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  [in Japanese] Crystal Structures and Electronic Properties of Saddle-Distorted and Protonated Phthalocyanines  [in Japanese]

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Abstract

サドル型に歪んだフリーベース及び亜鉛フタロシアニンのプロトン化体の結晶構造を明らかにした。ジクロロメタン中における吸収滴定から、フリーベースでは1段階のジプロトン化が起こるのに対し、亜鉛錯体では2段階のモノプロトン化が起こることが分かった。吸収スペクトル、電気化学測定の結果からプロトン化することでフタロシアニンのLUMOが大きく不安定化されることを明らかにした。

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 (Ph<SUB>8</SUB>Pc) by using HBr and HCl, respectively. Spectroscopic titration of H<SUB>2</SUB>Ph<SUB>8</SUB>Pc with trifluoroacetic acid (TFA) in benzonitrile revealed one-step diprotonation at the isoindole-N atoms, whereas, in the case of ZnPh<SUB>8</SUB>Pc, 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

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