Solution‐Processable Multi‐Substituted Buckybowls: Synthesis of Diindeno(1,2,3,4‐defg:1’,2’,3’,4’‐mnop)chrysene Derivatives

Abstract

Preparative synthesis of a new, soluble, and functionalized buckybowl is described. The precursor of dibenzo[g,p]chrysene having four bromine atoms at two fjord regions undertook palladium-catalyzed intramolecular cyclization to afford a skeletal buckybowl, namely, diindeno(1,2,3,4-defg:1',2',3',4'mnop)chrysene. The resulting curved scaffold possesses two important substituents: four-fold alkyls increasing solubility and four-fold methoxy groups that could be further functionalized. These two features, coupled with the gently curved π-system, enable general access to solution-compatible and multi-functional buckybowl molecules.

Post‐Formation of Fused Pentagonal Structure on Fjord Region of Polyaromatic Hydrocarbons under Hydrothermal Conditions

“…Particularly, limited examples have been reported on the CP-PAHs with internal pentagonal ring(s) heavily fused by multiple benzene rings, utilizing methods such as flush vacuum pyrolysis (FVP), [3,18] metal-catalyzed or mediated carbon-halogen bond activation, [19][20][21] on-metal-surface reaction, [22,23] Pt-mediated solid-state or flow condition reactions with tandem CÀ H activation/CÀ C bond formation at elevated temperature [24] and other methods. [25][26][27] In this manuscript, we demonstrate that the Pt-catalyzed cyclization at fjord region promotes the 5-on-6 synthesis at lower temperature, 200-260 °C in water to furnish singly cyclized CP-PAHs.…”

Electrochemical and spectroscopic properties of twisted dibenzo[g,p]chrysene derivatives

“…These remarkable substituent effects are an interesting and important finding for molecular design, but the effects of X and Z substituents and the twisting of the naphthalene moiety have not been reported. We previously studied the synthesis of solution-processable DBC derivatives with various substituents attached [47][48][49][50][51]. We also recently reported on a synthetic strategy for preparing DBC derivatives using DBC-H with four isopropyl groups at X as a key template for the derivatization (Figure 1c).…”

Acenaphthenoannulation Induced by the Dual Lewis Acidity of Alumina

“…[17][18][19][20][21][22][23] Thus, the incorporation of pentagons into the hexagonal lattice is accompanied by strain energies related to the deviation of the valence angles leading to the positive Gaussian curvature. Due to the similarity of the acquired shape with a bowl, this class of compounds is oftentimes referred to as buckybowls, which, despite recent advances, [21,[23][24][25][26][27] remain extremely elusive targets. For example, incorporation of a pentagon (by indenoannulation) is a challenging reaction that can be implemented using only a few methods, such as flash vacuum pyrolysis, [28,29] Pd-catalyzed aryl-aryl coupling, [30] or CÀ F bond activation [31,32] using hard σ-Lewis acids such as silyl carboranes [33,34] or activated γ-alumina.…”