Analysis of kinetic asymmetry in a multi-cycle reaction network establishes the principles for autonomous compartmentalized molecular ratchets

Chem, Journal Year: 2024, Volume and Issue: 10(12), P. 3644 - 3655

Published: Sept. 13, 2024

Language: Английский

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Shape-Persistent Tetraphenylethylene Macrocycle: Highly Efficient Synthesis and Circularly Polarized Luminescence

Materials, Journal Year: 2025, Volume and Issue: 18(1), P. 200 - 200

Published: Jan. 5, 2025

Circularly polarized luminescence (CPL) is an emerging field with significant applications in molecular electronics, optical materials, and chiroptical sensing. Achieving efficient CPL emission organic systems remains a major challenge, particularly the development of materials high fluorescence quantum yields (ΦF) large dissymmetry factors (glum). Herein, we report synthesis shape-persistent tetraphenylethylene macrocycles investigate its potential as material. Chiral side chains were introduced to induce properties. The their properties characterized using NMR, MALDI-TOF MS, FT-IR, TGA, DSC, UV-Vis spectroscopy, SEM, ECD, CPL. A enhancement was observed upon aggregation, demonstrating typical aggregation-induced (AIE) behavior. Moreover, one solid state displayed distinct glum 2 × 10−2 ΦF value reaching 60%, exhibited circularly (AICPL). These findings highlight advantage macrocycle noncollapsible backbone for design property, offering promising materials.

Language: Английский

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Hydrogen-bonded macrocycle-mediated dimerization for orthogonal supramolecular polymerization

Beilstein Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 21, P. 179 - 188

Published: Jan. 17, 2025

Orthogonal self-assembly represents a useful methodology to construct supramolecular polymers with AA- and AB-type monomers, as commonly used for covalently linked polymers. So far, the design of such monomers has relied heavily on three-dimensional macrocycles, use two-dimensional shape-persistent macrocycles this purpose remains rather rare. Here, we demonstrate dimerization motif based hydrogen-bonded macrocycle that can be effectively applied form orthogonal The macrocycle-mediated connectivity was confirmed by single-crystal X-ray diffraction, which revealed unique 2:2 binding between host guest, bridged two cationic pyridinium end groups through π-stacking interactions other cooperative intermolecular forces. Zinc ion-induced coordination terpyridinium derivative enabled polymerization, 1H NMR, DLS, TEM techniques. In addition, viscosity measurements showed transition from oligomers at critical polymerization concentration 17 μM. These were highly concentration-dependent. Establishing new H-bonded widens scope noncovalent building blocks augurs well future development functional materials.

Language: Английский

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Manipulating the Isomerization of a Tris-azobenzene Cage by Anion Binding

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

Published: April 22, 2025

Here, we report a C3-symmetric tris-azobenzene cage 1 comprising azobenzene cores and bis(urea) units. This system demonstrates efficient reversible photoisomerization unprecedented anion-mediated switching modes. Specifically, the phosphate anion induces concerted ZZZ → EEE isomerization with prolonged thermal relaxation (t1/2 = 37.5 h at 298 K). In contrast, bulky benzene-1,3,5-tricarboxylate enforces stepwise pathway (ZZZ EZZ EEZ EEE) rapid 54.4, 44.5, 12.9 min for each step). study represents first demonstration of selective control over multi-azobenzene switch, mimicking biological adaptability through environmental changes.

Language: Английский

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