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

Authors
  • Kobayashi, Nagao1
  • Narita, Fumiko
  • Ishii, Kazuyuki
  • Muranaka, Atsuya
  • 1 Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578, Japan. [email protected] , (Japan)
Type
Published Article
Journal
Chemistry - A European Journal
Publisher
Wiley (John Wiley & Sons)
Publication Date
Oct 05, 2009
Volume
15
Issue
39
Pages
10173–10181
Identifiers
DOI: 10.1002/chem.200901306
PMID: 19711387
Source
Medline
License
Unknown

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 right-handed 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.

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