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

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 (Φ_F = 0.26) and 504 nm (Φ_F = 0.24) in CHCl₃ and in the powdered state, respectively.

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