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

Gluyas, J.B.G.; Manici, V.; Gückel, S.; Vincent, K.B.; Yufit, D.S.; Howard, J.A.K.; Skelton, B.W.; Beeby, A.; Kaupp, M.; Low, P.J.

Abstract

A series of cross-conjugated compounds based on an (E)-4,4′-(hexa-3-en-1,5-diyne-3,4-diyl)bis(N,N-bis(4-methoxyphenyl)aniline) skeleton (1–6) 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≡CSi(CH3)3, 3: C6H4COOCH3, 4: C6H4CF3, 5: C6H4C≡N, 6: C6H4C≡CC5H4N), 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 π-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.

Citation

Gluyas, J., Manici, V., Gückel, S., Vincent, K., Yufit, D., Howard, J., …Low, P. (2015). Cross-Conjugated Systems Based On An (E)-Hexa-3-en-1,5-diyne-3,4-diyl Skeleton: Spectroscopic and Spectroelectrochemical Investigations. Journal of Organic Chemistry, 80(22), 11501-11512. https://doi.org/10.1021/acs.joc.5b02240

• Journal Article Type: Article
• Online Publication Date: Oct 23, 2015
• Publication Date: Nov 20, 2015
• Deposit Date: Apr 14, 2016
• Publicly Available Date: Oct 23, 2016
• Journal: Journal of Organic Chemistry
• Print ISSN: 0022-3263
• Electronic ISSN: 1520-6904
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 80
• Issue: 22
• Pages: 11501-11512
• DOI: https://doi.org/10.1021/acs.joc.5b02240
• Public URL: https://durham-repository.worktribe.com/output/1384323