Optimal Synergy between Azulenes and Acenes in Azuacenes with 6-7-5 Ring Topology

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 7, 2025

Azuacenes, defined as azulene fused with acenes in a 6-7-5 ring topology and spanning lengths from 3 to 6 rings, have been synthesized using new skeleton editing [3 + 2] annulation synthesis protocol distinction regarding the procedures obtain 6-5-7 isomers. Comprehensive studies on ground-state excited-state spectroscopy, electrochemical properties, chemical stability, solid-state structure conducted compare these azuacenes acenes. For same number of we found that improve stability (i.e., smaller diradical character) their photophysical properties anti-Kasha emissions modulation energy strength visible bands) but they reduce transport features compared those Compared azulene, performance terms electrical properties. Overall, fusion known polycyclic compounds, such acene produces isomeric hybrid compounds enhanced Here, resulting turn out conserve most unique two building blocks associate facility π-delocalization positive charge zwitterion over fragment.

Language: Английский

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Perylene with Split‐Azulene Embedding

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(41)

Published: July 10, 2024

Splitting the five and seven-membered rings of azulene embedding them separately into a conjugated backbone provides azulene-like polycyclic aromatic hydrocarbons (PAHs), which are great interest in quantum material chemistry. However, synthetic accessibility poses significant challenge. In this study, we present synthesis novel PAH, Pery-57, can be viewed as integration perylene framework split azulene. The compact structure Pery-57 displays several intriguing characteristics, including NIR II absorption at 1200 nm, substantial dipole moment 3.5 D, head-to-tail alternating columnar packing. Furthermore, exhibits remarkable redox properties. cationic radical Pery-57⋅

Language: Английский

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Phenylenediamine-Linked, Folded Nanographene Dimers: Access to Structure-Dependent Redox Capability

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 19, 2025

Polycyclic aromatic hydrocarbons (PAHs) with open-shell or redox characteristics are highly desirable due to their intriguing electronic properties and potential applications. Here, we demonstrate a series of phenylenediamine-linked nanographenes (NGs) 1–3 by connecting two aza-hexa-peri-hexabenzocoronene (HBC) units p-phenylene, p,p'-biphenylene, p,p"-terphenylene, respectively, unveil 3D conformations, structures, properties. As proved X-ray crystallographic analysis quantum chemical calculation, adopted anti-folded, Z-shaped structures rotatable single bonds. The structure-dependent capabilities were disclosed. For 1, stable monoradical cation was generated one-electron oxidation as the terminal product. revealed an unprecedented syn-folded structure 1+. However, 2 3 demonstrated redox-active molecules from neutral dication that each oxidative state can be precisely controlled oxidation/reduction.

Language: Английский

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Chiral nanographenes exhibiting circularly polarized luminescence

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Chiral nanographenes: molecular architecture, key constituents, and their circularly polarized luminescence.

Language: Английский

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Synthesis and Characterization of Cycloocta[1,2-a:6,5-a′]diindene as an Octagon-Containing Nonalternant Isomer of Pentacyclic Benzenoid Aromatic Hydrocarbons with Hidden Diradical Character That Induces Dimerization

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 12, 2025

Recently, the interest in nonbenzenoid hydrocarbons has resurged, focusing on replacement of two benzenoid hexagons with a pentagon/heptagon pair, which led to abundant azulenoid hydrocarbons. For ortho-fused three or more rings, replacing set pentagons and one octagon is also possible. Following this concept, we designed pentacyclic cyclooctadiindenes 4 5 5-8-5 tricyclic skeleton. Although pronounced open-shell nature hampered its synthesis, five examples were synthesized characterized as stable closed-shell molecules. A thin film 5a exhibited p-type transistor behavior hole mobility 0.63 × 10-2 cm2/(V·s). Optoelectronic measurements clearly showed nonalternant character 5. Heating photoirradiation solution afforded formal [6 + 4] cycloadduct. Theoretical calculations mechanistic investigations revealed occurrence stepwise formation C-C bonds, hidden emerges molecules close contact. Notably, dimeric π-complex 5·5, alleviated. The increased spatial overlap frontier orbitals reduction energy gap facilitate diradical-based bond formations. Our results demonstrate that electronic structures π-stacked compound can be tuned even for monomer compounds negligible character. This study will contribute establishing design strategies novel functional molecular materials based condensed state.

Language: Английский

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In-Column Click Chemistry for the Preparation of Chromatographic Stationary Phase Materials and Online Evaluation of the Reaction by Chromatographic Behaviors

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

Published: May 29, 2025

Traditional chromatographic stationary phases are usually prepared in a round-bottom flask, which has some shortcomings such as complicated operation, poor flexibility, and environmental pollution, the extent of reaction time cannot be tracked. Here, we adhered to concept green chemistry innovatively designed flow-through modification program using column microreactor. Allyltrimethoxysilane-functionalized silica (Sil-ATS) (3-mercaptopropyl)trimethoxysilane-functionalized (Sil-MPS) materials were characterized by Fourier transform infrared spectrometry, scanning electron microscopy, elemental analysis, thermogravimetric analysis. In-column "click chemistry" was then used modify functional groups on Sil-ATS Sil-MPS prepare columns. The relationship between researched resolution toluene pentylbenzene. optimum reactive chosen different Chromatographic behaviors various compounds directly compared columns before after in-column reaction. results indicated that mini first perform enlarged synthetic device. In addition, method evaluate reactions micron-sized phase online time.

Language: Английский

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Perylene with Split‐Azulene Embedding

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(41)

Published: July 10, 2024

Abstract Splitting the five and seven‐membered rings of azulene embedding them separately into a conjugated backbone provides azulene‐like polycyclic aromatic hydrocarbons (PAHs), which are great interest in quantum material chemistry. However, synthetic accessibility poses significant challenge. In this study, we present synthesis novel PAH, Pery‐57 , can be viewed as integration perylene framework split azulene. The compact structure displays several intriguing characteristics, including NIR II absorption at 1200 nm, substantial dipole moment 3.5 D, head‐to‐tail alternating columnar packing. Furthermore, exhibits remarkable redox properties. cationic radical ⋅ + readily captures hydrogen atom. Variable‐temperature NMR (VT ) variable‐temperature EPR (VT‐EPR) studies reveal that dianion 2− possesses an open‐shell singlet ground state demonstrates global anti‐aromaticity. dication 2+ is also predicted to exhibit diradical character. Despite bearing three bulky substituents, p ‐type transport characteristics with mobility 0.03 cm 2 V −1 s attributed its unique structure. Overall, work directs PAHs, member nonalternant PAHs showcasing exceptional properties applications.

Language: Английский

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1,1′-Biolympicenyl: A Stable Non-Kekulé Diradical with a Small Singlet and Triplet Energy Gap

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(38), P. 26454 - 26465

Published: Sept. 10, 2024

Dimerization of delocalized polycyclic hydrocarbon radicals is a simple and versatile method to create diradicals with tailored electronic structures accessible high-spin states. However, the synthesis challenging, stability issue remains concern. In this study, we present stable non-Kekulé 1,1'-biolympicenyl diradical

Language: Английский

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Linear Non-benzenoid Isomer of Acene Fusing Chrysene with Azulene Units

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(33), P. 8410 - 8419

Published: Aug. 8, 2024

Non-benzenoid polycyclic aromatic hydrocarbons (PAHs) have received considerable attention owing to their distinctive optical and electrical properties. Nevertheless, the synthesis optoelectronic application of non-benzenoid PAHs remain challenging. Herein, we present a facile linear PAH with an armchair edge, diACh, by fusing chrysene two azulene units. We systematically investigated properties, which were also compared its isomers, including benzenoid zigzag edge isomers. diACh exhibits global aromaticity, good planarity, suitable highest occupied molecular orbital/lowest unoccupied orbital energy levels. The protonation in solution successively forms stable tropylium cation dication. Moreover, neutral, cationic, dicationic states can be transformed remarkable reversibility during protonation–deprotonation process, as confirmed ultraviolet–visible absorptions, fluorescence spectra, 1H nuclear magnetic resonance, theoretical calculations. Additionally, fabricate p-type organic field-effect transistor (OFET) devices based on hole mobility up 0.026 cm2 V–1 s–1, further develop OFET-based acid vapor sensors sensitivity, recyclability, selectivity. These findings underscore unique properties engendered fusion acene backbone, showcasing prospective applications optoelectronics.

Language: Английский

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Synthesis of Graphene Nanosheets Containing Ultra-Narrow Nonplanar Nanopores on Surfaces

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 19, 2024

Introduction of twisted structures into low-dimensional graphene-based nanostructures has important ramifications on their inherent physical behavior. The fabrication graphene derivatives with nonplanar characteristics remains challenging, especially for extended two-dimensional (2D) structures. Herein, we report the synthesis a novel porous [32]annulene nanosheet that contains narrowest periodic nanopores and exhibits highest negative curvature among one-dimensional (1D) 2D synthesized up to date. success is driven by dissymmetrical debromination regioselective coupling reactions precursor molecules Au(111) surface, as corroborated scanning tunneling microscopy (STM) synchrotron radiation photoemission spectroscopy (SRPES). We characterize electronic properties nanosheets aid (STS), demonstrate generation low-energy state resulting from hole doping at interface.

Language: Английский

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