Cross-Conjugated Systems Based On An (E)-Hexa-3-en-1,5-diyne-3,4-diyl Skeleton: Spectroscopic and Spectroelectrochemical Investigations.
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.
Josef B G
JB
Gluyas
Department of Chemistry, University of Durham , South Road, Durham DH1 3LE, United Kingdom.
Valentina
V
Manici
Institut für Chemie, Technische Universität Berlin , Sekr. C7, Strasse des 17. Juni 135, 10623 Berlin, Germany.
Simon
S
Gückel
Department of Chemistry, University of Durham , South Road, Durham DH1 3LE, United Kingdom.
Kevin B
KB
Vincent
Department of Chemistry, University of Durham , South Road, Durham DH1 3LE, United Kingdom.
Dmitry S
DS
Yufit
Department of Chemistry, University of Durham , South Road, Durham DH1 3LE, United Kingdom.
Judith A K
JA
Howard
Brian W
BW
Skelton
Department of Chemistry, University of Durham , South Road, Durham DH1 3LE, United Kingdom.
Andrew
A
Beeby
Institut für Chemie, Technische Universität Berlin , Sekr. C7, Strasse des 17. Juni 135, 10623 Berlin, Germany.
Martin
M
Kaupp
Paul J
PJ
Low