Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(1), P. 565 - 788

Published: Dec. 1, 2021

This review surveys recent progress in the chemistry of polycyclic heteroaromatic molecules with a focus on structural diversity and synthetic methodology. The article covers literature published during period 2016-2020, providing an update to our first this topic (

Language: Английский

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Intramolecular (directed) electrophilic C–H borylation

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(13), P. 4564 - 4591

Published: Jan. 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.

Language: Английский

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Organoboron molecules and polymers for organic solar cell applications

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 51(1), P. 153 - 187

Published: Dec. 1, 2021

This review summarizes the research progress in organoboron small molecules and polymers as photoactive materials for organic solar cells.

Language: Английский

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Multiple‐Resonance‐Induced Thermally Activated Delayed Fluorescence Materials Based on Indolo[3,2,1‐jk]carbazole with an Efficient Narrowband Pure‐Green Electroluminescence

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(41)

Published: Aug. 19, 2022

Herein, we report two multiple-resonance thermally activated delayed fluorescence emitters (VTCzBN and TCz-VTCzBN) based on indolo[3,2,1-jk]carbazole unit boron-nitrogen skeletons, whose emissions peaking at 496 521 nm with full width half maximum of 34 29 nm, respectively. Meanwhile, fast rate constants reverse intersystem crossing above 106 s-1 are obtained due to small singlet-triplet energy gaps large spin-orbital coupling values. Notably, planar molecular structures along the transition dipole moment direction endow them high horizontal emitting ratios up 94 %. Consequently, corresponding organic light-emitting diodes (OLEDs) show external quantum efficiencies 31.7 % 32.2 %, Particularly, OLED TCz-VTCzBN display ultra-pure green emission Commission Internationale de l'Eclairage coordinates (0.22, 0.71), consistent standard National Television System Committee.

Language: 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, Journal Year: 2021, Volume and Issue: 143(43), P. 18272 - 18279

Published: Oct. 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

Language: Английский

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Recent Research Progress of Organic Small‐Molecule Semiconductors with High Electron Mobilities

Advanced Materials, Journal Year: 2022, Volume and Issue: 35(11)

Published: Dec. 15, 2022

Organic electronics has made great progress in the past decades, which is inseparable from innovative development of organic electronic devices and diversity semiconductor materials. It worth mentioning that both these advances are inextricably linked to high-performance materials, especially representative n-type small-molecule materials with high electron mobilities. The small molecules have advantages simple synthesis process, strong intermolecular stacking, tunable molecular structure, easy functionalize structures. Furthermore, a remarkable important component for constructing complementary logic circuits p-n heterojunction Therefore, semiconductors play an extremely role field basis industrialization functional devices. This review focuses on modification strategies mobility at level, discusses detail applications field-effect transistors, light-emitting photodetectors, gas sensors.

Language: Английский

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Enhanced CO₂ Photoreduction through Spontaneous Charge Separation in End‐Capping Assembly of Heterostructured Covalent‐Organic Frameworks

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(50)

Published: Oct. 13, 2022

It is well known that charge separation crucial for efficient photocatalytic solar conversion. Although some covalent-organic frameworks (COFs) exhibit visible-light harvest, the large exciton binding energies reduce their efficiencies. Herein, we developed a novel method to post-treat olefin-linked COFs with end-capping polycyclic aromatic hydrocarbons (PAHs) spontaneous separation. Interestingly, type-II heterostructure constructed in our perylene-modified which displays drastically enhanced performance CO2 reduction, an efficiency of 8-fold higher than unmodified COF. A combination electrochemical, steady-state, and time-resolved spectroscopic measurements indicates such should be attributed photoinduced heterostructure. These results illustrate feasibility engineering charge-separation properties crystalline porous at molecular level artificial photosynthesis.

Language: Английский

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Boron-containing helicenes as new generation of chiral materials: opportunities and challenges of leaving the flatland

Chemical Science, Journal Year: 2024, Volume and Issue: 15(20), P. 7408 - 7440

Published: Jan. 1, 2024

Recent advances in synthesis have opened the way to a variety of boron helicenes. We highlight main achievements these chiral compounds and discuss their photophysical properties potential as functional materials.

Language: Английский

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Quadruply B←N-Fused Dibenzo-azaacene with High Electron Affinity and High Electron Mobility

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(42), P. 17015 - 17021

Published: Oct. 2, 2019

For many years, organoboron compounds have been expected to show excellent electron-injecting and -transporting properties. However, lowest unoccupied molecular orbital (LUMO) energy levels (ELUMO) of B-containing π-conjugated molecules are mostly higher than -4.0 eV their electron mobilities usually less 10-2 cm2 V-1 s-1. In this work, we experimentally prove the remarkably high affinity mobility compounds. Our strategy is incorporate multiple boron-nitrogen coordination bonds (B←N) into azaacenes. We synthesized quadruply B←N-fused dibenzo-azaacene (QBNA) through one-pot multifold borylation cyclization reaction. The incorporation four B←N units greatly changes electronic structures properties significantly downshifts QBNA. QBNA shows a ELUMO as low -4.58 eV, which among for n-type organic semiconductors. Single-crystal field-effect transistors display unipolar characteristic with an up 1.60 s-1 together ambient stability. This study thus provides design high-performance semiconductors electron-affinity π-systems based on chemistry.

Language: Английский

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Intramolecular Borylation via Sequential B−Mes Bond Cleavage for the Divergent Synthesis of B,N,B‐Doped Benzo[4]helicenes

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(8), P. 3156 - 3160

Published: Oct. 31, 2019

New symmetric and unsymmetric B,N,B-doped benzo[4]helicenes 3-6 a/b have been achieved in good yields, using a three-step process, starting from N(tolyl)3 highly divergent manner (7 examples). A borinic acid functionalized 1,4-B,N-anthracene 1 was found to display unprecedented reactivity, acting as convenient effective precursor for selective formation of bromo-substituted B,N,B-benzo[4]helicenes 2 a/2 b via intramolecular borylation sequential B-Mes bond cleavage the presence BBr3 . Subsequent reaction with Ar-Li provided toolbox preparation symmetrically/unsymmetrically B,N,B-helicenes. Their high photoluminescence quantum yields along small ΔEST suggest their potential thermally activated delayed fluorescence (TADF) emitters organic light-emitting diodes (OLEDs).

Language: Английский

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