Saddle-shaped aza-nanographene with multiple odd-membered rings

Krzeszewski, Maciej; Sobolewski, Andrzej L.; Cyrański, Michał K.; Gryko, Daniel T.

doi:10.1039/d2sc05858h

Cited by 25 publications

(12 citation statements)

References 83 publications

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“…Embedding nonhexagonal rings such as five-, seven-, and eight-membered rings into polycyclic aromatic hydrocarbons (PAHs) to construct curved π-surfaces and replacing the carbon atoms in carbonic PAHs with heteroatoms at the precise position to modulate electronic structures are regarded as two powerful functionalization strategies for exploring structure-dependent intriguing optoelectronic properties and potential synthetic applications in various curved nanographenes and nanotubes. , Among them, negatively curved polycyclic arenes fused with O- and S-containing heptagons have drawn scant attention so far compared to that with nitrogen-containing heptagons, probably due to the difference in structural diversity between the divalent oxygen and sulfur atoms compared to the trivalent nitrogen atom. In this context, we were interested in embedding heteroatom-containing heptagons into dibenzo[ g , p ]chrysene (DBC), an important class of PAHs with a large π-surface and a highly twisted geometry, to elucidate the structural conformation and optoelectronic properties of DBC-based polycyclic arenes, which have not been reported to date.…”

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confidence: 99%

Synthesis of Curved Polycyclic Arenes Embedded with Oxepine and Thiepine Using Ring Expansion Strategy

et al. 2023

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confidence: 99%

Synthesis of Curved Polycyclic Arenes Embedded with Oxepine and Thiepine Using Ring Expansion Strategy

et al. 2023

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“…[37] Very recently, this group introduced two additional heptagons into the molecular skeleton (Figure 1b). [38] Despite the swift development of N-doped polycyclic hydrocarbons in recent years, to the best of our knowledge, nanographenes bearing N-doped S-T-W defect have yet to be extensively investigated, and there is still a very large uncharted territory to be explored. [39] Here, using azulene and carbazole units as the starting building blocks, three novel saddle-shaped nanographenes (N-SW-1, N-SW-2 and N-SW-3, Figure 1c and Scheme 1) were successfully obtained through intramolecular direct arylation in solution.…”

Section: Introductionmentioning

confidence: 99%

Extension of Non‐alternant Nanographenes Containing Nitrogen‐Doped Stone‐Thrower‐Wales Defects

et al. 2023

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Non‐alternant topologies have attracted considerable attention due to their unique physiochemical characteristics in recent years. Here, three novel topological nanographenes molecular models of nitrogen‐doped Stone–Thrower–Wales (S–T–W) defects were achieved through intramolecular direct arylation. Their chemical structures were unambiguously elucidated by single‐crystal analysis. Among them, threefold intramolecular direct arylation compound (C42H21N) is the largest nanographene bearing a N‐doped non‐alternant topology to date, in which the non‐benzenoid rings account for 83 % of the total molecular skeleton. The absorption maxima of this compound was located in the near‐infrared region with a long tail up to 900 nm, which was much longer than those reported for similarly sized N‐doped nanographene with six‐membered rings (C40H15N). In addition, the electronic energy gaps of these series compounds clearly decreased with the introduction of non‐alternant topologies (from 2.27 eV to 1.50 eV). It is noteworthy that C42H21N possesses such a low energy gap (Egopt=1.40 eV; Egcv=1.50 eV), yet is highly stable under ambient conditions. Our work reported herein demonstrates that the non‐alternant topology could significantly influence the electronic configurations of nanocarbons, where the introduction of a non‐alternanting topology may be an effective way to narrow the energy gap without extending the molecular π‐conjugation.

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“…reported N‐doped bowl‐shaped nanographene 1 [10] (Figure 1a) bearing joined pentagons and heptagons, which was achieved through multiple arylation steps. Using the same strategy, they also prepared larger π‐conjugated nanographene 4 [11] with two more heptagons. Recently, Kivala et al.…”

Section: Introductionmentioning

confidence: 99%

Facile Synthesis of Nitrogen‐Doped Nanographenes with Joined Nonhexagons via a Ring Expansion Strategy

Luo

Liu

2023

Angew Chem Int Ed

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Synthetic methodology is considered a holy grail in both organic chemistry and materials science. Over the past few decades, researchers have explored graphene‐type molecules (or nanographenes) through classic Scholl oxidative cyclodehydrogenation. Despite the successes achieved with various nanographenes, the development of new methods to synthesize these highly desired molecules lags behind. Herein, we developed a facile and effective method to produce a series of nanographenes bearing nitrogen (N)‐doped pentagon‐heptagon pairs in acceptable yields. Modification of the heptagonal ring endowed the resultant nanographenes with tunable physicochemical properties; for instance, M9 exhibited both aggregation‐caused quenching and aggregation‐induced emission behavior. Most strikingly, novel nanographenes containing N‐doped pentagon‐octagon pairs were also obtained using the same synthetic strategy, demonstrating the superior versatility and efficiency of the proposed ring expansion method.

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Saddle-shaped aza-nanographene with multiple odd-membered rings

Abstract: A saddle-shaped aza-nanographene containing a central 1,4-dihydropyrrolo[3,2-b]pyrrole (DHPP) has been prepared via a rationally designed four-step synthetic pathway encompassing the intramolecular direct arylation, the Scholl reaction, and finally photo-induced radical...

Cited by 25 publications

References 83 publications

Synthesis of Curved Polycyclic Arenes Embedded with Oxepine and Thiepine Using Ring Expansion Strategy

Synthesis of Curved Polycyclic Arenes Embedded with Oxepine and Thiepine Using Ring Expansion Strategy

Extension of Non‐alternant Nanographenes Containing Nitrogen‐Doped Stone‐Thrower‐Wales Defects

Facile Synthesis of Nitrogen‐Doped Nanographenes with Joined Nonhexagons via a Ring Expansion Strategy

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