Optically active oxo(phthalocyaninato)vanadium(IV) with geometric asymmetry: Synthesis and correlation between the circular dichroism sign and conformation

Nagao Kobayashi, Fumiko Narita, Kazuyuki Ishii, Atsuya Muranaka

Research output: Contribution to journalArticlepeer-review

22 Citations (Scopus)

Abstract

Oxovanadium(IV) phthalocyanines (VOPcs) with a single-handed rotation have been prepared, and their right- and left-handed enantiomers resolved on a chiral HPLC column. These enantiomers gave circular dichroism (CD) spectra of opposite signs; the correlation between the CD sign and conformation was obtained by time-dependent density functional theory (TDDFT) calculations: an enantiomer showing a negative sign in the Q band was suggested to be the righthanded conformer viewing from the axial oxygen side, whereas that giving a positive CD sign was assigned to the left-handed conformer. Although silicon phthalocyanines (SiPcs) with two different alkoxy axial ligands have been resolved similarly, the absence of a meaningful CD difference probably reflects the flat character of the SiPc plane compared to the VOPc plane. Changes in the Q-band CD, depending on the relative orientation of the peripheral substituents, have been worked out theoretically and the origin of the chiroptical properties is discussed.

Original languageEnglish
Pages (from-to)10173-10181
Number of pages9
JournalChemistry - A European Journal
Volume15
Issue number39
DOIs
Publication statusPublished - 2009 Oct 5

Keywords

  • Circular dichroism
  • Configuration determination
  • Density functional calculations
  • Phthalocyanines
  • UV/Vis spectroscopy

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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