title: Synthesis of NBN-Type Zigzag-Edged Polycyclic Aromatic Hydrocarbons: 1,9-Diaza-9a-boraphenalene as a Structural Motif.
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.
authors.affiliation: School of Chemistry and Chemical Engineering, State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University , Shanghai 200240, P. R. China.
authors.forename: Xinyang
authors.initials: X
authors.lastname: Wang
authors.affiliation: School of Chemistry and Chemical Engineering, State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University , Shanghai 200240, P. R. China.
authors.forename: Fan
authors.initials: F
authors.lastname: Zhang
authors.affiliation: Institute for Materials Science, Max Bergmann Center of Biomaterials and Dresden Center for Computational Materials Science, Technische Universität Dresden , 01062 Dresden, Germany.|Center for Advancing Electronics Dresden (cfaed) and Department of Chemistry and Food Chemistry, Technische Universität Dresden , 01062 Dresden, Germany.
authors.forename: Karl Sebastian
authors.initials: KS
authors.lastname: Schellhammer
authors.affiliation: Center of Spectroelectrochemistry, Department of Electrochemistry and Conducting Polymers, Leibniz Institute for Solid State and Materials Research , 01069 Dresden, Germany.
authors.forename: Peter
authors.initials: P
authors.lastname: Machata
authors.affiliation: Institute for Materials Science, Max Bergmann Center of Biomaterials and Dresden Center for Computational Materials Science, Technische Universität Dresden , 01062 Dresden, Germany.
authors.forename: Frank
authors.initials: F
authors.lastname: Ortmann
authors.affiliation: Institute for Materials Science, Max Bergmann Center of Biomaterials and Dresden Center for Computational Materials Science, Technische Universität Dresden , 01062 Dresden, Germany.|Center for Advancing Electronics Dresden (cfaed) and Department of Chemistry and Food Chemistry, Technische Universität Dresden , 01062 Dresden, Germany.
authors.forename: Gianaurelio
authors.initials: G
authors.lastname: Cuniberti
authors.affiliation: Center for Advancing Electronics Dresden (cfaed) and Department of Chemistry and Food Chemistry, Technische Universität Dresden , 01062 Dresden, Germany.
authors.forename: Yubin
authors.initials: Y
authors.lastname: Fu
authors.affiliation: Center for Advancing Electronics Dresden (cfaed) and Department of Chemistry and Food Chemistry, Technische Universität Dresden , 01062 Dresden, Germany.
authors.forename: Jens
authors.initials: J
authors.lastname: Hunger
authors.affiliation: School of Chemistry and Chemical Engineering, State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University , Shanghai 200240, P. R. China.
authors.forename: Ruizhi
authors.initials: R
authors.lastname: Tang
authors.affiliation: Center of Spectroelectrochemistry, Department of Electrochemistry and Conducting Polymers, Leibniz Institute for Solid State and Materials Research , 01069 Dresden, Germany.
authors.forename: Alexey A
authors.initials: AA
authors.lastname: Popov
authors.affiliation: Center for Advancing Electronics Dresden (cfaed) and Department of Chemistry and Food Chemistry, Technische Universität Dresden , 01062 Dresden, Germany.
authors.forename: Reinhard
authors.initials: R
authors.lastname: Berger
authors.affiliation: Max Planck Institute for Polymer Research , Ackermannweg 10, 55128 Mainz, Germany.
authors.forename: Klaus
authors.initials: K
authors.lastname: Müllen
authors.affiliation: School of Chemistry and Chemical Engineering, State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University , Shanghai 200240, P. R. China.|Center for Advancing Electronics Dresden (cfaed) and Department of Chemistry and Food Chemistry, Technische Universität Dresden , 01062 Dresden, Germany.
authors.forename: Xinliang
authors.initials: X
authors.lastname: Feng