title: Optically active oxo(phthalocyaninato)vanadium(IV) with geometric asymmetry: synthesis and correlation between the circular dichroism sign and conformation.
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.
authors.affiliation: Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578, Japan. nagaok@mail.tains.tohoku.ac.jp
authors.forename: Nagao
authors.initials: N
authors.lastname: Kobayashi
authors.forename: Fumiko
authors.initials: F
authors.lastname: Narita
authors.forename: Kazuyuki
authors.initials: K
authors.lastname: Ishii
authors.forename: Atsuya
authors.initials: A
authors.lastname: Muranaka