Water-Soluble Self-Assembled Cage with Triangular Metal–Metal-Bonded Units Enabling the Sequential Selective Separation of Alkanes and Isomeric Molecules

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(35), P. 16191 - 16198

Published: Aug. 16, 2022

The selective separation of structurally similar aliphatic/aromatic hydrocarbons is an essential goal in industrial processes. In this study, we report the synthesis a water-soluble (Tr2M3)4L4 (Tr = cycloheptatrienyl ring; M metal; L organosulfur ligand) molecular cage (1) via self-assembly acceptor tripalladium sandwich species [(Tr2Pd3)(CH3CN)][NO3]2 and attachment onto solubilizing methoxyethoxy appendants to be utilized energy-friendly alternative approach molecules under ambient conditions. Cage 1, comprising hydrophobic inner cavity, exhibited good solubility stability aqueous media. It also demonstrated excellent performance sequential alkanes (C6–C9), xylene, other disubstituted benzene isomers cis/trans-decalin.

Language: Английский

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Molecular Barrels as Potential Hosts: From Synthesis to Applications

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(14), P. 7692 - 7711

Published: March 28, 2023

Self-assembled discrete molecular architectures that show selective recognition within their internal cavities are highly desirable. Such hosts often guest through several noncovalent interactions. This emulates the activity of naturally occurring enzymes and proteins. Research in formation 3D cages different shapes sizes has progressed rapidly since development coordination-driven self-assembly dynamic covalent chemistry. find applications catalysis, stabilization metastable molecules, purification isomeric mixtures via encapsulation, even biomedical applications. Most these stem from ability host to bind guests strongly a fashion, providing suitable environment for perform functions. Molecular having closed with small windows either poor encapsulation or inhibit easy release while those wide open structures fail form stable host-guest complexes. In this context, barrels obtained by metal-ligand/covalent bond techniques possess optimized architectures. With hollow-walled cavity two large openings, satisfy structural requirements many perspective, we will discuss detail synthetic strategies obtaining barrel-like employing coordination interactions, structure-based classification, storing transient separation chemicals, photoinduced antibacterial activity. We aim highlight advantages over other efficiently carrying out functions new

Language: Английский

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Potential of nonporous adaptive crystals for hydrocarbon separation

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(17), P. 6075 - 6119

Published: Jan. 1, 2023

The adsorptive separation based on nonporous adaptive crystals (NACs) is an attractive green technology. Herein, we comprehensively summarize recent advances in various supramolecular hosts-based NACs for hydrocarbon separation.

Language: Английский

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Double-walled Al-based MOF with large microporous specific surface area for trace benzene adsorption

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: April 13, 2024

Abstract Double-walled metal-organic frameworks (MOFs), synthesized using Zn and Co, are potential porous materials for trace benzene adsorption. Aluminum is with low-toxicity abundance in nature, comparison Co. Therefore, a double-walled Al-based MOF, named as ZJU-520(Al), large microporous specific surface area of 2235 m 2 g –1 , pore size distribution the range 9.26–12.99 Å excellent chemical stability, was synthesized. ZJU-520(Al) consisted by helical chain AlO 6 clusters 4,6-Di(4-carboxyphenyl)pyrimidine ligands. Trace adsorption up to 5.98 mmol at 298 K P/P 0 = 0.01. Adsorbed molecules trapped on two types sites. One (site I) near clusters, another II) N atom ligands, Grand Canonical Monte Carlo simulations. can effectively separate from mixed vapor flow cyclohexane, due affinity higher than that cyclohexane. adsorbent benzene/cyclohexane separation.

Language: Английский

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Separation of benzene and toluene associated with vapochromic behaviors by hybrid[4]arene-based co-crystals

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 10, 2024

Abstract The combination of macrocyclic chemistry with co-crystal engineering has promoted the development materials vapochromic behaviors in supramolecular science. Herein, we develop a macrocycle based on hybrid[4]arene and 1,2,4,5-tetracyanobenzene that is able to construct materials. After capture benzene toluene vapors, activated hybrid[4]arene-based forms new structures, accompanied by color changes from brown yellow. However, when captures cyclohexane pyridine, neither structures nor colors change. Interestingly, can separate benzene/cyclohexane equal-volume mixture allow be removed toluene/ pyridine purities reaching 100%. In addition, process adsorptive separation visually monitored. selectivity attributed different charge-transfer interaction between vapors. Moreover, reused without losing performance. This work constructs material for hydrocarbon separation.

Language: Английский

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Palladium-Catalyzed Regioselective B(9)-Amination of o-Carboranes and m-Carboranes in HFIP with Broad Nitrogen Sources

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(18), P. 8371 - 8378

Published: May 2, 2022

Amination of carboranes has a good application prospect in organic and pharmaceutical synthesis. However, the current methods used for this transformation suffer from limitations. Herein, we report practical method highly regioselective formation B-N bond by Pd(II)-catalyzed B(9)-H amination o- m-carboranes hexafluoroisopropanol (HFIP) with different nitrogen sources under air atmosphere. The silver salt HFIP solvent play critical roles present protocol. mechanistic study reveals that acts as Lewis acid to promote electrophilic palladation step forming heterobimetallic active catalyst PdAg(OAc)3; strong hydrogen-bond-donating ability low nucleophilicity enhance Pd(II). It is believed these N-containing are potentially great importance synthesis new pharmaceuticals.

Language: Английский

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Single‐Fluorophore‐Based Organic Crystals with Distinct Conformers Enabling Wide‐Range Excitation‐Dependent Emissions

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(41)

Published: Aug. 18, 2022

Achieving wide-range tunable emission colors, especially in the solid state of single-fluorophore materials, remains a significant challenge. Herein, we report molecular design strategy that affords excitation-dependent emissions spanning over ≈230 nm crystalline states. Under donor-π-acceptor configuration, judiciously choose rotatable acceptor fragment, o-carborane, to enrich conformational diversities and generate conformation-dependent multicolor emissions. We further show this platform is generalizable creating materials with Based on these high-capacity information storage device finite-state machine were fabricated showcase displays storage.

Language: Английский

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Trefoil-Shaped Metal–Organic Cages as Fluorescent Chemosensors for Multiple Detection of Fe³⁺, Cr₂O₇^2–, and Antibiotics

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(4), P. 1297 - 1305

Published: Jan. 17, 2023

The construction of metal-organic cages (MOCs) with specific structures and fluorescence sensing properties is much importance challenging. Herein, a novel phenanthroline-based cage, [Cd3L3·6MeOH·6H2O] (1), was synthesized by metal-directed assembly the ligand 3,3'-[(1E,1'E)-(1,10-phenanthroline-2,9-diyl)bis(ethene-2,1-diyl)]dibenzoic acid (H2L) CdI2 using solvothermal method. According to single-crystal X-ray analysis, cage 1 exhibits rare trefoil-shaped structure. Meanwhile, discrete MOCs are further stacked into 3D porous supramolecular structure through abundant intermolecular C-H···O interactions. Additionally, exploration on cations, anions, antibiotics in aqueous solution, experimental results indicate that has excellent abilities for Fe3+, Cr2O72-, nitrofuran nitroimidazole antibiotics. ability remains unaltered five cycles toward all analytes. above suggested can be considered potential multiple sensor detection some

Language: Английский

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Carborane-Based Three-Dimensional Covalent Organic Frameworks

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(44), P. 24202 - 24209

Published: Oct. 27, 2023

The predesignable porous structure and high structural flexibility of covalent organic frameworks (COFs) render this material desirable as a platform for addressing various cutting-edge issues. Precise control over their composition, topological structure, porosity, stability to realize tailor-made functionality still remains great challenge. In work, we developed new kind three-dimensional (3D) carborane-based COF with 7-fold interpenetrating dia diagram. resulting COFs exhibited crystallinity, exceptional strong robustness. slightly lower electronegativity boron (2.04) than that hydrogen (2.20) can lead the polarization B-H bond into Bδ+-Hδ- mode, which renders these high-performance materials adsorption separation hexane isomers through B-Hδ-···Hδ+-C interaction. Significantly, carborane content obtained reached up 54.2 wt %, gets highest rank among all reported materials. Combining surface area, robustness, carborane, work efficient adsorbents five factors. This not only enhances diversity 3D functional but also constitutes further step toward alkane isomers.

Language: Английский

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Self-Assembly and Photothermal Conversion of MetallaRussian Doll and Metalla[2]catenanes Induced via Multiple Stacking Interactions

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(32), P. 18036 - 18047

Published: July 17, 2023

A variety of organometallic supramolecular architectures have been constructed over the past decades and their properties were also explored via different strategies. However, synthesis metalla-Russian doll is still a fascinating challenge. Herein, series new coordination complexes, including doll, metalla[2]catenanes, metallarectangles, synthesized by using meticulously selected Cp*Rh (Cp* = η5-C5Me5) building units (E1, E2, E3) three rigid anthracylpyridine ligands (L1, L2, L3) self-assembly strategy. While combination short ligand L1 E1 or E2 generated two longer L2 containing an alkynyl group resulted in [2]catenanes, most likely due to which strong electron-donating effect groups causes self-accumulation. Interestingly, unusual Russian assembly was obtained through reaction L3 E3 based on sextuple π···π stacking interactions. Furthermore, dynamic structural conversion between [2]catenanes corresponding metallarectangles could be observed concentration-, solvent-, guest-induced effects. The [2]catenane complexes 4b displayed efficient photothermal efficiency solution (20.2%), comparison with other macrocycles. We believe that interactions generate active nonradiative pathways promote radiative photodeactivation pathways. This study proves versatility half-sandwich units, not only build complicated topologies but effective functional materials for various appealing applications.

Language: Английский

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