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Stable (B III ‐Subporphyrin‐5‐yl)dicyanomethyl Radicals
Author(s) -
Adinarayana Bellamkonda,
Shimizu Daiki,
Osuka Atsuhiro
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201805601
Subject(s) - radical , chemistry , antiferromagnetism , dimer , delocalized electron , monomer , malononitrile , crystallography , photochemistry , solid state , polymer , organic chemistry , catalysis , physics , condensed matter physics
Stable B III ‐subporphyrin‐substituted dicyanomethyl radicals were synthesized by S N Ar reaction of meso ‐bromo‐ or meso ‐chlorosubporphyrins with malononitrile followed by oxidation with PbO 2 . 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.