Electron Transfer and Unusual Chemical Transformations of F4-TCNQ in a Reaction with Mn-Phthalocyanine

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Olga Kataeva - , Russian Academy of Sciences (Author)
  • Kirill Metlushka - , Russian Academy of Sciences, Kazan Volga Region Federal University (Author)
  • Kamil Ivshin - , Russian Academy of Sciences, Kazan Volga Region Federal University (Author)
  • Airat Kiiamov - , Kazan Volga Region Federal University (Author)
  • Vladimir Alfonsov - , Russian Academy of Sciences, Kazan Volga Region Federal University (Author)
  • Mikhail Khrizanforov - , Russian Academy of Sciences (Author)
  • Yulia Budnikova - , Russian Academy of Sciences (Author)
  • Oleg Sinyashin - , Russian Academy of Sciences (Author)
  • Yulia Krupskaya - , Leibniz Institute for Solid State and Materials Research Dresden (Author)
  • Vladislav Kataev - , Leibniz Institute for Solid State and Materials Research Dresden (Author)
  • Bernd Büchner - , Chair of Experimental Solid State Physics, Leibniz Institute for Solid State and Materials Research Dresden (Author)
  • Martin Knupfer - , Leibniz Institute for Solid State and Materials Research Dresden (Author)

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 languageEnglish
Pages (from-to)3344-3353
Number of pages10
JournalEuropean journal of inorganic chemistry
Volume2018
Issue number28
Publication statusPublished - 31 Jul 2018
Peer-reviewedYes

Keywords

ASJC Scopus subject areas

Keywords

  • Electron transfer, Fluorinated ligands, Manganese, Phthalocyanines