Crystal Structures and Electronic Properties of Saddle-Distorted and Protonated Phthalocyanines

• Honda Tatsuhiko

  Osaka Univ.

• Kojima Takahiko

  Univ. of Tsukuba

• Kobayashi Nagao

  Tohoku Univ.

• Fukuzumi Shunichi

  Osaka Univ.

Bibliographic Information

Other Title

• サドル型歪みを有するプロトン化フタロシアニンの結晶構造と電子状態

Abstract

We report herein the formation and the crystal structure determination of meso- and isoindole-nitrogen protonated phthalocyanines for the first time by using saddle-distorted free-base and zinc octaphenylphthalocyanine (Ph₈Pc) by using HBr and HCl, respectively. Spectroscopic titration of H₂Ph₈Pc with trifluoroacetic acid (TFA) in benzonitrile revealed one-step diprotonation at the isoindole-N atoms, whereas, in the case of ZnPh₈Pc, two-step diprotonation at meso-N atoms was observed. The formation constants of protonated phthalocyanines indicate that the deformed structure facilitates the protonation. From the electrochemical measurements, the protonation of the phthalocyanine ring provides the stabilization of HOMO energies and the significant destabilization of LUMO energies, which cannot be achieved by introduction of substituents and/or the expansion of the phthalocyanine ring.

Journal

• Abstracts of Symposium on Physical Organic Chemistry

  Abstracts of Symposium on Physical Organic Chemistry 2010 (0), 2P66-2P66, 2011

  The Society of Physical Organic Chemistry, Japan

Keywords

• Phthalocyanine
• Protonation
• Crystal Structure
• Electronic property

Details

• CRID: 1390001205555957632
• NII Article ID: 130004729203
• DOI: 10.11494/kisoyuki.2010.0.2p66.0
• Text Lang: ja
• Data Source:
  • JaLC
  • CiNii Articles
  • KAKEN
• Abstract License Flag: Disallowed