Electron Transfer and Unusual Chemical Transformations of F4-TCNQ in a Reaction with Mn-Phthalocyanine
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Contributors
Abstract
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 MnIII 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 MnIII 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.
Details
Original language | English |
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Pages (from-to) | 3344-3353 |
Number of pages | 10 |
Journal | European journal of inorganic chemistry |
Volume | 2018 |
Issue number | 28 |
Publication status | Published - 31 Jul 2018 |
Peer-reviewed | Yes |
Keywords
ASJC Scopus subject areas
Keywords
- Electron transfer, Fluorinated ligands, Manganese, Phthalocyanines