Benzene‐Fused Azacorannulene Bearing an Internal Nitrogen Atom

Abstract

A novel nitrogen-doped corannulene derivative, 8-tert-butyl-6b(2) -azapentabenzo[bc,ef,hi,kl,no]corannulene, was synthesized by 1,3-dipolar cycloaddition of a polycyclic aromatic azomethine ylide with a diarylethyne and subsequent palladium-catalyzed intramolecular cyclization. This molecule represents the first example of a corannulene derivative bearing an internal heteroatom, and exhibits unique structural and physical properties caused by the introduction of the nitrogen atom and extended π-conjugation, as compared to the parent corannulene.

New advances in nanographene chemistry

“…152 Nozaki et al found that 61 can also react with fullerene C 60 to form an adduct. 154 N-doped corannulene derivative 64 is a rare example of bowl-shaped PAHs with heteroatom doping inside the aromatic framework, and demonstrated distinctly different structural and opto-electronic properties compared to the parent corannulene. 151 In 2015, Ito and Nozaki et al achieved an unprecedented synthesis of 6b 2 -azapentabenzo[bc,ef,hi,kl,no]corannulene 64 based on the 1,3-dipolar cycloaddition of azomethine ylide 61 with 2,2 0 ,6-trichlorodiphenylacetylene, followed by three-fold Pd-catalysed cyclisation (Fig.…”

Synthesis of Nitrogen‐Containing Rubicene and Tetrabenzopentacene Derivatives

“…[51,52] [d] The values were determined from the density functionalt heory calculations. Diels-Alder (Povarov) reaction, [38,39] the Heck coupling, [40,41] and base-mediated cyclodehydrohalogenation, [42,43] making it potentially useful for ab road range of researchers.T hird, given the difficulties inherent to designing n-type and ambipolar organic semiconductors [53,54] and the known utility of nitrogen substitution for coaxing such behavior from acenes, [32,33] the reported rubicenes and tetrabenzopentacenes hold particular promise as organic electronic functional materials.F inally,n itrogen-containing fullerenes and graphene nanoribbons remain relatively rare and challenging to prepare, [19][20][21][22][23][24][25] and as such, we envision that our approach could eventually prove valuable for the design and construction of extended doped carbonaceous frameworks.A ltogether, our findings may open new research avenues and provide unique opportunities for the solution-phase synthesis of novel carbon-based materials.…”

“…[7][8][9][10][11][12][13][14][15][16][17][18] However,asmaller number of studies have reported the solutionphase synthesis of analogous nitrogen-doped constructs. [19][20][21][22][23][24][25][26][27] Indeed, the rational incorporation of nitrogen heteroatoms, while frequently challenging,i sk nown to be valuable for tuning the properties of graphitic systems, [28][29][30][31] as demonstrated by the successful molecular engineering of various Nheteroacenes for improved transistor performance. [32,33] Consequently,t he development of new routes to nitrogencontaining acenes,f ullerenes,a nd GNRs remains important for the next generation of semiconductor devices and technologies.…”

Synthesis of Pyrrole‐Fused Corannulenes: 1,3‐Dipolar Cycloaddition of Azomethine Ylides to Corannulene

“…540 nm) and absorption spectra were virtually inert to the polarity of solvents.T he observed absorption wavelengths are bathochromically shifted relative to those of 1 [37] and similar to those of related molecules bearing an ullazine structure. [26,27] TheHOMO and LUMO energies of 6 and 7 were estimated by combining the results of UV absorption analysis and the oxidation potentials of 6 and 7 measured by cyclic voltammetry (see Figure S14 and Table S4). Thee mission spectra of 6 and 7 exhibited remarkable solvatofluorochromism.…”

“…Themost noteworthy feature of 3 is its high reactivity towards dipolarophiles,that is, 3 even converts sterically crowded 1,2diarylethynes into the corresponding cycloadducts. [27] Herein, we report unprecedented 1,3-dipolar cycloadditions of 3 to the rim double bond of 1,a nd it affords the corresponding mono-and diadducts, 4 and 5,r espectively.T his reaction represents the first example of a1 ,3-dipolar cycloaddition to 1.F urthermore,u pon subsequent aromatizations,c ycloadducts 4 and 5 were converted into the pyrrole-fused corannulenes, 6 and 7,r espectively (Scheme 1). [28,29] The1,3-dipolar cycloaddition of 1 with 3,generated in situ from 2,was carried out under the reaction conditions outlined in Scheme 1.…”