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Electrochemical and in situ spectroelectrochemical behavior of 2,3,7,8,12,13,17,18-octakis(hexyl-thio) tetraazaporphyrin (H₂OHTTAP) and [Zn(II)OHTTAP]

Department of Chemical Engineering, Chemistry and Material Science, Polytechnic University, Six Metrotech Center, Brooklyn, NY 11201, USA

Corresponding author, Department of Chemical Engineering, Chemistry and Material Science, Polytechnic University, Six Metrotech Center, Brooklyn, NY 11201, USA.

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ZHENXING WANG

Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, People's Republic of, China

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DAIKE WANG

Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, People's Republic of, China

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KENICHI SUGIURA

The Institute of Science and Industrial Research, Osaka University, Ibaraki Osaka 567, Japan

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, and

YOSHITERU SAKATA

The Institute of Science and Industrial Research, Osaka University, Ibaraki Osaka 567, Japan

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https://doi.org/10.1002/jpp.358Cited by:5 (Source: Crossref)

Abstract

The characterization of free base porphyrin 2,3,7,8,12,13,17,18-octakis(hexyl-thio) tetraazaporphyrin (H₂OHTTAP) and its zinc(II) complexes [Zn(II)OHTTAP] containing eight thioether groups at the β-pyrrole positions of the macrocycle was reported. Results obtained by cyclic voltammetry and differential pulse voltammetry indicated a five-electron reduction in five steps for each complex. They were oxidized in two single-electron-transfer steps to yield π-cation radicals and dications and reduced in three single-electron-transfer steps to yield π-anion radicals, dianions and trianions, respectively. The redox property of H₂OHTTAP was unusual as compared to porphyrins (PPs) and phthalocyanines (Pcs). Each process was monitored by in situ thin-layer spectroelectrochemistry, which indicated that only the ligand was electroactive. The existence of the eight hexylthio groups was responsible for the intrastack interactions and enhanced intracolumnar and intercolumnar electron motions, resulting in improved conductivity.

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