Synthesis of NBN-Type Zigzag-Edged Polycyclic Aromatic Hydrocarbons: 1,9-Diaza-9a-boraphenalene as a Structural Motif
Wang X, Zhang F, Schellharnmer KS, Machata P, Ortmann F, Cuniberti G, Fu Y, Hunger J, Tang R, Popov AA, Berger R, Muellen K, Feng X (2016)
Publication Type: Journal article
Publication year: 2016
Journal
Book Volume: 138
Pages Range: 11606-11615
Journal Issue: 36
DOI: 10.1021/jacs.6b04445
Abstract
A novel class of dibenzo-fused 1,9-diaza-9a-boraphenalenes featuring zigzag edges with a nitrogen-boron-nitrogen bonding pattern named NBN-dibenzophenalenes (NBN-DBPs) has been synthesized. Alternating nitrogen and boron atoms impart high chemical stability to these zigzag-edged polycyclic aromatic hydrocarbons (PAHs), and this motif even allows for postsynthetic modifications, as demonstrated here through electrophilic bromination and subsequent palladium-catalyzed cross-coupling reactions. Upon oxidation, as a typical example, NBN-DBP 5a was nearly quantitatively converted to σ-dimer 5a-2 through an open-shell intermediate, as indicated by UV-vis-NIR absorption spectroscopy and electron paramagnetic resonance spectroscopy corroborated by spectroscopic calculations, as well as 2D NMR spectra analyses. In situ spectroelectrochemistry was used to confirm the formation process of the dimer radical cation 5a-2•+. Finally, the developed new synthetic strategy could also be applied to obtain π-extended NBN-dibenzoheptazethrene (NBN-DBHZ), representing an efficient pathway toward NBN-doped zigzag-edged graphene nanoribbons.
Involved external institutions
Shanghai Jiao Tong University / 上海交通大学
China (CN)
Technische Universität Dresden
Germany (DE)
Leibniz-Institut für Festkörper- und Werkstoffforschung Dresden e.V. (IFW) / Leibniz Institute for Solid State and Materials Research Dresden
Germany (DE)
Max-Planck-Institut für Polymerforschung (MPI-P) / Max Planck Institute for Polymer Research
Germany (DE)
China (CN)
Technische Universität Dresden
Germany (DE)
Leibniz-Institut für Festkörper- und Werkstoffforschung Dresden e.V. (IFW) / Leibniz Institute for Solid State and Materials Research Dresden
Germany (DE)
Max-Planck-Institut für Polymerforschung (MPI-P) / Max Planck Institute for Polymer Research
Germany (DE)
How to cite
APA:
Wang, X., Zhang, F., Schellharnmer, K.S., Machata, P., Ortmann, F., Cuniberti, G.,... Feng, X. (2016). Synthesis of NBN-Type Zigzag-Edged Polycyclic Aromatic Hydrocarbons: 1,9-Diaza-9a-boraphenalene as a Structural Motif. Journal of the American Chemical Society, 138(36), 11606-11615. https://doi.org/10.1021/jacs.6b04445
MLA:
Wang, Xinyang, et al. "Synthesis of NBN-Type Zigzag-Edged Polycyclic Aromatic Hydrocarbons: 1,9-Diaza-9a-boraphenalene as a Structural Motif." Journal of the American Chemical Society 138.36 (2016): 11606-11615.
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