Unexpected Scholl Reaction of 6,7,13,14-Tetraarylbenzo[k]tetraphene: Selective Formation of Five-Membered Rings in Polycyclic Aromatic Hydrocarbons
Liu J, Narita A, Osella S, Zhang W, Schollmeyer D, Beljonne D, Feng X, Muellen K (2016)
Publication Type: Journal article
Publication year: 2016
Journal
Book Volume: 138
Pages Range: 2602-2608
Journal Issue: 8
DOI: 10.1021/jacs.5b10399
Abstract
Cyclodehydrogenation is a versatile reaction that has enabled the syntheses of numerous polycyclic aromatic hydrocarbons (PAHs). We now describe a unique Scholl reaction of 6,7,13,14-tetraarylbenzo[k]tetraphene, which "unexpectedly" forms five-membered rings accompanying highly selective 1,2-shift of aryl groups. The geometric and optoelectronic nature of the resulting bistetracene analogue with five-membered rings is comprehensively investigated by single-crystal X-ray, NMR, UV-vis absorption, and cyclic voltammetry analyses. Furthermore, a possible mechanism is proposed to account for the selective five-membered-ring formation with the rearrangement of the aryl groups, which can be rationalized by density functional theory (DFT) calculations. The theoretical results suggest that the formation of the bistetracene analogue with five-membered rings is kinetically controlled while an "expected" product with six-membered rings is thermodynamically more favored. These experimental and theoretical results provide further insights into the still controversial mechanism of the Scholl reaction as well as open up an unprecedented entry to extend the variety of PAHs by programing otherwise unpredictable rearrangements during the Scholl reaction.
Involved external institutions
Max-Planck-Institut für Polymerforschung (MPI-P) / Max Planck Institute for Polymer Research
Germany (DE)
University of Mons / Université de Mons
Belgium (BE)
Johannes Gutenberg-Universität Mainz (JGU)
Germany (DE)
Technische Universität Dresden
Germany (DE)
Germany (DE)
University of Mons / Université de Mons
Belgium (BE)
Johannes Gutenberg-Universität Mainz (JGU)
Germany (DE)
Technische Universität Dresden
Germany (DE)
How to cite
APA:
Liu, J., Narita, A., Osella, S., Zhang, W., Schollmeyer, D., Beljonne, D.,... Muellen, K. (2016). Unexpected Scholl Reaction of 6,7,13,14-Tetraarylbenzo[k]tetraphene: Selective Formation of Five-Membered Rings in Polycyclic Aromatic Hydrocarbons. Journal of the American Chemical Society, 138(8), 2602-2608. https://doi.org/10.1021/jacs.5b10399
MLA:
Liu, Junzhi, et al. "Unexpected Scholl Reaction of 6,7,13,14-Tetraarylbenzo[k]tetraphene: Selective Formation of Five-Membered Rings in Polycyclic Aromatic Hydrocarbons." Journal of the American Chemical Society 138.8 (2016): 2602-2608.
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