Adaptive Catalysts for the Selective Hydrogenation of Bicyclic Heteroaromatics using Ruthenium Nanoparticles on a CO2‐Responsive Support DOI Creative Commons
Yuyan Zhang,

Sami El Sayed,

Liqun Kang

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(48)

Published: Sept. 7, 2023

Abstract Ruthenium nanoparticles (NPs) immobilized on an amine‐functionalized polymer‐grafted silica support act as adaptive catalysts for the hydrogenation of bicyclic heteroaromatics. Whereas full benzofuran and quinoline derivatives is achieved under pure H 2 , introducing CO into gas phase leads to effective shutdown arene while preserving activity heteroaromatic part. The selectivity switch originates from generation ammonium formate species surface materials by catalytic . fully reversible, resulting in a robust rapid between two states catalyst adapting its performance response feed composition. A variety were hydrogenated or partially saturated products high yields simply altering composition /CO system thus provides controlled access valuable using single rather than specific distinct with static reactivity.

Language: Английский

Photoresponsive Rotaxane-Branched Dendrimers: From Nanoscale Dimension Modulation to Macroscopic Soft Actuators DOI

Wei-Jian Li,

Weitao Xu,

Xu-Qing Wang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(26), P. 14498 - 14509

Published: June 16, 2023

Aiming at the construction of novel soft actuators through amplified motions molecular machines nanoscale, design and synthesis a new family photoresponsive rotaxane-branched dendrimers an efficient controllable divergent approach was successfully realized for first time. In third-generation dendrimers, up to 21 azobenzene-based rotaxane units located each branch, thus making them successful light-control integrated artificial machines. Notably, upon alternative irradiation with UV visible light, photoisomerization azobenzene stoppers leads collective precisely arranged units, resulting in reversible dimension modulation integrating solution. Moreover, macroscopic were further constructed based on these which revealed fast shape transformation behaviors actuating speed 21.2 ± 0.2° s-1 ultraviolet irradiation. More importantly, resultant could produce mechanical work light control that has been employed weight-lifting cargo transporting, laying foundation toward smart materials can perform programmed events.

Language: Английский

Citations

35
Adaptive Catalytic Systems for Chemical Energy Conversion DOI Creative Commons
Alexis Bordet, Walter Leitner

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(33)

Published: June 22, 2023

Abstract The rapidly growing importance of green hydrogen and renewable carbon resources as essential feedstocks for sustainable chemical value chains opens room disruptive innovations regarding production processes. fluctuation variability associated with non‐fossil energy raw material supply holds many challenges catalysts to cope the resulting dynamics. However, new opportunities also arise once catalyst design starts aim at performance that is “adaptive” rather than “task‐specific”. In this Scientific Perspective, we propose define adaptivity in catalysis on basis three properties are reversibility, rapidity, robustness ( R 3 rule). Promising strategies selected examples described substantiate scientific concept highlight its potential conversion.

Language: Английский

Citations

29
Polyrotaxane‐Based Functional Materials Enabled by Molecular Mobility and Conformational Transition† DOI

Qinke Cui,

Xinxing Zhang

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(20), P. 2715 - 2729

Published: May 22, 2023

Comprehensive Summary Slide‐ring structured polyrotaxanes with high molecular mobility and reversible conformational transition ability can achieve performance multifunctionality of the material in various applications. There have been many reviews describing advances research rotaxanes polyrotaxanes. However, most them typically focus on precise synthesis mechanically interlocked molecules control microscopic shuttles. In this review, we examine effects motion activity due to slide latest functional Different designs polyrotaxane‐based materials are presented improve potential for applications including self‐healing stretchable elastomers/gels, stimuli‐responsive smart devices, battery electrode binders, biomedical drug delivery. It is anticipated that review will provide insights guidance future developments design, application materials.

Language: Английский

Citations

15
A Thiourea-Based Rotaxane Catalyst: Nucleophilic Fluorination Phase-Transfer Process Unlocked by the Mechanical Bond DOI
Julio Puigcerver, Juan S. Dato-Santiago, Mateo Alajarı́n

et al.

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

Published: March 18, 2025

We report a five-component clipping approach using activated isophthaloyl-derived esters to synthesize an amide-based thiourea rotaxane. This method overcomes acyl chloride limitations with nucleophilic threads. The steric hindrance of the mechanical bond enables, for first time, interlocked as hydrogen-bonding phase-transfer organocatalyst in fluorinations. highlights how bonds expand catalysis processes previously incompatible conventional catalysts.

Language: Английский

Citations

0
Guest‐Shuttling in a Nanosized Metallobox DOI Creative Commons
Susana Ibáñez,

Paula Salvà,

Louise N. Dawe

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(11)

Published: Jan. 5, 2024

An iridium-conjoined long and narrow metallorectangle was obtained by combining a quinoxalinophenanthrophenazine-connected Janus-di-imidazolylidene ligand pyrazine. The size shape of this assembly together with the fused polyaromatic nature its panels provides it properties that are uncommon for other metallosupramolecular assemblies. For example, nanosized 'slit-like' metallobox is able show very large binding affinities planar organic molecules in such way, cavity asymmetrically occupied guest molecule. This unsymmetrical conformation leads to existence amplitude motion these guests, which slide between two sides host, thus constituting rare examples molecular shuttles.

Language: Английский

Citations

3
An Inorganic Click Reaction for the Synthesis of Interlocked Molecules DOI Creative Commons

Alex Mapp,

Jamie T. Wilmore, Paul D. Beer

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(38)

Published: July 14, 2023

We describe the use of cyaphide-azide 1,3-dipolar cycloaddition reaction for synthesis a new class inorganic rotaxanes containing gold(I) triazaphosphole stoppers. Electron-deficient bis-azides, which thread perethylated pillar[5]arene in aromatic solvents, readily react with two equivalents Au(IDipp)(CP) (IDipp=1,3-bis-(2,6-diisopropylphenyl)-imidazol-2-ylidene) to afford interlocked molecules via an click reaction. These transformations proceed good yields (ca. 65 %) and absence catalyst. The resulting organometallic are air- moisture-stable can be purified by column chromatography under aerobic conditions. targeted were characterized multi-element nuclear magnetic resonance (NMR) spectroscopy, mass-spectrometry, single-crystal X-ray diffraction.

Language: Английский

Citations

7
Adaptive Catalysts for the Selective Hydrogenation of Bicyclic Heteroaromatics using Ruthenium Nanoparticles on a CO2‐Responsive Support DOI Creative Commons
Yuyan Zhang,

Sami El Sayed,

Liqun Kang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(48)

Published: Sept. 7, 2023

Ruthenium nanoparticles (NPs) immobilized on an amine-functionalized polymer-grafted silica support act as adaptive catalysts for the hydrogenation of bicyclic heteroaromatics. Whereas full benzofuran and quinoline derivatives is achieved under pure H2 , introducing CO2 into gas phase leads to effective shutdown arene while preserving activity heteroaromatic part. The selectivity switch originates from generation ammonium formate species surface materials by catalytic . fully reversible, resulting in a robust rapid between two states catalyst adapting its performance response feed composition. A variety were hydrogenated or partially saturated products high yields simply altering composition /CO2 system thus provides controlled access valuable using single rather than specific distinct with static reactivity.

Language: Английский

Citations

7
A 2D Array of Copper(I) Catenane Catalyst Grafted on a Metal-Organic Layer for High Fidelity Cross-Coupling DOI Creative Commons
Yixiang Shi, Lihui Zhu, Yulin Deng

et al.

Published: May 10, 2024

While Earth abundant metals are green and sustainable alternatives to precious for catalytic chemical conversions, the fast ligand exchange involving most of these renders their development into robust, reusable catalysts very challenging. Described in this work is a new type heterogeneous catalyst derived from 2D metal-organic layer (MOL) grafted with catenane-coordinated Cu(I) complexes. In addition good substrate accessibility, easy functionalization other favorable features due MOL support, anchored catenane ligands also provide well-defined coordination environment kinetic stability coordinated Cu(I). Catalytic studies using phenols bromodicarbonyls as substrates showed that catenane-grafted resulted exclusive C–O coupling substrates, whereas control which catenanes replaced by non-interlocked macrocyclic was found lead C–C uncontrolled formation oxidized copper active site. The integration mechanically interlocked extended framework support thus represent an unexplored potential exploiting labile, Earth-abundant catalysis under challenging conditions.

Language: Английский

Citations

2
Speed Tuning of the Formation/Dissociation of a Metallorotaxane DOI
Yoko Sakata,

Ryosuke Nakamura,

Toshihiro Hibi

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(11)

Published: Jan. 11, 2023

Switching between the formation/dissociation of rotaxanes is important to control function various types rotaxane-based materials. We have developed a convenient and simple strategy, so-called "accelerator addition", make static rotaxane dynamic without apparently affecting chemical structure. As an interlocked molecule that enables tuning speed, metallorotaxane was quantitatively generated by complexation triptycene-based dumbbell-shaped mononuclear complex, [PdL2 ]2+ (L=2,3-diaminotriptycene), with 27C9. result inertness Pd2+ -based coordination structure, slowly formed (the state). This formation accelerated 27 times simply adding Br- as accelerator A similar drastic acceleration also demonstrated during dissociation process when Cs+ added form free axle 27C9-Cs+ complex.

Language: Английский

Citations

6
The Mobility of Homomeric Lasso‐ and Daisy Chain‐Like Rotaxanes in Solution and in the Gas Phase as a means to Study Structure and Switching Behaviour DOI Creative Commons
Adrián Saura-Sanmartín, Christoph A. Schalley

Israel Journal of Chemistry, Journal Year: 2023, Volume and Issue: 63(7-8)

Published: March 14, 2023

Abstract A precise structural determination of supramolecular architectures is a non‐trivial challenge. This daunting task can be made even more difficult when interlocked species are to analysed having macrocycles covalently equipped with thread as repeating units, such molecular lassos and daisy chains. When functionalized included scaffolds, different products analogous NMR spectra well dynamic libraries obtained. Furthermore, if control over the motion parts relative each other achieved, full understanding machinery's operation mechanism requires detailed insight into structures involved. also helps designing improved synthetic machines. Diffusion‐ordered spectroscopy ion‐mobility MS techniques ideal tools study compounds in depth. review covers recent examples on use above‐mentioned characterize these architectures.

Language: Английский

Citations

5