Precise Non-Equilibrium Polypropylene Glycol Polyrotaxanes DOI
James S. W. Seale, Bo Song, Yunyan Qiu

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(37), P. 16898 - 16904

Published: Sept. 8, 2022

Traditionally, the synthesis of polyrotaxanes has been limited by synthetic methods that rely on an innate affinity between rings and polymer chains. The use rotaxane-forming molecular pumps allows this limitation to be circumvented in production non-equilibrium which are trapped chains for they have little or no affinity. Pumping cassettes, each composed a bipyridinium unit linked (i) bismethylene bridge terminal 2,6-dimethylpyridinium cationic (ii) methylene group isopropylphenylene steric barrier, were attached using copper-catalyzed azide-alkyne cycloadditions ends polypropylene glycol (PPG) chain number-average weight Mn ≈ 2200. Using one-pot electrosynthetic protocol, series PPG-based with cyclobis(paraquat-p-phenylene) as synthesized. Despite bulk PPG backbone, it was found suitable collecting threading up 10 rings. pumping two is sufficient render these hydrophobic polymers soluble aqueous solution. Their hydrodynamic diameters diffusion constants vary according number pumped nature manifested their gradual degradation dethreading at elevated temperatures.

Language: Английский

What can molecular assembly learn from catalysed assembly in living organisms? DOI
Zhi‐Chao Lei, Xinchang Wang,

Liulin Yang

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(4), P. 1892 - 1914

Published: Jan. 1, 2024

We discuss how living organisms utilize the catalysed assembly (catassembly) way to construct and control complex systems with high efficiency selectivity, we can harness catassembly design functional molecular assemblies.

Language: Английский

Citations

9
Single-Electron Catalysis of Reversible Cycloadditions under Nanoconfinement DOI
Xin Zhu, Hongliang Chen, Jinying Wang

et al.

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

Published: Feb. 6, 2025

Electron transfer (ET) is crucial in many chemical reactions, but its mechanism and role are hardly understood nanobiotechnology due to the complexity of reaction species pathways involved. By modulating monitoring electron behavior at single-molecule level, we can better understand fundamental mechanisms ways control them for technological use. Here, unravel a single-electron catalysis under positively charged nanoconfinement. We demonstrate that both (2 + 2) (4 4) cycloadditions be catalyzed reversibly by single electron. Key discovered sequential electrical signals through advanced detection platforms. Experimental theoretical results consistently combining ET processes with nanoconfinement involving cucurbit[8]uril lower energy barrier promote reversible cycloaddition. Moreover, show bias voltage fine-tune equilibria bond formation cleavage. Our provide novel approach elucidate, modulate, design electron-involved reactions functionalized devices.

Language: Английский

Citations

1
Stable Crystalline Nanohoop Radical and Its Self‐Association Promoted by van der Waals Interactions DOI

Bingxia Hou,

Ke Li,

Huijie He

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(14)

Published: Feb. 9, 2023

A stable nanohoop radical (OR3) combining the structures of cycloparaphenylene and an olympicenyl is synthesized isolated in crystalline state. X-ray crystallographic analysis reveals that OR3 forms a unique head-to-tail dimer further aggregates into one-dimensional chain solid Variable-temperature NMR concentration-dependent absorption measurements indicate π-dimer not formed solution. An energy decomposition indicates van der Waals interactions are driving force for self-association process, contrast with other derivatives favor π-dimerization. The physical properties solution phase have been studied, cationic species obtained by one-electron chemical oxidation. This study offers new molecular design to modulate organic radicals overcoming spin-Peierls transition, prepare novel compounds spin-related properties.

Language: Английский

Citations

21
Electron‐Driven Nitration of Unsaturated Hydrocarbons DOI Creative Commons
Subrata Patra, Ivan Mosiagin, Rahul Giri

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(28)

Published: April 25, 2023

Herein, we introduce an electrochemically assisted generation of nitryl radicals from ferric nitrate under mild reaction conditions using a simple setup with inexpensive graphite and stainless-steel electrodes. The mechanism the is supported by detailed spectroscopic experimental studies. Powered electricity driven electrons, synthetic diversity this has been demonstrated through development highly efficient nitration protocols various unsaturated hydrocarbons. In addition to broad application area, these are easy scale for decagram quantities, exhibit exceptional substrate generality functional-group compatibility.

Language: Английский

Citations

19
Supramolecular Radical Electronics DOI

Tengyang Gao,

Abdalghani Daaoub, Zhichao Pan

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(31), P. 17232 - 17241

Published: July 26, 2023

Supramolecular radical chemistry is an emerging area bridging supramolecular and chemistry, the integration of radicals into architecture offers a new dimension for tuning their structures functions. Although various efforts have been devoted to fabrication junctions, charge transport characterization through remained unexplored due challenges in creating at single-molecule level. Here, we demonstrate investigation junction using electrochemical scanning tunneling microscope-based break (EC-STM-BJ) technique. We found that conductance was more than 1 order magnitude higher without even fully conjugated oligophenylenediamine molecule with similar length. The combined experimental theoretical investigations revealed increased binding energy decreased gap junction, which leads near-resonant radical. Our work demonstrated can provide not only strong but also efficient electrical coupling between building blocks, provides insights materials radicals.

Language: Английский

Citations

18
Analytical noncovalent electrochemistry for battery engineering DOI Creative Commons
Zhao Chang-xin, Xi‐Yao Li, Han Han

et al.

Nature Chemical Engineering, Journal Year: 2024, Volume and Issue: 1(3), P. 251 - 260

Published: March 8, 2024

Despite the fact that noncovalent bonding interactions are ubiquitous, it is primarily those interactions, which amenable to spectroscopic analysis, have been well investigated and applied in chemical engineering. New principles techniques for characterizing required gain insight into their detailed nature explore potential applications. Here we introduce practice of analytical electrochemistry probing such interactions. The strengths can be determined more accurately by electrochemical means than relying on measurements. Specifically, analyses capable recording/identifying minor signals, leading discovery an unexpected 2:1 host–guest complex. Moreover, proposed technique multiple properties facilitates design screening active complexes as catalysts. We also demonstrate achieving a high energy density 495 Wh kg−1 rechargeable batteries. procedure provides fresh perspective supramolecular science takes chemistry closer practical Quantifying strength systems key guiding molecular desired application. Now, quantitative relationship between established new dimension investigations enables control battery

Language: Английский

Citations

8
Artificial molecular pumps DOI
Long Zhang, Huang Wu, Xuesong Li

et al.

Nature Reviews Methods Primers, Journal Year: 2024, Volume and Issue: 4(1)

Published: Feb. 22, 2024

Language: Английский

Citations

7
Precise recognition of benzonitrile derivatives with supramolecular macrocycle of phosphorylated cavitand by co-crystallization method DOI Creative Commons
Heng Li,

Zhijin Li,

Lin Chen

et al.

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

Published: June 22, 2024

The importance of molecular docking in drug discovery lies the precise recognition between potential compounds and their target receptors, which is generally based on computational method. However, it will become quite interesting if rigid cavity structure supramolecular macrocycles can precisely recognize a series guests with specific fragments by mimicking through co-crystallization experiments. Herein, we report phenylphosphine oxide-bridged aromatic macrocycle, F[3]A1-[P(O)Ph]

Language: Английский

Citations

7
Through-Space Conjugated Supramolecular Polymer Radicals from Spatial Organization of Cucurbit[8]uril: An Efficient Approach for Electron Transfer and Smart Photochromism Materials DOI

Haigen Nie,

Yutao Rao, Jianxin Song

et al.

Chemistry of Materials, Journal Year: 2022, Volume and Issue: 34(19), P. 8925 - 8934

Published: Sept. 21, 2022

Electron transfer-based long-lived radicals are highly challenging because of the limited control over relative orientation, distance, electronic coupling, and nonradiative recombination channels donor acceptor on a molecular level. Herein, cavity macrocyclic cucurbit[8]uril (Q[8]) was found to exhibit excellent advantages in controlling orientation distance moieties via spatial organization, i.e., 4-carboxylphenyl appended viologen-derived guest (BcpV2+) elegantly rearranged as rigid linear J-type supramolecular polymer by Q[8] host noncovalent interactions. Thus, an unprecedented photoinduced electron transfer (PET) triggered through-space conjugated organic radical with distinct photochromism NIR-II photothermal effect observed. Further studies have indicated that encapsulation-triggered PET cycle exhibited good repeatability without significant loss its efficiency had potential application fabrication smart windows erasable printing under photoirradiation or sunlight. These results suggest can be used new tool light-energy conversion materials science.

Language: Английский

Citations

23
Functionalization of Supramolecular Polymers by Dynamic Covalent Boroxine Chemistry DOI Creative Commons
Marco D. Preuss, Tobias Schnitzer, Stef A. H. Jansen

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(24)

Published: May 8, 2024

Abstract Molecular scaffolds that enable the combinatorial synthesis of new supramolecular building blocks are promising targets for construction functional molecular systems. Here, we report a scaffold based on boroxine enables formation chiral and ordered 1D polymers, which can be easily functionalized circularly polarized luminescence. The monomers quantitatively synthesized in situ, both bulk solution, from boronic acid precursors cooperatively polymerize into helical aggregates stabilized by threefold hydrogen‐bonding π–π stacking. We then demonstrate amplification asymmetry co‐assembly chiral/achiral co‐condensation classical situ sergeant‐and‐soldiers experiments, respectively, showing fast exchange reactions occurring system. Remarkably, pyrene with results aggregation excimer emission g ‐values order 10 −3 . Yet, electron deficiency boron makes them chemically addressable nucleophiles, but also sensitive to hydrolysis. With this sensitivity mind, provide first insights prospects offered boroxine‐based polymers make addressable, functional, adaptive

Language: Английский

Citations

6