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Electron Transfer and Unusual Chemical Transformations of F4‐TCNQ in a Reaction with Mn‐Phthalocyanine
Author(s) -
Kataeva Olga,
Metlushka Kirill,
Ivshin Kamil,
Kiiamov Airat,
Alfonsov Vladimir,
Khrizanforov Mikhail,
Budnikova Yulia,
Sinyashin Oleg,
Krupskaya Yulia,
Kataev Vladislav,
Büchner Bernd,
Knupfer Martin
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201800641
Subject(s) - superexchange , chemistry , phthalocyanine , acceptor , molecule , manganese , redox , photochemistry , ligand (biochemistry) , electrochemistry , electron transfer , crystallography , electron acceptor , ion , inorganic chemistry , organic chemistry , electrode , biochemistry , physics , receptor , condensed matter physics
The interaction of manganese phthalocyanine with F4‐TCNQ is accompanied by the transformation of the acceptor molecule into a new organic ligand, the 4‐(dicyanomethanido)tetra‐fluorobenzoate dianion, resulting in the formation of a unique Mn III charge‐transfer complex, in which two Mn phthalocyanine moieties are bridged by the dianion, with parallel arrangement of all aromatic fragments and an interplanar distance of 3.30 Å. The formation of the complex takes place in a 2:1 ratio, with the two electrons transferring from two donor molecules to an acceptor molecule. Magnetic measurements reveal that Mn III ions in the studied complex occur in the high‐spin state S = 2 and are coupled antiferromagnetically, presumably by the superexchange mechanism through the 4‐(dicyanomethanido)tetrafluorobenzoate dianion bridge, with an interaction constant of J = 5 cm –1 (7 K). According to the electrochemical data, the new complex appears to have unusual redox properties and might be described as an electronic reservoir with strong acceptor ability, being able to take seven electrons. Notably, all of the reduction–oxidation steps are reversible, proceeding without structural changes.