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Phenylene‐bridged Porphyrin meso ‐Oxy Radical Dimers
Author(s) -
Yamamoto Takayuki,
Kato Kenichi,
Shimizu Daiki,
Tanaka Takayuki,
Osuka Atsuhiro
Publication year - 2019
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201901033
Subject(s) - porphyrin , phenylene , chemistry , polymer chemistry , photochemistry , organic chemistry , polymer
Stable meta ‐ and para ‐phenylene bridged porphyrin meso ‐oxy radical dimers and their Ni II and Zn II complexes were synthesized. All the dimers exhibited optical and electrochemical properties similar to the corresponding porphyrin meso ‐oxy radical monomers, indicating small electronic interaction between the two spins. Intramolecular spin‐spin interaction through the π‐spacer was determined to be J / k B =−15.9 K for m ‐phenylene bridged Zn II porphyrin dimer. The observed weak antiferromagnetic interaction has been attributed to less effective conjugation between the porphyrin radical and linking π‐spacer due to large dihedral angle. In the case of Zn II complexes, both para ‐ and meta ‐phenylene bridged dimers formed 1D‐chain in solutions and in the solid states through Zn‐O coordination.