[4 + 2] Cycloaddition Reaction To Approach Diazatwistpentacenes : Synthesis, Structures, Physical Properties, and Self-assembly

Three novel diazatwistpentacenes (1,4,6,13-tetraphenyl-7:8,11:12-bisbenzo- 2,3-diazatwistpentacene (1, IUPAC name: 9,11,14,16-tetraphenyl-1,6- dihydrobenzo[8,9]triphenyleno[2,3-g]phthalazine); 1,4-di(pyridin-2-yl)-6,13- diphenyl-7:8,11:12-bisbenzo-2,3-diazatwistpentacene (2, IUPAC name: 9,16-diphenyl-11,14-di(pyridin-2-yl)-1,6-dihydrobenzo[8,9]triphenyleno[2,3-g] phthalazine); and 1,4-di(thien-2-yl)-6,13-diphenyl-7:8,11:12-bisbenzo-2,3- diazatwistpentacene (3, IUPAC name: 9,16-diphenyl-11,14-di(thien-2-yl)-1,6- dihydrobenzo[8,9]triphenyleno[2,3-g]phthalazine)) have been successfully synthesized through [4 + 2] cycloaddition reaction involving in situ arynes as dienophiles and substituted 1,2,4,5-tetrazines as dienes. Their structures have been determined by single-crystal X-ray diffraction, confirming that all compounds have twisted configurations with torsion angles between the pyrene unit and the 2,3-diazaanthrance part as high as 21.52° (for 1), 24.74° (for 2), and 21.14° (for 3). The optical bandgaps for all compounds corroborate the values derived from CV. The calculation done by DFT shows that the HOMO-LUMO bandgaps are in good agreement with experimental data. Interestingly, the substituted groups (phenyl, pyridyl, thienyl) in the 1,4-positions did affect their self-assembly and the optical properties of as-resulted nanostructures. Under the same conditions, compounds 1-3 could self-assemble into different morphologies such as microrods (for 1), nanoprisms (for 2), and nanobelts (for 3). Moreover, the UV-vis absorption and emission spectra of as-prepared nanostructures were largely red-shifted, indicating J-type aggregation for all materials. Surprisingly, both 1 and 2 showed aggregation-induced emission (AIE) effect, while compound 3 showed aggregation-caused quenching (ACQ) effect. Our method to approach novel twisted azaacenes through [4 + 2] reaction could offer a new tool to develop unusual twisted conjugated materials for future optoelectronic applications. © 2014 American Chemical Society.