Palladium-Catalyzed Cross-Coupling Reactions of Carboranes with Alkenes via Selective B–H Bond Activation

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 17, 2025

A palladium-catalyzed Heck-type cross-coupling reaction of carboranes with alkenes in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was realized. This shows good B(9) selectivity for m-carboranes and is also suitable o- p-carborane. Meanwhile, a series mono-, di-, trisubstituted were compatible substrates to afford the alkenylated products 16–89% yields. The 1,2-bis(carboranyl)ethylene first synthesized by vinyltrimethylsilane m-carborane. Further transformations C═C bond product examined hydroboration oxidation, hydroboration, bromination generate corresponding B(9)-functionalized m-carboranes.

Language: Английский

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Constructing Three-Dimensional Covalent Organic Framework with aea Topology and Flattened Spherical Cages

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

Published: Feb. 27, 2025

Language: Английский

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Machine Learning Accelerated Discovery of Covalent Organic Frameworks for Environmental and Energy Applications

Environmental Science & Technology, Journal Year: 2025, Volume and Issue: unknown

Published: March 30, 2025

Covalent organic frameworks (COFs) are porous crystalline materials obtained by linking ligands covalently. Their high surface area and adjustable pore sizes make them ideal for a range of applications, including CO2 capture, CH4 storage, gas separation, catalysis, etc. Traditional methods material research, which mainly rely on manual experimentation, not particularly efficient, while with advancements in computer science, high-throughput computational screening based molecular simulation have become crucial discovery, yet they face limitations terms resources time. Currently, machine learning (ML) has emerged as transformative tool many fields, capable analyzing large data sets, identifying underlying patterns, predicting performance efficiently accurately. This approach, termed "materials genomics", combines ML to predict design high-performance materials, significantly speeding up the discovery process compared traditional methods. review discusses functions screening, design, prediction COFs highlights their applications across various domains like thereby providing new research directions enhancing understanding COF applications.

Language: Английский

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Isomeric Separation of C6 Alkanes via Organic Solvent Reverse Osmosis with Covalent Organic Framework Membranes

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

Published: April 21, 2025

Membrane separation represents cutting-edge technology for the isomeric of C6 alkanes in petrochemical sector. However, it remains challenging to design membranes with sub-0.1 nm resolution that can effectively discriminate between alkane isomers. In this study, we report a molecularly selective, ultramicroporous covalent organic framework (COF) membrane featuring an accessible pore size ∼4.5 Å alkanes. High permeance 2.56 kg m-2 h-1 bar-1 together high selectivity 70.9 are achieved binary linear n-hexane (nHEX) and branched 2,3-dimethylbutane (23DMB) through solvent reverse osmosis (OSRO). Notably, research octane number (RON) five-component mixture be improved from 67.7 92.8 continuous using COF membrane. The exceptional performance suggests new next-generation selective toward efficient separation.

Language: Английский

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Semiconducting Polyaromatic Covalent Organic Frameworks Constructed through Self-Aldol Condensation

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

Published: April 30, 2025

The construction of semiconducting covalent organic frameworks (COFs) via single-component self-polymerization is broad interest in reticular chemistry. Herein, two polyaromatic COFs with all-fused-ring conjugation structures were synthesized through the self-aldol condensation indanone-based building blocks. resulting exhibit n-type properties and exceptional stability under harsh acidic alkaline conditions. electrical conductivity charge carrier mobility reached up to 5.5 × 10-3 S cm-1 0.62 cm2 V-1 s-1, which ranked as highest values among COFs. high crystallinity, intrinsic porosity, excellent conductivity, abundant five-membered rings active sites render these effective metal-free electrocatalysts toward oxygen reduction reaction (ORR). Notably, one shows a half-wave potential 0.77 V conditions, constitutes reported ORR electrocatalysts. In addition, owing strong robustness COFs, they also long-term catalytic durability. This study not only expands diversity but establishes new paradigms for development high-performance process.

Language: Английский

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3D interpenetrated covalent organic frameworks

Coordination Chemistry Reviews, Journal Year: 2025, Volume and Issue: 535, P. 216614 - 216614

Published: March 18, 2025

Language: Английский

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Phenyl-Substituted Thiaboranes─Linked 2D and 3D Aromatics as Noncovalent Organic Framework Materials

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

Published: April 9, 2025

A series of 12-phenyl-closo-thiaboranes (12-(4-X-C6H4)-closo-1-SB11H10, where X = OMe (2), SMe (3), Ph (4), and NMe2 (5)) has been prepared. Except for 2, all compounds exhibit a chalcogen bond thiaborane to the phenyl ring or neighboring molecule as major supramolecular structural motif. 5, having strongest (-12.47 kcal/mol) structure-making intermolecular interaction via noncovalent S···π(phenyl) bond, was crystallized from different solvents in form various solvatopolymorphs. n-Hexane diethyl ether can be removed 5 easily upon formation porous material with large cavities (up 20.5% unit cell). This first stable useful noncovalently bound organic framework an ultramicroporous structure exhibits molecular sieve effect. The selective repeatable adsorption CO2 n-hexane explained on basis cooperative consecutive machine-like interactions quadrupolar B-H amino groups inside rectangular cavities.

Language: Английский

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C₂H₂/CO₂ Separation by a Carborane Hybrid 2D Metal–Organic Framework

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

Published: May 6, 2025

The separation of acetylene (C2H2) from carbon dioxide (CO2) is important in industry but challenging due to their similar physical properties. Herein, a boron-rich 2D metal-organic framework ZNU-14 based on the carborane backbone was readily prepared by supramolecular assembly Zn2+, p-C2B10H10-(COOH)2, and di(pyridin-4-yl) amine under mild conditions for C2H2/CO2 separation. displays straight 1D channel (7.6 × 12.5 Å2) with an electronegative pore surface. Gas adsorption isotherms show that has good C2H2 capacity 43.6 cm3 g-1, 181% CO2 uptake capacity. calculated ideal adsorbed solution theory (IAST) selectivity as high 6.3-9.7, outperforming many popular materials. moderate heat 34.3 kJ mol-1 facilitates straightforward desorption regeneration ZNU-14. Furthermore, theoretical study confirmed stronger binding compared CO2. practical performance fully demonstrated breakthrough experiments excellent dynamic recyclability various conditions.

Language: Английский

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Covalent organic polyrotaxanes based on β-cyclodextrin for iodine capture

RSC Advances, Journal Year: 2024, Volume and Issue: 14(41), P. 30077 - 30083

Published: Jan. 1, 2024

Herein, covalent organic polyrotaxanes (COPRs) were integrated with supermolecule self-assembly and dynamic imine bond formation to act as absorbents that captured radioactive iodine from water. The aromatic building blocks initially complexed β-cyclodextrin (β-CD) form pseudorotaxanes, which then condensed tri-aldehyde

Language: Английский

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Multiple Energy Transfer Modes From o‐Carborane Dyad Induced by Synergetic Conformational Regulations and Intense Circularly Polarized Luminescence in Self‐Assembly Aggregates

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

Published: Oct. 15, 2024

Abstract Photothermal modulated excited conformations in traditional optoelectronic materials have been extensively investigated for the manipulation of emissive properties. However, photoinduced molecular synergetic conformational changes, which are promising controlling intramolecular energy transfer modes through orbital breaking, never explored. Herein, a novel o ‐carborane dyad composed carbazole units as electron donors and triazine derivatives acceptors is demonstrated to achieve conformation‐dependent emissions abundant via changes. Notably, resulting exhibited multiple changes that induced different involved “through space” bond.” Exactly, spin from singlet triplet state took flip accompanied by orbitals π–π space charge style π σ bond mode. The circularly polarized luminescence (CPL) properties systematically investigated, exhibiting intense CPL with large g lum values. These results provide perspectives elucidating complicated emission aggregated states, well unique on relationship between conformations, modes, breaking.

Language: Английский

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