Azaphenalene Phthalocyanines: Phthalocyanine Analogues with Six-Membered-Ring Units Instead of Five-Membered-Ring Units

作者：Shimizu Soji; Zhu Hua; Kobayashi Nagao^*

来源：Chemistry - A European Journal, 2010, 16(36): 11151-11159.

DOI：10.1002/chem.201000642

• aromaticity
• azaphenalene
• conjugation
• phthalocyanines
• UV/Vis spectroscopy

Mixed-condensation reaction of 1,8-naphthalenedicarbonitrile and a 4,5-disubstituted phthalonitrile provided a series of phthalocyanine (Pc) analogues with azaphenalene (AP) moieties in place of the isoindole moieties. Monosubstituted species, APPc, and the two structural isomers of disubstitutecl species, adj-AP(2)Pc and opp-AP(2)Pc, were successfully isolated by gel-permeation chromatography on HPLC apparatus. Their structures were elucidated by (1)H NMR spectroscopy and X-ray crystallographic analysis. Replacement of the isoindole moieties with azaphenalene moieties created six-membered-ring units in the core and caused distortion of the molecular structures. The Q-band absorption shifted to the red upon an increase in the number of azaphenalene units; the shape of the absorption spectra depended on the molecular symmetries. APPc and opp-AP(2)Pc showed a large splitting of the Q band, whereas adj-AP(2)Pc exhibited a single broad Q band. These changes in the absorption spectra, as well as the unique electronic structures, are discussed in detail, based on magnetic circular dichroism spectra, electrochemical measurements, and density functional theory calculations.

• 出版日期2010