108
S. Shimizu
Fig. 4.19 Synthesis of SuperPc and UV/vis/NIR absorption spectra of H 2 Pc and SuperPc in 1chloronaphthalene. SuperPc is termed as PcUO 2 in the figure due to the false characterization.
The absorption spectra are from the first paper (Bloor et al. 1964) and redrawn with permission.
Copyright 1964 Canadian Science Publishing
the Q-like band was slightly red-shifted, but the splitting was rather modest so that
the MCD signal corresponding to the Q-like band appeared as a pseudo-Faraday
A term. The observed changes in the optical property by low-symmetrization of
SuperPz chromophore are similar to those seen for Pcs. MO calculations based on
the DFT method reproduced the degenerate LUMO for SuperPc and SuperPz and
non-degenerate LUMO and LUMO+1 for low-symmetry SuperPz (Fig. 4.21).
To solve the difficulty in the synthesis of isoindole oligomers as precursors, the
introduction of other heterocycles has been investigated. Two of such expanded Pc
analogues have been known to date (Fig. 4.22). Torres reported the synthesis of [4
+ 2] macrocycle comprising four isoindole units and two triazole units from a selfcondensation of [2 + 1] linear precursor (Rodríguez-Morgade et al. 2001). This kind
of structure is often referred to as hemiporphyrazine. The other example independently reported by Kobayashi and Torres is called [3 + 3] hemiporphyrazine, which
S. Shimizu
Fig. 4.19 Synthesis of SuperPc and UV/vis/NIR absorption spectra of H 2 Pc and SuperPc in 1chloronaphthalene. SuperPc is termed as PcUO 2 in the figure due to the false characterization.
The absorption spectra are from the first paper (Bloor et al. 1964) and redrawn with permission.
Copyright 1964 Canadian Science Publishing
the Q-like band was slightly red-shifted, but the splitting was rather modest so that
the MCD signal corresponding to the Q-like band appeared as a pseudo-Faraday
A term. The observed changes in the optical property by low-symmetrization of
SuperPz chromophore are similar to those seen for Pcs. MO calculations based on
the DFT method reproduced the degenerate LUMO for SuperPc and SuperPz and
non-degenerate LUMO and LUMO+1 for low-symmetry SuperPz (Fig. 4.21).
To solve the difficulty in the synthesis of isoindole oligomers as precursors, the
introduction of other heterocycles has been investigated. Two of such expanded Pc
analogues have been known to date (Fig. 4.22). Torres reported the synthesis of [4
+ 2] macrocycle comprising four isoindole units and two triazole units from a selfcondensation of [2 + 1] linear precursor (Rodríguez-Morgade et al. 2001). This kind
of structure is often referred to as hemiporphyrazine. The other example independently reported by Kobayashi and Torres is called [3 + 3] hemiporphyrazine, which