Selective Formation of Conductive Network by Radical-Induced Oxidation

Cd-based coordination networks having channels were formed selectively by using a redox-active aromatic ligand 2,5,8-tri­(4-pyridyl)­1,3-diazaphenalene (TPDAP, H + 1 – ). An electron-conductive network having a π–π stacking columnar structure of TPDAP formed in the presence of a trace amount of TPDA...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2016-02, Vol.138 (6), p.1776-1779
Main Authors: Koo, Jin Young, Yakiyama, Yumi, Lee, Gil Ryeong, Lee, Jinho, Choi, Hee Cheul, Morita, Yasushi, Kawano, Masaki
Format: Article
Language:English
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Summary:Cd-based coordination networks having channels were formed selectively by using a redox-active aromatic ligand 2,5,8-tri­(4-pyridyl)­1,3-diazaphenalene (TPDAP, H + 1 – ). An electron-conductive network having a π–π stacking columnar structure of TPDAP formed in the presence of a trace amount of TPDAP radical (1 •). In contrast, a nonconductive network having a dimer unit of H + 1 – formed in the absence of 1 •. These results suggest the presence of a unique oxidation mechanism of TPDAP induced by formation of H + 1 – -1 • dimer, which was initiated by a trace amount of 1 •. The dimerization increased HOMO level of H + 1 – moiety within the dimer to generate further radicals that could not form when H + 1 – was well isolated in CH3OH.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.5b12355