Highly Luminescent Chiral Double π-Helical Nanoribbons

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5295 - 5304

Published: Feb. 16, 2024

Unveiling the mechanism behind chirality propagation and dissymmetry amplification at molecular level is of significance for development chiral systems with comprehensively outstanding chiroptical performances. Herein, we have presented a straightforward Cu-mediated Ullmann homocoupling approach to synthesize perylene diimide-entwined double π-helical nanoribbons encompassing dimer, trimer, tetramer while producing homochiral or heterochiral linking centers. A significant was achieved, absorption factors (|gabs|) increasing from 0.009 0.017 further 0.019, luminescence (|glum|) rising 0.007 0.013 eventually 0.015 oligomers. The disparity magnetic transition dipole moment (m) densities in tetramers by time-dependent density functional theory calculations confirmed that oligomerization can maximize total m, which favorable achieving ever-increasing g factors. Notably, these π-helices exhibited exceptional photoluminescence quantum yields (ΦPL) ranging 83 95%. circularly polarized brightness (BCPL) reached remarkable 575 M–1 cm–1 tetramer, among highest values reported small molecules. This kind linearly extended offers platform comprehensive understanding amplification.

Language: Английский

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Nonalternant Nanographenes Containing N-Centered Cyclopenta[ef]heptalene and Aza[7]Helicene Units

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(23), P. 16161 - 16172

Published: May 9, 2024

Introducing helical subunits into negatively curved π-systems has a significant effect on both the molecular geometry and photophysical properties; however, synthesis of these embedded with nonbenzenoid remains challenging due to high strain deriving from curvature helix. Here, we report family nonalternant nanographenes containing nitrogen (N)-doped cyclopenta[ef]heptalene unit. Among them, CPH-2 CPH-3 can be viewed as hybrids benzoannulated aza[7]helicene. The crystal structures revealed saddle for CPH-1, saddle-helix hybrid CPH-2, twist-helix CPH-3. Experimental measurements theoretical calculations indicate that moieties in CPHs undergo flexible conformational changes at room temperature, while aza[7]helicene subunit exhibits dramatically increased racemization energy barrier (78.2 kcal mol–1 143.2 CPH-3). combination lone electron pairs N-doped unit twisted helix fragments results rich photophysics distinctive fluorescence phosphorescence CPH-1 similar Both enantiopure display distinct circular dichroism (CD) signals UV–vis range. Notably, compared reported fully π-extended nanographenes, excellent chiroptical properties |gabs| value 1.0 × 10–2 |glum| 7.0 10–3; values are among highest nanographenes.

Language: Английский

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bay/ortho-Octa-substituted Perylene: A Versatile Building Block toward Novel Polycyclic (Hetero)Aromatic Hydrocarbons

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(5), P. 763 - 775

Published: Feb. 22, 2024

ConspectusPolycyclic (hetero)aromatic hydrocarbons (PAHs) have emerged as a focal point in current interdisciplinary research, spanning the realms of chemistry, physics, and materials science. Possessing distinctive optical, electronic, magnetic properties, these π-functional exhibit significant potential across diverse applications, including molecular electronic devices, organic spintronics, biomedical functions, among others. Despite extensive documentation various PAHs over decades, efficient precise synthesis π-extended remains formidable challenge, hindering their broader application. This challenge is primarily attributed to intricate often elusive nature synthesis, compounded by issues related low solubility unfavored stability.The development π-building blocks that can be facilely modularly transformed into π-frameworks constitutes potent strategy for creation novel PAH materials. For instance, based on classic perylene diimide (PDI) unit, researchers such Würthner, Wang, Nuckolls successfully synthesized plethora structurally PAHs, well numerous other However, until now availability versatile building still severely limited, especially those simultaneously having facile preparation process, adequate solubilizing groups, favored material stability, critically, rich possibilities structural extension spaces.In this Account, we present an overview our invention highly bay-/ortho-octa-substituted block, designated Per-4Br, construction series scaffolds with tailor-made structures optoelectronic properties. First, starting brief discussion challenges associated bottom-up rationalize key features Per-4Br enable access new molecules its ease large-scale preparation, stability solubility, multiple flexible reaction sites, comparison PDI motif. Then, showcase rational design sophisticated body neutral or charged, closed- open-shell, curved, planar via controlled annulative π-extensions different directions peripheral, diagonal, dimensions skeleton. In part, fundamental structure–property relationships between conformations, structures, self-assembly behaviors unique physiochemical properties unusual open-shell ground states, global aromaticity, state-associated/stimuli-responsive activity, charge transport characteristics will emphatically elaborated. Finally, offer perspective continued advancement which, posit, may stimulate heightened research interest motifs typified consequently catalyzing further progress realm

Language: Английский

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Assembly and Utility of a Drawstring‐Mimetic Supramolecular Complex

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(8)

Published: Jan. 2, 2024

Abstract Inspired by the drawstring structure in daily life, here we report development of a drawstring‐mimetic supramolecular complex at molecular scale. This consists rigid figure‐of‐eight macrocyclic host molecule and flexible linear guest which could interact through three‐point non‐covalent binding to form highly selective efficient host‐guest assembly. The not only resembles structure, but also mimics properties with regard deformations under external forces. can be utilized as an interlocked crosslinker for poly(methyl acrylate), corresponding polymer samples exhibit comprehensive enhancement macroscopic mechanical performance including stiffness, strength, toughness.

Language: Английский

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Dithio-Fused Boron Dipyrromethenes: Synthesis and Impact of S-Heteroaromatic Annulation Mode

Organic Letters, Journal Year: 2024, Volume and Issue: 26(26), P. 5472 - 5477

Published: June 24, 2024

Three dithio-fused boron dipyrromethenes (BODIPYs), DTFB-1, DTFB-2, and DTFB-3, in which symmetrically S-heteroaromatic ring units fused at [a], zigzag, [b] bonds of the parent BODIPY core, respectively, were prepared from facile efficient post-functionalization tetra-halogenated BODIPYs through Pd-catalyzed cyclization. Dithio-fusion various positions effectively tunes their photophysical properties single-crystal structural packing arrangements. The single-crystalline microribbons DTFB-2 exhibit commendable hole mobilities air, reaching up to 0.03 cm2 V–1 s–1.

Language: Английский

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Near-Infrared Perylenecarboximide Fluorophores for Live-Cell Super-Resolution Imaging

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7135 - 7139

Published: March 5, 2024

Organic near-infrared (NIR) photoblinking fluorophores are highly desirable for live-cell super-resolution imaging based on single-molecule localization microscopy (SMLM). Herein we introduce a novel small chromophore, PMIP, through the fusion of perylenecarboximide with 2,2-dimetheylpyrimidine. PMIP exhibits an emission maximum at 732 nm high fluorescence quantum yield 60% in wavelength range 700–1000 and excellent without any additives. With resorcinol-functionalized (PMIP-OH), NIR SMLM lysosomes is demonstrated first time living mammalian cells under physiological conditions. Moreover, metabolically labeled nascent DNA site-specifically detected using azido-functionalized (PMIP-N3) via click chemistry, thereby enabling phosphate-buffered saline 9-fold improvement spatial resolution. These results indicate potential PMIP-based blinking biological applications SMLM.

Language: Английский

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Advances in Molecular Design and Photophysical Engineering of Perylene Bisimide-Containing Polyads and Multichromophores for Film-Based Fluorescent Sensors

The Journal of Physical Chemistry B, Journal Year: 2023, Volume and Issue: 127(4), P. 828 - 837

Published: Jan. 24, 2023

Film-based fluorescent sensors (FFSs) represent an important chemistry technology for meeting the urgent needs of on-site and real-time analysis, thereby enabling significant applications in environmental health monitoring. As core FFSs, innovative design sensing fluorophores their intrinsic excited-state-related response nature endow FFSs with superior performances endless expansion. In this Perspective, we specifically focus on perylene bisimide (PBI)-containing polyads multichromophores rigid configuration notable photochemical stability developing high-performance FFSs. These nonplanar structures mitigate aggregation create abundant gaps sake mass transfer availability units adlayer films. We also comprehensively discuss how to adjust electronic coupling governing excited-state events by appropriate functionalization strategies, thus providing a plethora valuable insights exploration structure-property relationships these orchestrated molecular systems. Throughout identify opportunities future developments.

Language: Английский

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Commercializable Naphthalene Diimide Anolytes for Neutral Aqueous Organic Redox Flow Batteries

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(25)

Published: April 11, 2024

Neutral aqueous organic redox flow batteries (AORFBs) hold the potential to facilitate transition of renewable energy sources from auxiliary primary energy, commercial production anolyte materials still suffers insufficient performance high-concentration and high cost preparation problem. To overcome these challenges, this study provides a hydrothermal synthesis methodology introduces charged functional groups into hydrophobic naphthalene diimide cores, prepares series high-performance anolytes. Under synergistic effect π-π stacking H-bonding networks, exhibits excellent structural stability highest water solubility (1.85 M for dex-NDI) reported date. By employing method, low-cost diimides are successfully synthesized on hundred-gram scale $0.16 g

Language: Английский

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Recent Advances of Chiral Isolated and Small Organic Molecules: Structure and Properties for Circularly Polarized Luminescence

Chemistry - An Asian Journal, Journal Year: 2024, Volume and Issue: 19(9)

Published: March 7, 2024

Abstract This paper explores recent advancements in the field of circularly polarized luminescence (CPL) exhibited by small and isolated organic molecules. The development application CPL molecule are systematically reviewed through eight different chiral skeleton sections. Investigating intricate interplay between molecular structure properties, aims at providing enlighting novel strategies for CPL‐based applications.

Language: Английский

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Room‐Temperature Near‐Infrared Phosphorescence from C₆₄ Nanographene Tetraimide by π‐Stacking Complexation with Platinum Porphyrin

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(33)

Published: May 7, 2024

Abstract Near‐Infrared (NIR) phosphorescence at room temperature is challenging to achieve for organic molecules due negligible spin–orbit coupling and a low energy gap leading fast non‐radiative transitions. Here, we show supramolecular host–guest strategy harvest the from low‐lying triplet state of C 64 nanographene tetraimide 1 . H NMR X‐ray analysis confirmed : 2 stoichiometric binding Pt(II) porphyrin on two π‐surfaces While free does not emission in NIR, complex solution shows NIR 77 K. Further, between 860–1100 nm, ( λ max =900 τ avg =142 μs) was observed solid‐state sample drop‐casted preformed solution. Theoretical calculations reveal non‐zero isoenergetic S T 3 π‐stacked [ ⋅ porphyrin] complex. External heavy‐atom‐induced along with rigidification protection oxygen promotes both intersystem crossing first excited singlet into manifold lowest

Language: Английский

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