Organic & Biomolecular Chemistry, Год журнала: 2024, Номер unknown
Опубликована: Ноя. 26, 2024
Herein, we report a novel Schiff base macrocyclic receptor which was characterized by NMR, UV–vis and fluorescence spectroscopy, revealing it rigid preorganized planar π-conjugated fluorescent macrocycle showing anion binding properties.
Язык: Английский
Journal of the American Chemical Society, Год журнала: 2025, Номер unknown
Опубликована: Фев. 26, 2025
Cycloarenes and heterocycloarenes, characterized by fused macrocyclic π-conjugated structures, hold significant promise in synthetic chemistry materials science. However, their further development remains constrained formidable challenges, particularly for those with contracted cavities. Inspired advances the synthesis of organoboron-based multiresonance thermally activated delayed fluorescence (TADF) emitters, we herein report convenient access detailed characterization a 1,4-azaborine-embedded cycloarene that features smallest cavity among known (hetero)cycloarenes. The induces bowl-shaped molecular geometry, as confirmed crystallographic analysis, while also triggering through-space conjugation delocalized π-electrons at site. Comparative studies between this compound its helical analogue reveal substantial topological impact on photophysical properties, including bathochromic-shifted broadened emission band, prolonged radiative decay process, more efficient triplet-to-singlet spin-flip. Capitalizing TADF remarkably high quantum yield, successfully fabricated first (hetero)cycloarene-based organic light-emitting diodes, achieving over 30% external efficiency minimal roll-off. These findings offer new insights into design topologically distinct compounds unique properties.
Язык: Английский
Процитировано
2
Small, Год журнала: 2025, Номер unknown
Опубликована: Март 5, 2025
The recovery of radioactive iodine from nuclear waste and contaminated water sources is a critical environmental concern, which poses significant technical challenges. Herein, the study has demonstrated that tuning electronic properties diketopyrrolopyrrole-based donor-acceptor covalent organic frameworks (COFs) enhances trapping, improves charge transport, strengthens interactions - establishing structure-property relationship. This achieved by synthesizing COFs with linker 3,6-bis(4-(1,3-dioxolan-2-yl)phenyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (DKP) in combination either electron acceptor 4,4',4″-(1,3,5-triazine-2,4,6-triyl)trianiline (TTT-DKP) or donor N1,N1-bis(4-aminophenyl)benzene-1,4-diamine (TAPA-DKP) linkers. These COFs, abundant sorption sites, thermal chemical stability, optimized pore environments, efficiently bind vapor solution phases. TAPA-DKP COF, containing electron-donating moieties, showed high uptake 3.52 g/g, exceeding 2.81 g/g electron-deficient TTT-DKP phase, both following pseudo-second-order kinetics. Density functional theory (DFT) calculations reveal adsorption sites showing COF binds I2 more effectively via its electron-rich highlighting role property modulation adsorption.
Язык: Английский
Процитировано
2
Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown
Опубликована: Март 5, 2025
Nanographenes, known for their exceptional optoelectronic properties, have garnered significant interest tunable electronic structures, particularly through heteroatom doping. Herein, we report the synthesis of two twisted hetero-nanographenes (h-NGs) co-doped with nitrogen and oxygen via a three-step strategy, where tandem Pictet-Spengler cyclization ipso-aromatic substitution serve as key step. Both h-NGs incorporate unique bis-fused diazacoronene (BFDAC) core, one further extending π-system peri-fusion four benzopyran units. Single-crystal analyses reveal that BFDAC core both adopts highly geometry, whereas benzopyran-fused has enhanced rigidity. Theoretical studies confirm global aromaticity 30 π-electrons delocalized along periphery. Notably, co-doping enables precise tuning, pyridinic lowering LUMO level raising HOMO level. display red photoluminescence (PL), derivative exhibits an ultra-narrow emission full-width at half-maximum 19 nm, among narrowest reported organic red-emitting materials. exhibit acid-responsive optical behavior including near-infrared absorption shift PL quenching, providing additional functional versatility.
Язык: Английский
Процитировано
1
Angewandte Chemie, Год журнала: 2025, Номер unknown
Опубликована: Март 5, 2025
Abstract Nanographenes, known for their exceptional optoelectronic properties, have garnered significant interest tunable electronic structures, particularly through heteroatom doping. Herein, we report the synthesis of two twisted hetero‐nanographenes (h‐NGs) co‐doped with nitrogen and oxygen via a three‐step strategy, where tandem Pictet‐Spengler cyclization ipso ‐aromatic substitution serve as key step. Both h‐NGs incorporate unique bis‐fused diazacoronene (BFDAC) core, one further extending π‐system peri‐fusion four benzopyran units. Single‐crystal analyses reveal that BFDAC core both adopts highly geometry, whereas benzopyran‐fused has enhanced rigidity. Theoretical studies confirm global aromaticity 30 π‐electrons delocalized along periphery. Notably, co‐doping enables precise tuning, pyridinic lowering LUMO level raising HOMO level. display red photoluminescence (PL), derivative exhibits an ultra‐narrow emission full‐width at half‐maximum 19 nm, among narrowest reported organic red‐emitting materials. exhibit acid‐responsive optical behavior including near‐infrared absorption shift PL quenching, providing additional functional versatility.
Язык: Английский
Процитировано
0
Small, Год журнала: 2025, Номер unknown
Опубликована: Март 25, 2025
Stimulus-responsive covalent organic frameworks (COFs) own color-switching characteristics when exposed to external stimuli. However, the investigations on multiple solvent-responsive COFs remain a challenge due synthetic difficulties and uncontrollable charge transfer process toward various solvents. In this contribution, two novel isomeric with regulated intramolecular (ICT) by modulating distance between donor/acceptor linkage are synthesized. The as-prepared exhibited significantly distinct solvatochromic behaviors in water, acid, halogenated solvents, respectively. These functions attributed enhancement degrees of ICT hydrogen bond interactions, protonation halogen/π addition, employed as stimulation-responsive powder or ink, displaying excellent image data encryption performances. work can not only offer viewpoint for creation but also expand COFs' potential applications information anti-counterfeiting.
Язык: Английский
Процитировано
0
Accounts of Materials Research, Год журнала: 2025, Номер unknown
Опубликована: Март 27, 2025
Язык: Английский
Процитировано
0
Chemistry - An Asian Journal, Год журнала: 2025, Номер unknown
Опубликована: Май 22, 2025
Abstract Kekulene and expanded kekulenes are rigid, nearly planar cycloarenes with potential optoelectronic applications. However, their highly symmetric structures localized aromaticity typically result in low photoluminescence quantum yield (PLQY). Here, we incorporate a perylene unit into the kekulene framework synthesize π‐extended derivative ( 1 ) via macrocy‐clization using Suzuki coupling, followed by bismuth(III) triflate‐catalyzed cyclization of vinyl ethers. X‐ray crystallography reveals slightly distorted extended backbone, while peripheral aryl substituents effectively suppress intermolecular π–π stacking. Notably, retains frontier molecular orbital characteristics exhibits high oscillator strengths for electronic transitions, achieving PLQY up to 60% solution.
Язык: Английский
Процитировано
0
Organic & Biomolecular Chemistry, Год журнала: 2024, Номер unknown
Опубликована: Ноя. 26, 2024
Herein, we report a novel Schiff base macrocyclic receptor which was characterized by NMR, UV–vis and fluorescence spectroscopy, revealing it rigid preorganized planar π-conjugated fluorescent macrocycle showing anion binding properties.
Язык: Английский
Процитировано
0