1.
Chemistry
; 25(7): 1706-1710, 2019 Feb 01.
Artigo
em Inglês
| MEDLINE
| ID: mdl-30471150
RESUMO
Stable BIII -subporphyrin-substituted dicyanomethyl radicals were synthesized by SN Ar reaction of meso-bromo- or meso-chlorosubporphyrins with malononitrile followed by oxidation with PbO2 . Different from previously reported dicyanomethyl radicals that underwent σ- or π-dimer formation both in the solid state and in solutions, subporphyrin-stabilized dicyanomethyl radicals exist as monomers in solutions even at low temperature. DFT calculations revealed efficient spin delocalization over the entire subporphyrin. In the solid state, these radicals form weak π-dimers with antiferromagnetic interactions depending on the crystal packing structures.