Heteroatom-Doped Nanographenes with Structural Precision

Accounts of Chemical Research, Год журнала: 2019, Номер 52(9), С. 2491 - 2505

Опубликована: Сен. 3, 2019

Nanographenes, which are defined as nanoscale (1-100 nm) graphene cutouts, include quasi-one-dimensional nanoribbons (GNRs) and quasi-zero-dimensional quantum dots (GQDs). Polycyclic aromatic hydrocarbons (PAHs) larger than 1 nm can be viewed GQDs with atomically precise molecular structures thus termed nanographene molecules. As a result of confinement, nanographenes promising for next-generation semiconductor applications finite band gaps, significant advantage compared gapless two-dimensional graphene. Similar to the atomic doping strategy in inorganic semiconductors, incorporation heteroatoms into is viable way tune their optical, electronic, catalytic, magnetic properties. Such properties highly dependent not only on size edge structure but also heteroatom type, position, concentration. Therefore, reliable synthetic methods required precisely control these structural features. In this regard, bottom-up organic synthesis provides an indispensable achieve structurally well-defined heteroatom-doped nanographenes. heteroaromatic compounds have attracted great attention chemists decades. Research direction has been further promoted by modern interest supramolecular chemistry electronics. The rise 21st century endowed large polycyclic new role model systems Heteroatom-doped molecules own right materials photonic, optoelectronic, spintronic because extended π conjugation. Despite advances compounds, sizes over relevant GNRs still scarce. Account, we describe nanographenes, mainly summarizing our group past decade. We first present several examples based prototypical molecule, i.e., hexa-peri-hexabenzocoronene (HBC), including nitrogen-doped HBC analogues formal replacement benzene other heterocycles (e.g., pyrimidine pyrrole antiaromatic pyrazine) sulfur-doped via thiophene annulation. then introduce zigzag edges variety zigzag-edged incorporating nitrogen, boron, oxygen atoms. finally summarize success cases. hope that Account will stimulate combined effort from different disciplines.

Язык: Английский

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Advances in carbon dots: from the perspective of traditional quantum dots

Materials Chemistry Frontiers, Год журнала: 2020, Номер 4(6), С. 1586 - 1613

Опубликована: Янв. 1, 2020

A brief review of CDots from the perspective traditional QDs clarifies basic concepts, unique characteristics and challenges.

Язык: Английский

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Top-down synthesis of graphene: A comprehensive review

FlatChem, Год журнала: 2021, Номер 27, С. 100224 - 100224

Опубликована: Фев. 8, 2021

Язык: Английский

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Azulene-Based π-Functional Materials: Design, Synthesis, and Applications

Accounts of Chemical Research, Год журнала: 2021, Номер 54(7), С. 1737 - 1753

Опубликована: Март 11, 2021

ConspectusAzulene, an isomer of naphthalene, is a molecule historical interest for its unusual photophysical properties, including beautiful blue color derived from the narrow HOMO–LUMO energy gap and anti-Kasha fluorescence S2 to S0. More recently, it has attracted increasing attention novel electronic structure, electron-rich five-membered ring electron-deficient seven-membered with dipole moment 1.08 D resulting resonance delocalization, different reactivities at odd even positions, stimuli-responsive behavior. As key building block, azulene been used in various fields because unique physicochemical properties. Recent studies have demonstrated great potential constructing advanced organic materials. However, exploring azulene-based materials long hindered by challenges molecular design synthesis. Most reported unit incorporated through or ring. Creating blocks optoelectronics using 2,6-connected units construct conjugated polymers that can adequately utilize "donor–acceptor" structure remained underexplored before our contributions. Besides, most azulene-fused polycyclic aromatic hydrocarbons (PAHs) heteroaromatics, substructures were created during later synthesis stages, use derivatives as starting synthesize PAHs heteroaromatics intelligently still limited.In this Account, we summarize efforts on design, synthesis, applications π-functional Our start creation π-conjugated structures based azulene. The strategy, optoelectronic performance first class diimides, 2,2′-biazulene-1,1′,3,3′-tetracarboxylic diimide (BAzDI) π-extended π-bridged derivatives, are presented. Notably, antiparallel stacking between adjacent azulene's was observed single crystals BAzDI derivatives. developed isoindigo analogue, azulenoisoindigo, which combines merits both azulene, reversible redox behavior proton responsiveness. Then discuss contributions 2,6-azulene-based polymers. By incorporation into polymeric backbone, two high field-effect transistor (OFET) developed. Two responsiveness electrical conductivity upon protonation also provided. We recent heteroaromatics. BN-heteroaromatics designed synthesized, they exhibited selective response fluoride ion unexpected deboronization addition trifluoroacetic acid. An azulene–pyridine-fused (Az-Py) reductive cyclization 1-nitroazulenes OFET Az-Py-1 included. Afterward, several examples azulene-capped molecules. molecules capped favor hole transport, whereas ones electron transport.

Язык: Английский

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Intramolecular (directed) electrophilic C–H borylation

Chemical Society Reviews, Год журнала: 2020, Номер 49(13), С. 4564 - 4591

Опубликована: Янв. 1, 2020

The intramolecular C-H borylation of (hetero)arenes and alkenes using electrophilic boranes is a powerful transition metal free methodology for forming C-B bonds. These reactions are preceded by intermolecular bond (both dative covalent) formation, with examples proceeding via initial N-B formation dominating this field thus both discussed in depth herein. Less prevalent that proceed O-B, S-B P-B also summarised. Mechanistic studies presented reveal two mechanisms borylation, (i) aromatic substitution (prevalent B-X electrophiles); (ii) σ-bond metathesis mediated B-H B-R electrophiles). To date, utilised mainly accessing boron containing conjugated organic materials, however recent developments, summarized herein alongside early studies, have highlighted the applicability synthetically versatile organo-boronate esters bioactives. multitude synthetic procedures reported contain many common features enables key requirements successful factors effecting regioselectivity substrate scope to be identified, summarized.

Язык: Английский

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Amplification of Dissymmetry Factors in π-Extended [7]- and [9]Helicenes

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(12), С. 4661 - 4667

Опубликована: Март 18, 2021

π-Extended helicenes constitute an important class of polycyclic aromatic hydrocarbons with intrinsic chirality. Herein, we report the syntheses π-extended [7]helicene 4 and [9]helicene 6 through regioselective cyclodehydrogenation in high yields, where a "prefusion" strategy plays key role preventing undesirable aryl rearrangements. The unique helical structures are unambiguously confirmed by X-ray crystal structure analysis. Compared to parent pristine [9]helicene, these novel display significantly improved photophysical properties, quantum yield 0.41 for 6. After optical resolution chiral high-performance liquid chromatography, chiroptical properties enantiomers 4-P/M 6-P/M investigated, revealing that small variation length from [7] [9] can cause approximately 10-fold increase dissymmetry factors. circularly polarized luminescence brightness reaches 12.6 M–1 cm–1 as one highest among carbohelicenes.

Язык: Английский

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Boron-Containing Organic Diradicaloids: Dynamically Modulating Singlet Diradical Character by Lewis Acid–Base Coordination

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(43), С. 18272 - 18279

Опубликована: Окт. 19, 2021

Organic diradicaloids have unique open-shell structures and properties promising applications in organic electronics spintronics. Incorporation of heteroatoms is an effective strategy to alter the electronic diradicaloids. However, B-containing are very challenging due their high reactivities, which caused by not only diradical nature but also B atom. In this article, we report a new kind containing boron atoms. Our incorporate planarized triarylboranes antiaromatic polycyclic hydrocarbons (PHs). We synthesized two isomeric PHs composed indenofluorene π-skeletons dioxa-bridged triphenylborane moieties. As proved theoretical experimental results, both them excellent ambient stability singlet structures, as well intriguing magnetic optoelectronic properties, such thermally accessible triplet species, reversible multiredox ability, narrow energy gaps. Notably, they possess sufficient Lewis acidity, has never been observed for addition, can coordinate with bases form adducts, achieving unprecedented dynamic modulations (anti)aromaticity thus character

Язык: Английский

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Molecular Carbon Imides

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(33), С. 14976 - 14991

Опубликована: Июль 29, 2022

The creation and development of new forms nanocarbons have fundamentally transformed the scientific landscape in past three decades. As members nanocarbon family with accurate size, shape, edge structure, molecular carbon imides (MCIs) shown unexpected unique properties. Particularly, imide functionalization strategy has endowed these rylene-based carbons fascinating characteristics involving flexible syntheses, tailor-made structures, diverse properties, excellent processability, good stability. This Perspective elaborates design evolution to functional landscapes, illustrative examples are given, including a promising library multi-size multi-dimensional MCIs rigidly conjugated π-architectures, ranging from 1D nanoribbon 2D nanographene cross-dimensional MCIs. Although researchers achieved substantial progress using as components for exploration charge transport, photoelectric conversion, chiral luminescence performances, they far unleashing their full potential. Developing highly efficient regioselective coupling/ring-closure reactions formation multiple C–C bonds annulation electron-deficient aromatic units is crucial. Prediction by theory help machine learning artificial intelligence research along reliable nanotechnology characterization will give an impetus blossom related fields. Future investigations also advance toward─or even focus on─the emerging potential functions, especially fields electronics spin electronics, which expected open avenues.

Язык: Английский

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The Rise of 1,4‐BN‐Heteroarenes: Synthesis, Properties, and Applications

Advanced Science, Год журнала: 2022, Номер 9(19)

Опубликована: Апрель 14, 2022

BN-heteroarenes, which employ both boron and nitrogen in aromatic hydrocarbons, have gained great attention the fields of organic chemistry materials science. Nevertheless, extensive studies on BN-heteroarenes are largely limited to 1,2-azaborine-based compounds with B-N covalent bonds, whereas 1,3- 1,4-BN-heteroarenes relatively rare due their greater challenge synthesis. Recently, significant progresses been achieved synthesis applications featuring 1,4-azaborines, especially driven by potential as multiresonant thermally activated delayed fluorescence (MR-TADF) materials. Therefore, it is timely review these advances from perspective. This summarizes synthetic methods recent achievements 1,4-azaborine-based discusses unique properties this emerging class materials, highlighting value beyond MR-TADF It hoped that would stimulate conversation cooperation between chemists who interested azaborine scientists working optoelectronics, metal catalysis, carbon-based nanoscience etc.

Язык: Английский

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Sustainable carbon sources for green laser-induced graphene: A perspective on fundamental principles, applications, and challenges

Applied Physics Reviews, Год журнала: 2022, Номер 9(4)

Опубликована: Ноя. 10, 2022

Since the discovery of laser-induced graphene (LIG), significant advances have been made to obtain green LIG (gLIG) from abundant, eco-friendly, natural, and organic renewable bio-based carbon sources. Recently, some sustainable cost-effective electronic devices designed with gLIG, resulting in diverse solutions environmental impact caused by waste (e-waste). However, there are still several challenges that must be addressed regarding widespread market implementation gLIG-based products, synthesis practical applications. In this review, we focus on precursor sources, their conversion mechanisms, physical chemical properties applications, along related its implementation, showing future opportunities perspectives promising new material. Various systems based gLIG for energy storage, electrocatalysis, water treatment, sensors reported literature. Additionally, has proposed ink formulation or incorporation into polymer matrices, further expand use non-carbon-based substrates applications which pristine cannot directly used. way, it is possible apply substrates, aiming at emerging wearable edible electronics. Thus, review will bring an overview developments, accordance European Green Deal, United Nations Sustainable Development Goals era internet-of-things, demands components principles efficiency production methods.

Язык: Английский

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