Article
Chemistry, Multidisciplinary
Wei-Jian Li, Wei-Tao Xu, Xu-Qing Wang, Yefei Jiang, Yu Zhu, Dan-Yang Zhang, Xiao-Qin Xu, Lian-Rui Hu, Wei Wang, Hai-Bo Yang
Summary: A new family of photoresponsive rotaxane-branched dendrimers was successfully designed and synthesized for the construction of novel soft actuators. The precisely arranged rotaxane units can undergo collective and amplified motions upon alternate irradiation with UV and visible light, enabling controllable and reversible dimension modulation. These photoresponsive dendrimers were further utilized to construct macroscopic soft actuators that exhibit fast shape transformation behaviors and can perform weight-lifting and cargo transporting upon light control.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Jesus de Maria Perez, Julio Puigcerver, Tainara Orlando, Aurelia Pastor, Marcos A. P. Martins, Mateo Alajarin, Alberto Martinez-Cuezva, Jose Berna
Summary: In this study, a series of succinamide-based hydrogen-bonded [2]rotaxanes with acyclic secondary amine as the catalytically active sites were synthesized and evaluated for their catalytic activity in an iminium-type process. The presence of an interlocked polyamide macrocycle notably increased the catalytic efficiency of the entwined organocatalysts by rapidly forming a reactive iminium intermediate with the aldehyde. The hydrogen-bonding interaction between the macrocycle and the electrophile plays a crucial role in the rapid formation and stabilization of the key intermediate.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Giorgio Baggi, Benjamin H. Wilson, Ayan Dhara, Christopher A. O'Keefe, Robert W. Schurko, Stephen J. Loeb
Summary: An H-shaped [2]rotaxane composed of a bis(benzimidazole) axle and a 24-membered crown ether wheel with four trityl groups forms a highly crystalline material allowing large amplitude motion of the interlocked macrocycle, characterized using variable-temperature (VT) H-2 solid-state nuclear magnetic resonance (SSNMR).
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Somnath Bej, Mandira Nandi, Pradyut Ghosh
Summary: A new multi-functional [2]rotaxane, ROTX, was synthesized and functionalized with pyrene moieties to develop a bifluorophoric [2]rotaxane, PYROTX. Metal ion sensing studies showed that ROTX is selective for Zn(II) and Cd(II), while PYROTX exhibits exclusive selectivity towards Zn(II) over various other metal ions.
DALTON TRANSACTIONS
(2021)
Article
Biochemical Research Methods
Peiqiao Wu, Bhushan Dharmadhikari, Prabir Patra, Xingguo Xiong
Summary: In this study, molecular simulation was performed to investigate the switching mechanism of [2]rotaxane molecules. The results show that the solvent environment plays an important role in the switching characteristics of [2]rotaxane molecules. The switching behavior of [2]rotaxane is stable, controllable, reversible, and repeatable, indicating the potential for molecular memory and logic applications.
JOURNAL OF MOLECULAR GRAPHICS & MODELLING
(2022)
Article
Chemistry, Multidisciplinary
Qiu-yan Jin, Liao Meng, Zhi-hui Zhang, Yuan-yuan Liang, Wei Jin, Kong-qiu Hu, Li-yong Yuan, Zhi-fang Chai, Lei Mei, Wei-qun Shi
Summary: This study reports a novel metal-organic rotaxane compound with multi-responsive capability to both light and thermal stimuli. The compound exhibits photochromic behavior after light irradiation and exceptional thermal response in the form of volume expansion followed by contraction. These findings demonstrate the potential of such supramolecular assemblies as smart molecular components for applications such as sensors and switches.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Rosemary J. Goodwin, Andrew Docker, Hugo MacDermott-Opeskin, Heather M. Aitken, Megan L. O'Mara, Paul D. Beer, Nicholas G. White
Summary: This article describes the synthesis of two [2]rotaxanes containing interlocked three-dimensional binding cavities, with one receptor showing a higher selectivity preference for chloride ions. X-ray crystal structures showed the encapsulation of chloride ions within the binding cavity, with computational simulations indicating secondary intermolecular interactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Maxime Gauthier, Frederic Coutrot
Summary: This study synthesized new pH-sensitive [2]rotaxane molecular shuttles and found that the Weinreb amide was not a suitable secondary molecular station for DB24C8, while the ketone was successfully used for this purpose.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Multidisciplinary Sciences
Jun-shan Geng, Lei Mei, Yuan-yuan Liang, Li-yong Yuan, Ji-pan Yu, Kong-qiu Hu, Li-hua Yuan, Wen Feng, Zhi-fang Chai, Wei-qun Shi
Summary: The authors synthesized metal-organic rotaxane frameworks that exhibit macro-mechanical responses to light irradiation. This breakthrough has implications in the development of photoactuator devices as well as emerging fields such as optomechanical microdevices and smart microrobotics.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Shilin Yu, Arkady Kupryakov, James E. M. Lewis, Vicente Marti-Centelles, Stephen M. Goldup, Jean-Luc Pozzo, Gediminas Jonusauskas, Nathan D. McClenaghan
Summary: This paper demonstrates the first example of bidirectional reversible electronic energy transfer (REET) within a rotaxane, showing that cation binding can modulate the axle chromophore energy levels and provide a luminescence read-out. Modulation of REET processes represents an unexplored mechanism in luminescent molecular sensor development.
Article
Chemistry, Multidisciplinary
Lei-Min Zhao, Li-Shuo Zheng, Xiaoping Wang, Wei Jiang
Summary: This study reports a molecular shuttle based on a rotaxane, which is influenced by an acid-responsive asymmetric macrocycle. Upon protonation induced by trifluoroacetic acid (TFA), the macrocycle translocates and the shuttling kinetics are hindered by steric hindrance. The shuttling kinetics depend on the concentration of TFA and a kinetic intermediate can be captured.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Xia Li, Jialin Xie, Zhenglin Du, Ruiyang Yu, Jianhua Jia, Zhong Chen, Kelong Zhu
Summary: A mechanically interlocked [3]rotaxane was designed, synthesized, and used as a ligand for constructing metal-organic frameworks (MOFs). The nano-confinement effect of macrocycles rigidifies the flexible ligand and coordinates it to zinc(ii) ions, resulting in the formation of two- or three-dimensional MOFs under controlled conditions.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Jiang-Xiong Yang, Ze Li, Xu-Hai Gu, Tian-Guang Zhan, Jiecheng Cui, Kang-Da Zhang
Summary: In this study, a photoswitchable [2]rotaxane with unique photogated macrocyclic shuttling was constructed, enabling control over the shuttling movement through photoisomerization and cycloaddition reactions. This provides a new approach to improve the switching controllability of rotaxane, beneficial for fabricating high-performance rotaxane-based nanosystems and materials.
Article
Chemistry, Multidisciplinary
Mingoo Jin, Rempei Ando, Marcus J. Jellen, Miguel A. Garcia-Garibay, Hajime Ito
Summary: The study introduces a novel design of emission crystalline molecular rotors with the ability to rotate elements based on the type of implanted metal. The activation energy for rotation can be tuned by changing the metal, impacting the energy barrier and electronic stabilization during rotational motion. The design provides a platform for manipulation of rotary dynamics and solid-state emission in crystalline molecular materials.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Chengyuan Yu, Xiaodong Wang, Cai-Xin Zhao, Shun Yang, Jiaan Gan, Zhuo Wang, Zhanqi Cao, Da-Hui Qu
Summary: A bistable [2]rotaxane with a conformation-adaptive macrocycle was synthesized and utilized to probe the molecular shuttling motion. The fluorescence intensity was controlled by the modulation of intramolecular photo-induced electron transfer.
CHINESE CHEMICAL LETTERS
(2022)
News Item
Chemistry, Multidisciplinary
Karine Fournel-Marotte, Frederic Coutrot
Article
Biochemistry & Molecular Biology
Benjamin Riss-Yaw, Justine Morin, Caroline Clavel, Frederic Coutrot
Article
Chemistry, Multidisciplinary
Benjamin Riss-Yaw, Caroline Clavel, Philippe Laurent, Philip Waeles, Frederic Coutrot
CHEMISTRY-A EUROPEAN JOURNAL
(2018)
Article
Chemistry, Organic
Maxime Gauthier, Frederic Coutrot
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2019)
Review
Chemistry, Multidisciplinary
Philip Waeles, Maxime Gauthier, Frederic Coutrot
Summary: The synthesis of interlocked molecules often involves the challenging post-synthetic modifications while conserving the mechanical bond. To overcome synthetic problems, a strategy of synthesizing isolable and storable interlocked building blocks before modification is appealing. The reactivity of functional groups and preservation of the interlocked architecture are closely linked to the fundamental role of the mechanical bond in the strategy employed.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Maxime Gauthier, Victor Koehler, Caroline Clavel, Brice Kauffmann, Ivan Huc, Yann Ferrand, Frederic Coutrot
Summary: A novel rotaxane/foldaxane hybrid architecture was designed and synthesized, with the winding of an aromatic oligoamide helix host around a dumbbell-shaped thread-like guest already surrounded by a macrocycle evidenced by NMR spectroscopy and X-ray crystallography. The position of the macrocycle along the axle and the associated steric hindrance were found to affect this process, with the macrocycle acting as a switchable shield modulating the affinity of the helix for the axle. Conversely, the foldamer helix acted as a supramolecular auxiliary compartmentalizing the axle.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Maxime Gauthier, Frederic Coutrot
Summary: This study synthesized new pH-sensitive [2]rotaxane molecular shuttles and found that the Weinreb amide was not a suitable secondary molecular station for DB24C8, while the ketone was successfully used for this purpose.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Maxime Gauthier, Frederic Coutrot
Summary: This study synthesized and characterized four new DB24C8-based ammonium-containing pseudorotaxanes, and found that the perfluorobutyl extremity of the axle allows for dethreading of DB24C8, with the rate depending on the strength of the template-to-DB24C8 complex and the nature of the axle. The dethreading process may be assisted by the presence of a poor secondary site of interaction for the DB24C8 in the threaded axle, especially when this site is close to the DB24C8.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Philip Waeles, Maxime Gauthier, Frederic Coutrot
Summary: This article reports the synthesis and study of [2]- and [3]rotaxanes based on DB24C8, with ammonium as the best molecular station and carbamate as secondary molecular stations. The post-interlocking synthesis relies on the aminolysis of an activated though insulated pseudorotaxane. The activated carbonate end of the encircled thread allows conversion into mechanically interlocked rotaxanes.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Maxime Gauthier, Philip Waeles, Frederic Coutrot
Summary: Cyclic interlocked molecules have unique restrained tridimensional structure, and preserving the mechanical bond can facilitate post-synthetic intramolecular cyclization. However, the chemical linkage between reactive sites in interlocked rotaxanes remains an underexploited route in post-synthetic reactions.
Article
Chemistry, Multidisciplinary
Maxime Gauthier, Karine Fournel-Marotte, Caroline Clavel, Philip Waeles, Philippe Laurent, Frederic Coutrot
Summary: The synthesis and characterization of a complex interlocked figure-of-eight rotaxane molecular shuttle are reported. The shuttle contains two molecular chains, which can react together through click chemistry. The self-entanglement of the shuttle is driven by the complexation of an ammonium function with a dibenzo-24-crown-8 moiety. The shuttling of the shuttle along the threaded axle is achieved by deprotonation or deprotonation-then-carbamoylation of the ammonium, resulting in two discrete co-conformational states with adjustable folding and size of the loops.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Victor Koehler, Maxime Gauthier, Chenhao Yao, Karine Fournel-Marotte, Philip Waeles, Brice Kauffmann, Ivan Huc, Frederic Coutrot, Yann Ferrand
Summary: This study investigates the wrapping of an aromatic oligoamide helix around an active ester-containing [2]rotaxane, which enforces the sliding and sequestration of the surrounding macrocycle around a part of the axle without any formal affinity. The foldamer-mediated compartmentalization of the [2]rotaxane shuttle was subsequently used to prepare an improbable rotaxane.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Benjamin Riss-Yaw, Thomas-Xavier Metro, Frederic Lamaty, Frederic Coutrot
Article
Chemistry, Multidisciplinary
B. Riss-Yaw, C. Clavel, Ph. Laurent, F. Coutrot
CHEMICAL COMMUNICATIONS
(2017)
Article
Chemistry, Multidisciplinary
Philip Waeles, Karine Fournel-Marotte, Frederic Coutrot
CHEMISTRY-A EUROPEAN JOURNAL
(2017)