Deformed phthalocyanines: Synthesis and characterization of zinc phthalocyanines bearing phenyl substituents at the 1-, 4-, 8-, 11-, 15-, 18-, 22-, and/or 25-positions

Takamitsu Fukuda, Shigetsugu Homma, Nagao Kobayashi

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84 Citations (Scopus)

Abstract

The synthesis of a series of zinc phthalocyanines partially phenyl-substituted at the 1-, 4-, 8-, 11-, 15-, 18-, 22-, -and/or 25-positions (the so-called α-positions) is reported. Macrocycle formation based on 3,6-diphenylphthalonitrile, o-phthalonitrile, and zinc acetate predominantly yielded the near-planar disubstituted complex and opposite tetrasubstituted isomer, while the lithium method yielded the sterically hindered hexasubstituted complex and adjacent tetrasubstituted isomer. All compounds have been characterized by 1H NMR, MALDI-TOF-MS, and elemental analysis methods. In addition, crystal structures have been solved for the di-, hexa-, and octasubstituted complexes and the adjacent tetrasubstituted isomer. DFT geometry optimization calculations predict more highly deformed structures than those observed in the crystals. The packing force of the crystals cannot therefore be ignored, particularly for the less phenyl-substituted derivatives. The crystal structures have revealed that overlap of the phenyl groups causes substantial deformation of the phthalocyanine (Pc) ligands within the crystals, while strong π-π stacking in the remainder of the Pc moiety lacking phenyl substituents can suppress the impact of the deformation. Absorption spectra show sizable red shifts of the Q-band with increasing number of phenyl groups. Analysis of the results of absorption spectra and electrochemical measurements reveals that a substantial portion of the red shift is attributable to the ring deformations. Molecular orbital calculations lend further support to this conclusion. A moderately intense absorption band emerging at around 430 nm for highly deformed octaphenyl-substituted zinc Pc can be assigned to the HOMO→LUMO + 3 transition, which is parity-forbidden for planar Pcs, but becomes allowed since the ring deformations remove the center of symmetry.

Original languageEnglish
Pages (from-to)5205-5216
Number of pages12
JournalChemistry - A European Journal
Volume11
Issue number18
DOIs
Publication statusPublished - 2005 Sep 5

Keywords

  • Dyes/pigments
  • Electronic structure
  • Phthalocyanines
  • Porphyrinoids
  • UV/Vis spectroscopy

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

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