Artificial Light Harvesting Systems Based on Novel AIEgen-branched Rotaxane Dendrimers for Photocatalyzed Functionalization of C-H Bonds

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Novel AIEgen-branched rotaxane dendrimers with up to 42 precisely distributed TPE units were synthesized, enabling the construction of artificial LHSs that exhibit generation-dependent photocatalytic performance in C–H bond functionalization.

Language: Английский

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Xantphos–Cu‐Decorated Covalent Organic Frameworks for C─H Arylation through Sensitized Electron Transfer

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

Published: March 4, 2025

The isoindolinone scaffold is an important structural motif found in a wide range of naturally occurring and synthetic biologically active compounds. However, the synthesis derivatives typically requires multi-step procedures or use palladium-based catalysts, which are often hampered by low reaction yields high costs. Recently, covalent organic frameworks (COFs)-emerging crystalline porous materials-have gained considerable attention for their applications various transformations, particularly C─H functionalization, cross-coupling redox reactions. Although COFs have been extensively studied photocatalysis, development sustainable heterogeneous catalysts using low-cost transition metal-based photosensitizers still its early stages. Herein, strategy presented to incorporate copper-Xantphos complex with tetrahedral Cu(I) geometry into COF matrix. This modification enables unprecedented simultaneous electron energy transfer efficiency during photocatalysis. Cu-Xantphos coordinated exhibits potent photocatalytic activity via C─Br bond cleavage followed C─C formation. In addition, catalyst shows excellent recyclability as it can be rejuvenated reintroducing after multiple cycles-highlighting potential cost-effective solution valuable transformations.

Language: Английский

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Host–Guest Approach to Enhancing Photocatalysis via Photoinduced Energy and Electron Transfer from a Photoactive Triphenylamine-Based Metal–Organic Cage to Bound Guests

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

Published: March 26, 2025

The host-guest strategy presents an ideal way to construct versatile supramolecular systems that mimic the structure and functionality of natural enzymes and, therefore, achieve efficient chemical conversions. An emissive triphenylamine-based cage-like host donor was constructed as energy or electron photoinduced transfer (PEnT PET) by encapsulating acceptor into cavity cage. complexes, which served enzyme-mimicking systems, were successfully used photocatalysts for selective aerobic oxidation sulfides photocatalytic reduction aryl halides with high potentials. This work details a promising approach creating system via encapsulation enhance efficiency PEnT PET process. resulting designed artificial conversions mimicking enzymes.

Language: Английский

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Guest Molecule Induced FRET Enhancement of Photochromic Pillar[5]arene‐Based Phenothiazine Derivatives

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

Comprehensive Summary In recent years, the study of photochromic behavior phenothiazine derivatives has not only enriched variety color‐changing materials but also provided new donor molecules for construction Förster Resonance Energy Transfer (FRET). This advancement broadens application potential and offers fresh perspective FRET research. Herein, pillar[5]arene‐linked biphenothiazine derivative ( DPP5 ) was synthesized, while p ‐dibenzyl‐linked DPDB butyl‐linked DPB were designed comparative study. The demonstrated by UV‐vis spectra, electron paramagnetic resonance (EPR) chemical oxidation method, showing transformation molecule into radical cation •+ subsequently dication 2+ . Furthermore, a system constructed using species as energy Nile red (NiR) acceptor. introduction guest molecules, 1,6‐dibromohexane 1,6‐DBH 1,10‐dibromodecane 1,10‐DBD ), above enhanced transfer efficiency increasing aggregation degree utilizing cavity pillar[5]arene through host‐guest interaction. system, along with strategy to enhance properties, will contribute development novel materials.

Language: Английский

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Modulating the Aggregation States of a Pd6L4 Cage for Selectivity Flipping during the Stereo‐Divergent Semi‐Hydrogenation of Alkynes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 6, 2024

Abstract An enzyme‐mimicking catalytic system has been established using a singular palladium‐based octahedral cage as the supramolecular reactor, deftly unlocking off‐on‐off selectivity in semi‐hydrogenation of alkynes. Water serves critical regulator, modulating catalyst states, reaction rates, and endpoints. The choice solvent influences activity host–guest binding types homogeneous heterogeneous catalysis, effectively modifying steps involved Z → E isomerization during Kinetic inhibition experiments indicate that mimics activation characteristics enzymes towards substrates, enabling selective transformations within confined environment. utility this switchable cage‐confined catalysis demonstrated synthesis modification complex biologically active molecules with controllable / selectivity. This work sheds light on design control artificial counterparts enzymes, offering fundamental insights into factors influencing biological macromolecules.

Language: Английский

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Modulating the Aggregation States of a Pd6L4 Cage for Selectivity Flipping during the Stereo‐Divergent Semi‐Hydrogenation of Alkynes

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 6, 2024

Abstract An enzyme‐mimicking catalytic system has been established using a singular palladium‐based octahedral cage as the supramolecular reactor, deftly unlocking off‐on‐off selectivity in semi‐hydrogenation of alkynes. Water serves critical regulator, modulating catalyst states, reaction rates, and endpoints. The choice solvent influences activity host–guest binding types homogeneous heterogeneous catalysis, effectively modifying steps involved Z → E isomerization during Kinetic inhibition experiments indicate that mimics activation characteristics enzymes towards substrates, enabling selective transformations within confined environment. utility this switchable cage‐confined catalysis demonstrated synthesis modification complex biologically active molecules with controllable / selectivity. This work sheds light on design control artificial counterparts enzymes, offering fundamental insights into factors influencing biological macromolecules.

Language: Английский

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