Thermally Stable Photomechanical Molecular Hinge: Sterically Hindered Stiff-Stilbene Photoswitch Mechanically Isomerizes

JACS Au, Journal Year: 2023, Volume and Issue: 3(9), P. 2458 - 2466

Published: Aug. 21, 2023

Molecular photoswitches are extensively used as molecular machines because of the small structures, simple motions, and advantages light including high spatiotemporal resolution. Applications depend on mechanical responses, in other words, whether they can generate motions against forces actuators or be activated controlled by mechanophores. Sterically hindered stiff stilbene (HSS) is a promising photoswitch offering large hinge-like E/Z isomerization, thermal stability Z isomer, which relatively unstable compared to E with half-life ca. 1000 years at room temperature, near-quantitative two-way photoisomerization. However, its response entirely unexplored. Here, we elucidate mechanochemical reactivity HSS incorporating one isomer into center polymer chains, ultrasonicating solutions, stretching films apply elongational embedded HSS. The present study demonstrated that mechanically isomerizes only direction reversibly combination UV light, i.e., works photomechanical hinge. photomechanically inducible but thermally irreversible render unique promise unconventional applications differently from existing photoswitches, mechanophores, hinges.

Language: Английский

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Helical β‐isoindigo‐Based Chromophores with B−O−B Bridge: Facile Synthesis and Tunable Near‐Infrared Circularly Polarized Luminescence

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(8)

Published: Dec. 30, 2022

It is essential to create organic compounds that exhibit circularly polarized luminescence (CPL) in the near-infrared (NIR) range. Helicene-type emitters possess appealing chiroptical features, however, such NIR molecules are scarce due a paucity of synthetic strategies. Herein, we developed series helical β-isoindigo-based B-O-B bridged aza-BODIPY analogs were synthesized conveniently. The reaction diimino-β-isoindigo with heteroaromatic amine produced restricted ligand cavity, which triggered off generation bridge. bridge led distorted conformations satisfy requirements, resulting excellent spectroscopic and properties. Tunable CPL highest dissymmetry factor (glum ) 1.3×10-3 brightness (BCPL =11.5 M-1 cm-1 region was achieved. This approach expected offer new opportunity chiral chemistry increase flexibility for tuning.

Language: Английский

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Color-tuning and boosting circularly polarized luminescence performance of axially chiral tetra-BF₂complexes by post-modifications

Journal of Materials Chemistry C, Journal Year: 2023, Volume and Issue: 11(7), P. 2574 - 2581

Published: Jan. 1, 2023

Multicolored fluorescence, high Φ PL reaching 59%, and an efficient g lum up to 0.01 with the brightness for circularly polarized luminescence (125.2 M −1 cm ), were achieved in axially chiral tetra-BF 2 complexes by substituent engineering.

Language: Английский

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Axial and Helical Chirality in Multinuclear Group 13 Complexes: Pathways to Functional Optical Materials

Dalton Transactions, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Multinuclear group 13 complexes adopting axial and helical chirality exhibit unique structural chiroptical properties. This work highlights recent advances in their design, synthesis, photophysical behaviors.

Language: Английский

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Supramolecular‐Assembly and Surfactant‐Regulated Circularly Polarized Luminescence from a Spiranic BINOL‐Derived Borate Isoindolyl‐Indolenine (BBI) Dye

Advanced Optical Materials, Journal Year: 2025, Volume and Issue: unknown

Published: April 4, 2025

Abstract Circularly polarized luminescence (CPL) materials have attracted significant attention owing to their unique luminescent properties and broad range of applications. However, challenges remain, including controlling helical assembly, mitigating aggregation‐caused quenching, balancing quantum yield ( Φ PL ) with g values. Here, the study reports synthesis a novel asymmetric, spiranic O‐organoboranes bearing isoindolyl‐indolenine scaffold (BBI) axial chirality through BINOL substitution, as well its supramolecular assembly surfactant‐regulated tunable CPL behaviors. The newly designed BBI dye shows relative weak 10% in toluene. Supramolecular acetonitrile/water co‐solvents exhibit an obvious aggregation‐induced emission (AIE) process, leading formation spherical nanostructures red‐shifted orange‐yellow (554 nm, = 0.012, 7%). Moreover, surfactant sodium dodecyl sulfonate (SDS) can promote aggregation pure deionized water, producing nanofibers blue‐shifted yellow (536 0.006, 13%). Crystal growth toluene/hexane SDS aqueous/acetonitrile systems reveals chiral crystals P 212121 space group, offering insights into amplification. This demonstrates ability precisely control parameters, X‐ray single‐crystal analysis providing additional understanding regulation.

Language: Английский

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Planar-to-Bent Conformational Changes in Luminescent Tetra-BF₂ Complexes: Toward Smart Stimuli-Responsive Materials

ACS Applied Optical Materials, Journal Year: 2025, Volume and Issue: unknown

Published: May 22, 2025

Language: Английский

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Aromatic-Ring-Fused BOPPY Fluorophores: Synthesis, Spectral, Redox Properties, and Bioimaging Application

Inorganic Chemistry, Journal Year: 2022, Volume and Issue: 61(42), P. 16718 - 16729

Published: Oct. 7, 2022

Tetracoordinated organoboron dyes exhibiting strong fluorescence in either solution or the solid state are currently receiving much attraction view of their photovoltaic, optoelectronic, and biological applications. Herein, a series aromatic-ring-fused BOPPY have been developed by one-pot condensation formylated isoindoles indoles pyridinylhydrazine followed subsequent borylation coordination. The facile synthesis provides excellent diversity these unsymmetrical α-benzo- β-benzothiophene-fused with intriguing photophysical properties owing to rigid planar structure extended π-conjugation while containing reactive site. They display intense green orange red-to-near-infrared emission state, high quantum yields up 92 21%, respectively, relatively large Stokes shifts, photostability. Furthermore, two representative benzo-fused probes morpholine benzenesulfonamide groups were used selectively "light up" subcellular organelles such as lysosomes endoplasmic reticulum under ultralow concentration, respectively.

Language: Английский

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Advanced Molecular Design for Efficient Multicolor Electrochemiluminescence and Amplified Spontaneous Emission Based on Tetra‐BF₂ Complexes

Advanced Optical Materials, Journal Year: 2024, Volume and Issue: 12(14)

Published: Jan. 19, 2024

Abstract Advanced organoboron dyes, incorporating tetra‐boron difluoride (tetra‐BF 2 ) moieties, are developed, demonstrating efficient electrochemiluminescence (ECL) emissions in the green to orange regions through direct ion annihilation. By introducing diverse alkyl modifications molecules, luminescence color tuning is achieved via alterations conjugation and bending angle. A photoluminescence quantum yield of 100% dilute solutions successfully achieved. Notably, introduction groups methine side stabilizes radical ionic state, resulting a high ECL efficiency 74% an radical‐ion annihilation pathway. The key factor that energy reaction exceeds S 1 required for luminescence. Spin density calculations further elucidate substituent effects on ions complexes. Moreover, lasing properties these materials solution‐processed blend films investigated, revealing low amplified spontaneous emission (ASE) threshold ( E th 6.40 ± 0.24 µJ cm −2 , which notably lower among organic laser materials. This attributed their large Stokes shifts yield. excellent ASE performances establish as valuable addition existing library offering fresh insights into development solid‐state lasers.

Language: Английский

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Unraveling the Remarkable Influence of Substituents on the Emission Variation and Circularly Polarized Luminescence of Dinuclear Aluminum Triple-Stranded Helicates

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(14), P. 6296 - 6304

Published: March 25, 2024

This study explored the development of functional dyes using aluminum, focusing on aluminum-based dinuclear triple-stranded helicates, and examined effects substituent variations their structural optical properties. Key findings revealed that modification methyl groups to pyrrole positions significantly extended conjugation system, resulting in a red shift absorption emission spectra. Conversely, at methine due steric hindrances increased torsion angle ligands, leading blue A common feature across all complexes was excited state, one three ligands underwent significant relaxation. led pronounced Stokes minimal spectra overlap with high photoluminescence behaviors. Moreover, our research resolution newly synthesized by analyzing chiroptical properties enantiomers, including circular dichroism circularly polarized luminescence. These insights offer valuable contributions design application novel dyes, potentially influencing range fields, from materials science optoelectronics.

Language: Английский

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Highly efficient luminescence from boron β-dialdiminates and their π-conjugated polymers in both solutions and solids: significant impact of the substituent position on luminescence behavior

Materials Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 7(20), P. 4971 - 4983

Published: Jan. 1, 2023

We report that substituents on imine carbons of β-diiminate have significant impact the emission efficiency their boron complexes and polymers.

Language: Английский

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