%0 Journal Article %1 Zhu_2020 %A Zhu, Chongwei %A Shoyama, Kazutaka %A Würthner, Frank %D 2020 %I Wiley %J Angew. Chem. Int. Ed. %K myown %N 48 %P 21505--21509 %R 10.1002/anie.202010077 %T Conformation and Aromaticity Switching in a Curved Non-Alternant sp2 Carbon Scaffold %U https://onlinelibrary.wiley.com/doi/10.1002/anie.202010077 %V 59 %X A curved sp2 carbon scaffold containing fused pentagon and heptagon units (1) was synthesized by Pd‐catalyzed 5+2 annulation from a 3,9‐diboraperylene precursor and shows two reversible oxidation processes at low redox potential, accompanied by a butterfly‐like motion. Stepwise oxidation produced radical cation 1.+ and dication 12+. In the crystal structure, 1 exhibits a chiral cisoid conformation and partial π‐overlap between the enantiomers. For the radical cation 1.+, a less curved cisoid conformation is observed with a π‐dimer‐type arrangement. 12+ adopts a more planar structure with transoid conformation and slip‐stacked π‐overlap with closest neighbors. We also observed an intermolecular mixed‐valence complex of 1⋅(1.+)3 that has a huge trigonal unit cell (1)72(SbF6)54⋅(hexane)101 and hexagonal columnar stacks. In addition to the conformational change, the aromaticity of 1 changes from localized to delocalized, as demonstrated by AICD and NICS(1)zz calculations.

@article{Zhu_2020, abstract = {A curved sp2 carbon scaffold containing fused pentagon and heptagon units (1) was synthesized by Pd‐catalyzed [5+2] annulation from a 3,9‐diboraperylene precursor and shows two reversible oxidation processes at low redox potential, accompanied by a butterfly‐like motion. Stepwise oxidation produced radical cation 1.+ and dication 12+. In the crystal structure, 1 exhibits a chiral cisoid conformation and partial π‐overlap between the enantiomers. For the radical cation 1.+, a less curved cisoid conformation is observed with a π‐dimer‐type arrangement. 12+ adopts a more planar structure with transoid conformation and slip‐stacked π‐overlap with closest neighbors. We also observed an intermolecular mixed‐valence complex of 1⋅(1.+)3 that has a huge trigonal unit cell [(1)72(SbF6)54⋅(hexane)101] and hexagonal columnar stacks. In addition to the conformational change, the aromaticity of 1 changes from localized to delocalized, as demonstrated by AICD and NICS(1)zz calculations.}, added-at = {2020-11-19T15:02:20.000+0100}, author = {Zhu, Chongwei and Shoyama, Kazutaka and Würthner, Frank}, biburl = {https://www.bibsonomy.org/bibtex/2f0e430556beaf69bc2e36b7a82292509/wuerthner_group}, doi = {10.1002/anie.202010077}, interhash = {01b755b7a82c25549440f4053d84cb98}, intrahash = {f0e430556beaf69bc2e36b7a82292509}, journal = {Angew. Chem. Int. Ed.}, keywords = {myown}, month = sep, number = 48, pages = {21505--21509}, publisher = {Wiley}, timestamp = {2020-11-19T15:02:20.000+0100}, title = {Conformation and Aromaticity Switching in a Curved Non-Alternant sp2 Carbon Scaffold}, url = {https://onlinelibrary.wiley.com/doi/10.1002/anie.202010077}, volume = 59, year = 2020 }