A Trinuclear Iron(III) Complex of a Triple Noninnocent Ligand for Spin-Structured Molecular Conductors

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Abstract

N,N′,N′′,N′′′,N′′′′,N′′′′′-(Triphenylene-2,3,6,7,10,11-hexayl)hexapicolinamide (H6hptp), a triangular ligand containing three noninnocent coordination sites, and its trinuclear iron(III) complex (PPh4)3[FeIII 3(hptp)6(CN)6] were prepared. In this complex, three low-spin Fe3+ ions are coordinated by the triangular hptp6− bridging ligand at its apices. Cyclic voltammetry of (PPh4)3[FeIII 3(hptp)6(CN)6] in PhCN solution showed one reductive wave for 3 Fe2+/3 Fe3+ and three oxidative waves for the hptp6− ligand. The controlled-potential electronic spectra of the solution presented broad absorption bands in the near-IR (NIR) region for oxidations because a π-radical is generated on the hptp6− ligand. The EPR spectra of frozen solutions also showed large oxidization-state dependent differences caused by the strong exchange interactions between the electrons in the d orbitals of the Fe3+ ions and those of the π-radicals in the hptp6− ligand. The electronic and magnetic states of the oxidized species were investigated using density functional theory.

Original languageEnglish
Pages (from-to)19323-19331
Number of pages9
JournalChemistry - A European Journal
Volume24
Issue number72
DOIs
Publication statusPublished - 2018 Dec 20

Keywords

  • EPR spectroscopy
  • UV/Vis spectroscopy
  • computational chemistry
  • magnetic properties
  • radical ions
  • redox chemistry

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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