Nonplanar Nanographene: A Hydrocarbon Hole‐Transporting Material That Competes with Triarylamines DOI Open Access

Yuta Morinaka,

Hideto Ito, Kazuhiro J. Fujimoto

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(44)

Published: Aug. 13, 2024

Abstract Hole‐transporting materials (HTMs) are essential for optoelectronic devices, such as organic light‐emitting diodes (OLEDs), dye‐sensitized solar cells, and perovskite cells. Triarylamines have been employed HTMs since they were introduced in 1987. However, heteroatoms or side chains embedded the core skeleton of triarylamines can cause thermal chemical stability problems. Herein, we report that hexabenzo[ a , c fg j l op ]tetracene (HBT), small nonplanar nanographene, functions hydrocarbon HTM with hole transport properties match those triarylamine‐based HTMs. X‐ray structural analysis theoretical calculations revealed effective multidirectional orbital interactions transfer integrals HBT. In‐depth experimental analyses nonplanarity‐inducing annulative π‐extension achieve not only stable amorphous state bulk films, but also higher increase highest occupied molecular level than conventional linear cyclic π‐extension. Furthermore, an in‐house manufactured HBT‐based OLED exhibited excellent performance, featuring superior curves current density–voltage, external quantum efficiency–luminance, lifetime compared to representative OLEDs. A notable improvement device was observed OLED, highlighting advantages HTM. This study demonstrates immense potential nanographenes applications.

Language: Английский

Synthesis of Chrysene-Based Nanographenes by a Successive APEX Reaction DOI Creative Commons

Yuichi Nakashige,

Hidefumi Nakatsuji,

Kaho Matsushima

et al.

Precision Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 18, 2025

Language: Английский

Citations

0
Enantiomer-enriched π-Extended Helicenes with a Perylene Core from Binaphthol: Axial-to-Helical Chirality Transfer with Stepwise Scholl Reaction Mechanism DOI Creative Commons

Zhi‐Ao Li,

Kelin Zhu, Nai‐Te Yao

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Axially chiral substrates were transformed into enantiomer-enriched π-extended helicenes via a chiral-transfer-based Scholl reaction, and enantiomers efficiently separated without labor-intensive high-performance liquid chromatography (HPLC).

Language: Английский

Citations

0
Mechanochemical Coupling of Alkylsilanes to Nanoparticles for Solvent-Free and Rapid Fabrication of Superhydrophobic Materials DOI Creative Commons
Nusret Çelik, Berk Sezen, Furkan Şahin

et al.

ACS Applied Nano Materials, Journal Year: 2023, Volume and Issue: 6(16), P. 14921 - 14930

Published: Aug. 9, 2023

Excellent repellency toward water is one of the main characteristics superhydrophobic coatings that endow application potential in various areas. However, complex and time-consuming process involved preparing universally applicable coatings, especially step involves modifying intrinsically hydrophilic inorganic oxide nanoparticles with hydrophobic alkylsilanes, limits their practical applications. This study demonstrates a rapid eco-friendly approach to surfaces by chemically grafting alkylsilane molecules onto silica using mechanochemical process. The key advantages this are (i) preparation times orders magnitude shorter than those conventional methods, (ii) zero-solvent usage, (iii) overcoming need for tedious separation drying steps. resultant surface exhibits superhydrophobicity contact angle 172° sliding 1°. A monolith prepared compressing powder superhydrophobicity, durability, antifouling ability against urine. inhibits growth two most common pathogenic bacteria. bacterial was reduced 107.07 Escherichia coli 105.78 Staphylococcus aureus. proposed practical, swift, cost-effective, making it scalable technique solvent-free surfaces.

Language: Английский

Citations

8
Mechanochemical synthesis of corannulene flanked N‐heterocyclic carbene (NHC) precursors and preparation of their metal complexes DOI Creative Commons

Gavin Hum,

Ezzah M. Muzammil,

Yongxin Li

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 20, 2024

The synthesis of new compounds is an important pillar for the advancement field chemistry and adjacent fields. In this regard, over last decades huge efforts have been made to not only develop molecular entities but also more efficient sustainable synthetic methodologies due increasing concerns environmental sustainability. context, we developed routes novel corannulene flanked imidazolium bromide NHC precursors both in solid-state solution phases. Our work presents a comprehensive comparative study mechanochemical conventional solution-based methods. Green metrics energy consumption comparison were performed revealing ball-milling generation these be environmentally greener technique produce such compared solvent-based addition, demonstrated proof-of-concept herein reported NHCs robust ligands transition metals their ligand substitution reactions.

Language: Английский

Citations

2
Nonplanar Nanographene: A Hydrocarbon Hole‐Transporting Material That Competes with Triarylamines DOI

Yuta Morinaka,

Hideto Ito, Kazuhiro J. Fujimoto

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: Aug. 13, 2024

Hole-transporting materials (HTMs) are essential for optoelectronic devices, such as organic light-emitting diodes (OLEDs), dye-sensitized solar cells, and perovskite cells. Triarylamines have been employed HTMs since they were introduced in 1987. However, heteroatoms or side chains embedded the core skeleton of triarylamines can cause thermal chemical stability problems. Herein, we report that hexabenzo[a,c,fg,j,l,op]tetracene (HBT), a small nonplanar nanographene, functions hydrocarbon HTM with hole transport properties match those triarylamine-based HTMs. X-ray structural analysis theoretical calculations revealed effective multidirectional orbital interactions transfer integrals HBT. In-depth experimental analyses nonplanarity-inducing annulative π-extension achieve not only stable amorphous state bulk films, but also higher increase highest occupied molecular level than conventional linear cyclic π-extension. Furthermore, an in-house manufactured HBT-based OLED exhibited excellent performance, featuring superior curves current density-voltage, external quantum efficiency-luminance, lifetime compared to representative OLEDs. A notable improvement device was observed OLED, highlighting advantages HTM. This study demonstrates immense potential nanographenes applications.

Language: Английский

Citations

2
Birch Reductive Arylation by Mechanochemical Anionic Activation of Polycyclic Aromatic Compounds DOI Creative Commons
Yoshifumi Toyama, Akiko Yagi, Kenichiro Itami

et al.

Published: Aug. 30, 2024

Birch reduction is a well-known process for producing aromatic compounds. The of rings using alkali metals produces anionic species that react with protons or electrophiles. However, this reaction generally accompanied by signifi-cant restrictions on the available substrates because only alkyl halides are in most cases. For example, reduction/transformation reactions related to alkylation compounds, whereas other elec-trophiles rare and have not yet been completely established. In particular, arylation unfunctionalized polycyclic ar-omatic hydrocarbons (PAHs), so-called reductive has investigated. Herein, we report re-ductive first time mechanochemical activation lithium(0) wire followed addition vari-ous fluoroarenes. Specifically, found products but also formal C–H were obtained from PAHs, achieving one-pot fissure-region annulative π-extension give nanogra-phenes. This newly unique rarely achieved solution, showed interesting reactivity metal lithium organofluorine compounds solid state.

Language: Английский

Citations

2
Mechanochemical Scholl Reaction on Phenylated Cyclopentadiene Core: One‐Step Synthesis of Fluoreno[5]helicenes DOI
Gábor Báti, Dániel Csókás, Mihaiela C. Stuparu

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(1)

Published: Oct. 23, 2023

In this study, we explore feasibility of the mechanochemical approach in synthesis tetrabenzofluorenes (fluoreno[5]helicenes). For this, commercially available phenylated cyclopentadiene precursors are subjected to Scholl reaction solid state using FeCl

Language: Английский

Citations

4
Mechanochemical Birch Reduction with Low Reactive Alkaline Earth Metals DOI
Jagadeesh Varma Nallaparaju,

Riin Satsi,

Danylo Merzhyievskyi

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(20)

Published: March 4, 2024

Abstract Birch reduction and similar dissolved metal‐type transformations hold significant importance in the organic synthesis toolbox. Historically, field has been dominated by alkali metal reductants. In this study, we report that largely neglected, low‐reactive alkaline earth metals can become powerful affordable reductants when used a ball mill under essentially solvent‐free conditions, presence of ethylenediamine THF as liquid additives. Calcium reduce both electron‐deficient electron‐rich arenes, with yields products to those obtained lithium metal. Magnesium reveals enhanced reducing power, enabling benzoic acids while keeping aromatic moieties intact allows for chemoselective transformations. The developed mechanochemical approach uses readily available safer‐to‐handle metals, operates air ambient temperature be gram‐scale preparations. Finally, demonstrate conditions other reductive transformations, including amination, deoxygenation, dehalogenation, alkene alkyne reductions.

Language: Английский

Citations

1
Mechanochemical Mitsunobu Reactions DOI Creative Commons

Matthew T. J. Williams,

Laura Adarve-Cardona, Carsten Bolm

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(10), P. 2220 - 2225

Published: March 22, 2024

Abstract A Mitsunobu process performed under neat grinding conditions, using a mixer mill, is reported. It proceeds in the absence of reaction solvent and short reactions times (10–20 min). broad substrate scope encompassing primary secondary alcohols, as well oxygen, nitrogen, sulfur, carbon‐centered nucleophiles demonstrated. Application to functionalization selection APIs shown, also. The developed amenable scale up on planetary ball‐mill, yielding over 2 grams product. Finally, representative alcohol inverted with excellent stereoselectivity.

Language: Английский

Citations

1
Luminescent Chiral Furanol‐PAHs via Straightforward Ni‐Catalysed Csp2−F Functionalization: Mechanistic Insights into the Scholl Reaction DOI Creative Commons
Judith Sala, Lorena Capdevila, Cristina Berga

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(5)

Published: Oct. 30, 2023

Abstract Here we report the stepwise synthesis of new nanographenes (NGs) and polycyclic aromatic hydrocarbons (PAHs) obtained via Scholl ring fusion applied at homologation compounds, which are through one‐step Ni‐catalysed C sp2 −F functionalization. The latter rapidly accessed valid precursors for reaction, screening experimental conditions allowed us to describe first time furanol‐bearing PAHs. Mechanistic insights by DFT rationalize formation furanol PAHs under moderately acidic conditions. All NGs synthesized show moderate/weak fluorescent properties, all crystallized some degree curvature as racemic mixtures. Enantiomeric separation chiral HPLC one PAH study their chiroptical CD properties.

Language: Английский

Citations

2