Fully-fused boron-doped olympicenes: modular synthesis, tunable optoelectronic properties, and one-electron reduction

Guo, Jing; Zhang, Kaihua; Wang, Yanpei; Wei, Haipeng; Wang, Xiao; Yang, Kun; Zeng, Zebing

doi:10.1039/d3sc00342f

Cited by 9 publications

(5 citation statements)

References 70 publications

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“…In 2023, Zeng and coworkers reported the synthesis of fully fused 11aboraolympicene 15 a/15 b by treating alkyne 14 a/14 b with BBr 3 via a triply borylation-based double-fold borocyclization reaction. [41] 15 a/15 b displayed an excellent stability against air and moisture on account of the strong p-π conjugation between the vacant p z orbital of B atom and the adjacent πsystem even without the protecting group at boron site. Such high material stability together with the pedant bromo functionalities allows their further reaction with organotin reagents to generate alkyl or aryl-attached boraolympicene derivatives.…”

Section: Boron-containing Olympicenylsmentioning

confidence: 99%

“…Boron‐containing olympicene 13 exhibits good stability and can undergo Negishi coupling with aryl‐zinc reagent. In 2023, Zeng and coworkers reported the synthesis of fully fused 11a‐boraolympicene 15 a / 15 b by treating alkyne 14 a / 14 b with BBr 3 via a triply borylation‐based double‐fold borocyclization reaction [41] . 15 a / 15 b displayed an excellent stability against air and moisture on account of the strong p‐π conjugation between the vacant p z orbital of B atom and the adjacent π‐system even without the protecting group at boron site.…”

Section: Boron‐containing Olympicenylsmentioning

confidence: 99%

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The Olympicenyl Radical and Its Derivatives

Xiang,

Ye,

et al. 2023

ChemPlusChem

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The olympicenyl radical (OR) has long been a fascinating spin doublet hydrocarbon radical that evoked theoretical and experimental research interests, but the chemistry of olympicenyl was limited by its inherent instability. Recently, this field was revived by the advent of stable, multi‐substituted ORs and the isolation of them in the crystalline phase. In this minireview, we summarize the early studies on the pristine OR, as well as the recent advances on the substituted OR derivatives, heteroatom‐containing OR derivatives, and OR‐based diradicals and polyradicals. The synthetic chemistry, stabilization strategies, self‐association behaviors, reactivities, and applications in the biological field of the abovementioned compounds were discussed.

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Section: Boron-containing Olympicenylsmentioning

confidence: 99%

Section: Boron‐containing Olympicenylsmentioning

confidence: 99%

The Olympicenyl Radical and Its Derivatives

Xiang,

Ye,

et al. 2023

ChemPlusChem

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“…Notably, with the recent rise of graphene science, a revived interest in the construction of structurally well-defined polycyclic aromatic hydrocarbons (PAHs) has emerged owing to their crucial role as primary models in the bottom-up synthesis and interpretation of structure–property relationships for monodispersed (nano)graphene or graphene nanoribbons . Therefore, a myriad of PAHs featuring diverse molecular sizes, dimensionalities, edge topologies, heteroatom doping patterns, and nonhexagonal defective rings have been developed. − Nevertheless, owing to the elusive and often intricate synthesis processes, troubling solubility, and compromised stabilityparticularly evident at augmented aromatic dimensionsthe precise and efficient preparation of novel PAHs with bespoke structures remains a significant and formidable challenge at present. , …”

Section: Introductionmentioning

confidence: 99%

bay/ortho-Octa-substituted Perylene: A Versatile Building Block toward Novel Polycyclic (Hetero)Aromatic Hydrocarbons

Yang,

Li,

Huang

et al. 2024

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations * sı Supporting Information CONSPECTUS: Polycyclic (hetero)aromatic hydrocarbons (PAHs) have emerged as a focal point in current interdisciplinary research, spanning the realms of chemistry, physics, and materials science. Possessing distinctive optical, electronic, and magnetic properties, these π-functional materials exhibit significant potential across diverse applications, including molecular electronic devices, organic spintronics, and biomedical functions, among others. Despite the extensive documentation of various PAHs over the decades, the efficient and precise synthesis of π-extended PAHs remains a formidable challenge, hindering their broader application. This challenge is primarily attributed to the intricate and often elusive nature of their synthesis, compounded by issues related to low solubility and unfavored stability.The development of π-building blocks that can be facilely and modularly transformed into diverse π-frameworks constitutes a potent strategy for the creation of novel PAH materials. For instance, based on the classic perylene diimide (PDI) unit, researchers such as Wurthner, Wang, and Nuckolls have successfully synthesized a plethora of structurally diverse PAHs, as well as numerous other π-functional materials. However, until now the availability of such versatile building blocks is still severely limited, especially for those simultaneously having a facile preparation process, adequate solubilizing groups, favored material stability, and critically, rich possibilities for structural extension spaces.In this Account, we present an overview of our invention of a highly versatile bay-/ortho-octa-substituted perylene building block, designated as Per-4Br, for the construction of a series of novel PAH scaffolds with tailor-made structures and rich optoelectronic and magnetic properties. First, starting with a brief discussion of current challenges associated with the bottom-up synthesis of πextended PAHs, we rationalize the key features of Per-4Br that enable facile access to new PAH molecules including its ease of largescale preparation, favored material stability and solubility, and multiple flexible reaction sites, with a comparison to the PDI motif. Then, we showcase our rational design and sophisticated synthesis of a body of neutral or charged, closed-or open-shell, curved, or planar PAHs via controlled annulative π-extensions in different directions such as peripheral, diagonal, or multiple dimensions of the Per-4Br skeleton. In this part, the fundamental structure−property relationships between molecular conformations, electronic structures, and self-assembly behaviors of these PAHs and their unique physiochemical properties such as unusual open-shell ground states, global aromaticity, state-associated/stimuli-responsive magnetic activity, and charge transport characteristics will be emphatically elaborated. Finally, we offer our perspective on the continued advancement of π-functional materials based on Per-4Br, which, we posit, may stimula...

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“…The reaction involves the electrophilic borylation of alkyne-incorporated arenes with BX 3 , followed by intramolecular cyclization to form a boracycle. The remaining reactive haloborane moiety after one borylative cyclization facilitates continuous borylation . Accordingly, we envisioned that 9b-boraphenalene analogues can be synthesized from C 3 -symmetric compounds through C–B bond formation via triple intramolecular borylative cyclization.…”

Section: Introductionmentioning

confidence: 99%

π-Extended 9b-Boraphenalenes: Synthesis, Structure, and Physical Properties

Ikeno,

Hayakawa,

Sakai

et al. 2024

J. Am. Chem. Soc.

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Fully-fused boron-doped olympicenes: modular synthesis, tunable optoelectronic properties, and one-electron reduction

Abstract: We report here a novel family of boraolympicenes, structurally featured boron-doping at the concave 11a-positon of their π-skeletons and synthetically prepared via a facile one-pot triply borylation-based double-fold borocyclization reaction....

Cited by 9 publications

References 70 publications

The Olympicenyl Radical and Its Derivatives

The Olympicenyl Radical and Its Derivatives

bay/ortho-Octa-substituted Perylene: A Versatile Building Block toward Novel Polycyclic (Hetero)Aromatic Hydrocarbons

π-Extended 9b-Boraphenalenes: Synthesis, Structure, and Physical Properties

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