Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2023 Jul 28;79(Pt 8):757-761.
doi: 10.1107/S2056989023006187. eCollection 2023 Jul 1.

Synthesis, optical properties and crystal structure of (E, E)-1,3-(3,4:9,10-dibenzododeca-1,11-diene-5,7-diyne-1,12-di-yl)benzene

Hikaru Watanabe  1 , Takuma Sato  1 , Michiki Sumita  1 , Mei Shiroyama  1 , Daichi Sugawara  1 , Tomoki Tokuyama  1 , Yasuhiro Okuda  1 , Kan Wakamatsu  2 , Haruo Akashi  3 , Akihiro Orita  1
Affiliations

Synthesis, optical properties and crystal structure of (E, E)-1,3-(3,4:9,10-dibenzododeca-1,11-diene-5,7-diyne-1,12-di-yl)benzene

Hikaru Watanabe et al. Acta Crystallogr E Crystallogr Commun. .

Abstract

The de-hydro-benzannulene (E,E)-1,3-(3,4:9,10-dibenzododeca-1,11-diene-5,7-diyne-1,12-di-yl)benzene, C26H16, was successfully synthesized via photocatalyst-assisted stereoselective reductive de-sulfonyl-ation of 1,3-bis-{1-phenyl-sulfonyl-2-[2-(tri-methyl-silylethyn-yl)phen-yl]ethen-yl}benzene, C44H42O4S2Si2, and subsequent desilylative cyclization of the resulting (E,E)-bis-silyl-protected dienyne, C32H34Si2. The structure of the de-hydro-benzannulene thus obtained was confirmed by single-crystal X-ray analysis; three benzene rings are connected to one another by a 1,3-butadiynylene and a pair of ethenylene arrays. Although the π-system expanded efficiently in the de-hydro-benzannulene, it was observed that the butadiynylene and ethenylene arrays were strained, showing smaller [171.3 (2)-172.6 (2) °] and larger bond angles [122.5 (2)-131.9 (2)°] than the conventional bond angles, respectively. In CHCl3, the de-hydro-benzannulene showed the longest absorption band at 377 nm. When irradiated by UV light, it emitted fluorescence at 468 nm (ΦF = 0.26) and 504 nm (ΦF = 0.24) in CHCl3 and in the powdered state, respectively.

Keywords: crystal structure; de­hydro­benzannulene; expanded π-system; reductive de­sulfonyl­ation.

PubMed Disclaimer

Figures

Figure 1
Figure 1
The mol­ecular structure of (E,E)-1 with displacement ellipsoids drawn at the 50% probability level.
Figure 2
Figure 2
A partial packing plot of (E,E)-1 viewed approximately down the crystallographic a-axis.
Figure 3
Figure 3
The synthetic route to (E,E)-1.
Figure 4
Figure 4
UV–Vis absorption and photoluminescence spectra of (E,E)-1.
Figure 5
Figure 5
Graphical representation of frontier orbitals (a) HOMO and (b) LUMO of (E,E)-1.
See this image and copyright information in PMC

References

    1. Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.
    1. Esser, B., Rominger, F. & Gleiter, R. (2008). J. Am. Chem. Soc. 130, 6716–6717. - PubMed
    1. Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. - PMC - PubMed
    1. Karki, S., Karas, L. J., Wang, X., Wu, J. I. & Miljanić, O. Š. (2022). Cryst. Growth Des. 22, 2076–2081.
    1. Ojima, J., Kakumi, H., Kitatani, K., Wada, K., Ejiri, E. & Nakada, T. (1985). Can. J. Chem. 63, 2885–2891.

LinkOut - more resources