summary: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 Cl 2 or Br 2 and led to complete radical oxidation (based on EPR studies) whereas the milder oxidant I 2 leads to incomplete oxidation. Inclusion chemistry of dithiadiazolyl and diselenadiazolyl radicals into the MIL-53(Al) host occurs via vapor phase diffusion.
ISSN:1477-9226
1477-9234
DOI:10.1039/c9dt03624e