Selective Formation of Conductive Network by Radical-Induced Oxidation

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• 作者：Jin Young Koo ; Yumi Yakiyama ; Gil Ryeong Lee ; Jinho Lee ; Hee Cheul Choi ; Yasushi Morita ; Masaki Kawano
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：February 17, 2016
• 年：2016
• 卷：138
• 期：6
• 页码：1776-1779
• 全文大小：344K
• ISSN：1520-5126

文摘

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.