Cross-Conjugated Systems Based On An (E)-Hexa-3-en-1,5-diyne-3,4-diyl Skeleton: Spectroscopic and Spectroelectrochemical Investigations

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• 作者：Josef B. G. Gluyas ; Valentina Manici ; Simon G眉ckel ; Kevin B. Vincent ; Dmitry S. Yufit ; Judith A. K. Howard ; Brian W. Skelton ; Andrew Beeby ; Martin Kaupp ; Paul J. Low
• 刊名：Journal of Organic Chemistry
• 出版年：2015
• 出版时间：November 20, 2015
• 年：2015
• 卷：80
• 期：22
• 页码：11501-11512
• 全文大小：808K
• ISSN：1520-6904

文摘

A series of cross-conjugated compounds based on an (E)-4,4鈥?(hexa-3-en-1,5-diyne-3,4-diyl)bis(N,N-bis(4-methoxyphenyl)aniline) skeleton (1鈥?b>6) have been synthesized. The linear optical absorption properties can be tuned by modification of the substituents at the 1 and 5 positions of the hexa-3-en-1,5-diynyl backbone (1: Si(CH(CH₃)₂)₃, 2: C₆H₄C鈮Si(CH₃)₃, 3: C₆H₄COOCH₃, 4: C₆H₄CF₃, 5: C₆H₄C鈮, 6: C₆H₄C鈮C₅H₄N), although attempts to introduce electron-donating (C₆H₄CH₃, C₆H₄OCH₃, C₆H₄Si(CH₃)₃) substituents at these positions were hampered by the ensuing decreased stability of the compounds. Spectroelectrochemical investigations of selected examples, supported by DFT-based computational studies, have shown that one- and two-electron oxidation of the 1,2-bis(triarylamine)ethene fragment also results in electronic changes to the perpendicular 蟺-system in the hexa-3-en-1,5-diynyl branch of the molecule. These properties suggest that (E)-hexa-3-en-1,5-diynyl-based compounds could have applications in molecular sensing and molecular electronics.