N-position isomerization to enhance the CO2 photoreduction performance of bipyridine-based covalent organic frameworks

Journal of Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 116177 - 116177

Published: April 1, 2025

Language: Английский

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Decoupling Interlayer Interactions Boosts Charge Separation in Covalent Organic Frameworks for High‐Efficiency Photocatalytic CO₂ Reduction

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

Published: April 29, 2025

Abstract Covalent organic frameworks (COFs) have emerged as promising photocatalysts owing to their structural diversity, tunable bandgaps, and exceptional light‐harvesting capabilities. While previous studies primarily focus on developing narrow‐bandgap COFs for broad‐spectrum solar energy utilization, the critical role of interlayer coupling in regulating charge transfer dynamics remains unclear. Conventional monolayer‐based theoretical models inadequately address effects that potentially hindering intralayer electron transport catalytic active sites. This work employs density functional theory (DFT) calculations investigate influence interactions imine‐based COFs. Theoretical analyses reveal bilayer architectures exhibit pronounced interference intramolecular processes which has not been observed monolayer models. Based these mechanistic insights, this designs two isomeric pyrene‐based incorporating identical donor (pyrene) acceptor (nickel bipyridine) units but with distinct strengths. Strikingly, optimized COF weakened demonstrates photocatalytic CO 2 reduction performance, achieving a evolution rate 553.3 µmol g −1 h 94% selectivity under visible light irradiation without additional photosensitizers or co‐catalysts. These findings establish engineering crucial design principle high‐performance COF‐based conversion applications.

Language: Английский

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Palladium/N-Heterocyclic Carbene-Decorated Covalent Organic Framework for Suzuki–Miyaura and Mizoroki–Heck Cross-Coupling

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

Published: May 2, 2025

Recently, significant breakthroughs have been achieved in covalent organic frameworks (COF) as well-defined porous materials for palladium catalysis. However, the development of modular decorated with readily available and strongly σ-donating N-heterocyclic ligands is unexplored. In this study, we report a novel Pd-NHC/COF framework, where active species incorporated into framework through accessible benzimidazolium. The system promotes Suzuki-Miyaura Mizoroki-Heck C-C cross-coupling highly reusable catalyst. Excellent catalytic efficiency high Z/E selectivity construction biaryls stilbenes using system.

Language: Английский

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Switching from Molecules to Functional Materials: Breakthroughs in Photochromism With MOFs

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 7, 2024

Abstract Photochromic materials with properties that can be dynamically tailored as a function of external stimuli are rapidly expanding field driven by applications in areas ranging from molecular computing, nanotechnology, or photopharmacology to programable heterogeneous catalysis. Challenges arise, however, when translating the rapid, solution‐like response stimuli‐responsive moieties solid‐state due intermolecular interactions imposed through close packing bulk solids. As result, integration photochromic compounds into synthetically porous matrices, such metal‐organic frameworks (MOFs), has come forefront an emerging strategy for material development. This review highlights how core principles reticular chemistry (on example MOFs) play critical role performance, surpassing limitations previously observed solution solid state. The symbiotic relationship between photoresponsive and focus on synthesis creates avenues toward tailorable photoisomerization kinetics, directional energy charge transfer, switchable gas sorption, synergistic chromophore communication is discussed. not only focuses recent cutting‐edge advancements development, but also novel, vital‐to‐pursue pathways multifaceted functional realms energy, technology, biomedicine.

Language: Английский

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Two‐Dimensional Conjugated Metal–Organic Frameworks with a Ring‐in‐Ring Topology and High Electrical Conductance

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(26)

Published: April 16, 2024

Abstract Electrically conducting two‐dimensional (2D) metal–organic frameworks (MOFs) have garnered significant interest due to their remarkable structural tunability and outstanding electrical properties. However, the design synthesis of high‐performance materials face challenges limited availability specific ligands pore structures. In this study, we employed a novel highly branched D 3h symmetrical planar conjugated ligand, dodechydroxylhexabenzotrinaphthylene (DHHBTN) fabricate series 2D conductive MOFs, named M–DHHBTN (M=Co, Ni, Cu). This new family MOFs offers two distinct types pores, elevating complexity more advanced level. The intricate tessellation patterns are elucidated through comprehensive analyses involving powder X‐ray diffraction, theoretical simulations, high‐resolution transmission electron microscope. Optical‐pump terahertz‐probe spectroscopic measurements unveiled carrier mobility in DHHBTN‐based spanning from 0.69 3.10 cm 2 V −1 s . Among famility, Cu‐DHHBTN displayed high conductivity reaching 0.21 S at 298 K with thermal activation behavior. work leverages “branched conjugation” ligand encode heteroporosity into underscoring potential heterogeneous double‐pore structures for future applications.

Language: Английский

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