Positional Isomers of Isocyanoazulenes as Axial Ligands Coordinated to Ruthenium(II) Tetraphenylporphyrin: Fine-Tuning Redox and Optical Profiles

Mahtab Fathi-Rasekh, Gregory T. Rohde, Mason D. Hart, Toshinori Nakakita, Yuriy V. Zatsikha, Rashid R. Valiev, Mikhail V. Barybin, Victor N. Nemykin

Research output: Contribution to journalArticlepeer-review

3 Citations (Scopus)

Abstract

Two isomeric ruthenium(II)/5,10,15,20-tetraphenylporphyrin complexes featuring axially coordinated redox-active, low-optical gap 2-or 6-isocyanoazulene ligands have been isolated and characterized by NMR, UV-vis, and magnetic circular dichroism (MCD) spectroscopic methods, high-resolution mass spectrometry, and single-crystal X-ray crystallography. The UV-vis and MCD spectra support the presence of the low-energy, azulene-centered transitions in the Q band region of the porphyrin chromophore. The first coordination sphere in new L2RuTPP complexes reflects compressed tetragonal geometry. The redox properties of the new compounds were assessed by electrochemical and spectroelectrochemical means and correlated with the electronic structures predicted by density functional theory and CASSCF calculations. Both experimental and theoretical data are consistent with the first two reduction processes involving the axial azulenic ligands, whereas the oxidation profile (in the direction of increasing potential) is exerted by the ruthenium ion, the porphyrin core, and the axial azulenic moieties.

Original languageEnglish
Pages (from-to)9316-9325
Number of pages10
JournalInorganic Chemistry
Volume58
Issue number14
DOIs
Publication statusPublished - 26 Jun 2019

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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