Article
Chemistry, Multidisciplinary
Faustine d'Orchymont, Jason P. Holland
Summary: This article describes a rotaxane-based approach to synthesizing radiolabeled proteins and peptides for molecular imaging of cancer biomarkers in vivo. The technology provides a platform to explore how mechanical bonding can improve drug delivery, enhance tumor specificity, control radiotracer pharmacokinetics, and reduce dosimetry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Inorganic & Nuclear
Federico Nicoli, Erica Paltrinieri, Marina Tranfic Bakic, Massimo Baroncini, Serena Silvi, Alberto Credi
Summary: Living systems rely on ions and molecules for information processing and motion control. Artificial mimics of biomolecular systems have been developed, and their combination can produce logic-controlled nanomachines with great potential for applications. These systems may lead to the development of 'molecular robots' capable of executing specific functions based on environmental stimuli.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Zhanqi Cao, Dongpu Wu, Mengzhen Li, Fan Yang, Zhikai Li, Wankai An, Song Jiang, Xin Zheng, Caoyuan Niu, Dahui Qu
Summary: In this paper, a linear-cyclic reversible topological structure polymer based on the bistable [1]rotaxane molecular shuttle is designed and prepared. The structural transformation between linear and cyclic state of the polymer is demonstrated by acid-base stimuli.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Leonardo Andreoni, Giovanni Mariano Beneventi, Gabriele Giovanardi, Gianpiero Cera, Alberto Credi, Arturo Arduini, Andrea Secchi, Serena Silvi
Summary: We synthesized and characterized a dansyl calix[6]arene derivative and its pseudorotaxane complex, and found that it has remarkable complexation ability. The dansyl moieties in the derivative can signal the state of the system through fluorescence, be reversibly protonated to modulate the complexation abilities, and participate in photoinduced electron transfer processes to tune the stability of the complex.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Gui-Yuan Wu, Chao Liang, Yi-Xiong Hu, Xu-Qing Wang, Guang-Qiang Yin, Zhou Lu
Summary: In this study, a discrete rhomboidal metallacycle R was successfully synthesized and a new family of cross-linked supramolecular polymers was formed by reacting a bis-[2]pseudorotaxane metallacycle with a bis-pillar[5]arene. These polymers exhibited interesting redox-responsive properties, with weight-average diffusion coefficients D adjusted by changing the redox state of the Cu(i)/Cu(ii) complexes.
Article
Chemistry, Multidisciplinary
Rebecca L. L. Spicer, Curtis C. C. Shearman, Nicholas H. H. Evans
Summary: This study presents the synthesis of two mechanically chiral rotaxanes with urea and squaramide motifs, with yields of 33% and 22% respectively. H-1 NMR spectroscopic titrations reveal the possibility of shuttling the macrocycle, detectable through modulation of mechanical chirality expression in the NMR spectrum, by the addition of achiral chloride anions, which can be reversed by the addition of sodium cations.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Pablo Corton, Natalia Fernandez-Labandeira, Mauro Diaz-Abellas, Carlos Peinador, Elena Pazos, Arturo Blanco-Gomez, Marcos D. Garcia
Summary: A new polycationic pseudo[1]rotaxane was successfully synthesized through hydrazone bonds, self-assembled in excellent yield in aqueous media. The thermodynamically controlled process involves the [1 + 1] reaction of a bisaldehyde and a trishydrazine, formation of the macrocyclic part, conversion into pseudo[1]rotaxane, and the one-pot [1 + 1 + 1] condensation process. The obtained molecule exhibited the ability to form self-inclusion complexes and supramolecular aggregates in different concentration ranges.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Miguel A. Soto, Veronica Carta, Ingrid Suzana, Brian O. Patrick, Francesco Lelj, Mark J. MacLachlan
Summary: Macrocycle engineering is a key topic in supramolecular chemistry. This study combines different approaches and post-synthetic modifications to transform a single tether into multiple rings. The macrocycles undergo redox reactions, allowing for control of conformational changes and host activity, enabling the capture and release of guests, ring transformations, and control of pseudorotaxane-to-pseudorotaxane conversions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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)
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
Bingbing Shi, Xupeng Li, Yongping Chai, Peng Qin, Yi Zhou, Wen-Juan Qu, Qi Lin, Tai-Bao Wei, Yan Sun, Peter J. Stang
Summary: In this study, a [2]rotaxane was efficiently prepared by the host-guest complexation between a platinum(II) metallacycle and a polycyclic aromatic hydrocarbon molecule, naphthalene. The [2]rotaxane was further utilized in the fabrication of an efficient light-harvesting system. This work provides a significant supplement to macrocycle-based host-guest systems and demonstrates a strategy for the efficient production of well-defined mechanically interlocked molecules with practical applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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
Sayaka Hoshino, Kosuke Ono, Hidetoshi Kawai
Summary: In this study, ring-over-ring deslipping process was successfully observed through the cleavage of imine bridges under dynamic equilibrium, revealing that steric hindrance between rings and reduced mobility of larger macrocycle M are the key factors affecting the deslipping process.
FRONTIERS IN CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Johnny Hu, Sonia Adrouche, Etienne S. Gauthier, Nolwenn Le Breton, Marco Cecchini, Christophe Gourlaouen, Sylvie Choua, Valerie Heitz, Henri-Pierre Jacquot de Rouville
Summary: A [2]rotaxane built around a multi-responsive bis-acridinium macrocycle has been synthesized, and its interlocked nature and conformational dynamics have been investigated. The mechanical response and electronic changes in the bis-acridinium [2]rotaxane were explored using halochromic and redox-switching properties, and easily detected by UV/Vis spectroscopy and electrochemistry.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Yosuke Akae, Jun Sawada, Ken Nakajima, Toshikazu Takata
Summary: A rotaxane crosslinker (RC) toughens rotaxane crosslinked polymer (RCP) through a stress dispersion effect attributed to the movable nature of the crosslinking structure. In this study, a series of structure-definite RCs with different axle end structures or wheel components were synthesized and used to create RCPs. Analysis showed that the size of the axle end structure and the type of rotaxane crosslinker affected the toughening effect, with [3]rotaxane crosslinker being more effective than [2]rotaxane. The mobility of the crosslinking points, specifically rotational and flipping movements, was found to be crucial for toughening RCPs.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Anquan Li, Zhengqi Tan, Yiheng Hu, Zonghuan Lu, Jun Yuan, Xia Li, Jialin Xie, Jiangwei Zhang, Kelong Zhu
Summary: An unprecedented molecular pumping cassette was designed and implemented for the construction of molecular necklaces, including radial [n]catenanes and a pair of [3]catenane diastereomers. This success offers new insights into complex molecular architectures and expands the application of molecular machines in synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Eva Meirovitch, Zhichun Liang, Robert W. Schurko, Stephen J. Loeb, Jack H. Freed
Summary: The application of the microscopic-order-macroscopic-disorder (MOMD) approach for analyzing dynamic H-2 NMR lineshapes in metal-organic frameworks (MOFs) is described in this study. By comparing the experimental results of UiO-68-d(4) and UWDM-9-d(4), it is found that MOFs with different structures exhibit different dynamic characteristics, and the phenyl-d(4) dynamics is more isotropic in a more crowded environment.
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Chemistry, Multidisciplinary
Wanqian Lv, Yunyi Song, Xinyuan Lv, Jun Yuan, Kelong Zhu
Summary: A pair of selenanthrene-bridged molecular cages were synthesized using a one-step cyclization reaction. One cage featured a tubular belt-shaped structure with an adaptable cavity that can accommodate electron-deficient guests. The other cage had a Mobius strip structure and exhibited slower twist-migration dynamics. The use of selenanthrene as joints provides an alternative method for designing and regulating the properties of molecular cages.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Mengdi Lin, Lifang Bian, Qing Chen, Houyang Xu, Zhichang Liu, Kelong Zhu
Summary: Macrocyclization of 2,7-dimethoxythianthrene with methylene linkages resulted in homochiral macrocycles with a hex-nut-like structure. Characterization of their structures was done using NMR spectroscopy, mass spectrometry, and X-ray diffraction analysis. The macrocycles exhibited stable planar chirality, enabling efficient resolution of enantiomers and easy derivatization. Addition of phenylethynyl groups led to luminescent tubular macrocycles with circularly polarized luminescence and potential for the development of switchable chiroptical systems through supramolecular binding.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Zonghuan Lu, Hongyi Liu, Xinyuan Lv, Wanqian Lv, Yandie Liu, Kelong Zhu
Summary: A series of hinge-like molecules, dipyrrolo-1,4-dithiins (PDs), were synthesized and characterized. The fusion of pyrroles with 1,4-dithiins resulted in increased redox-activity and susceptibility to radical cations. The PDs displayed flexible molecular geometries that could be regulated by crystal packing or host-guest complexation, and showed excellent donor properties in forming inclusion complexes.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Zonghuan Lu, Wanqian Lv, Hongyi Liu, Yandie Liu, Shuhua Liao, Xijie Wang, Kelong Zhu
Summary: A pyrrolodithiin-derived cyclophane with an adaptive and stimuli-responsive geometry was designed and constructed. The foldable dithiin subunit enabled the cyclophane to have a compressible cavity that can transform from a hex-nut to a rectangular box upon complexing guests. The resulting pseudorotaxane complexes can be dethreaded via electrochemical oxidation, highlighting the potential applications in molecular switches and machines.
Article
Chemistry, Multidisciplinary
Ayan Dhara, Anton Dmitrienko, Rahaf N. N. Hussein, Ariel Sotomayor, Benjamin H. H. Wilson, Stephen J. J. Loeb
Summary: A rigid H-shaped [2]rotaxane molecular shuttle was synthesized, which consists of an axle containing benzimidazole recognition sites and a central bipyridyl group interlocked with a 24-crown-8 wheel. The central bipy unit acts as a speed bump that raises the barrier to shuttling for the [2]rotaxane. Coordination of a PtCl2 moiety to the bipy unit creates a steric barrier to shuttling, while addition of Zn(II) ions allows shuttling to occur through a ligand exchange mechanism.
Article
Chemistry, Multidisciplinary
Xia Li, Jialin Xie, Zhenglin Du, Long Jiang, Guangqin Li, Sanliang Ling, Kelong Zhu
Summary: A zirconium metal-organic framework with a T-shaped benzimidazole strut was constructed and successfully used as a sponge-like material for selectively absorbing macrocyclic guests. The binding process was reversible and acid-base switchable. This study provides an alternative route for creating complex functional materials with interpenetrated structures.
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, Multidisciplinary
Jun Yuan, Wanqian Lv, Anquan Li, Kelong Zhu
Summary: A novel metallamacrocycle incorporating thianthrene was designed and synthesized, showing strong binding affinity, adaptive complexation, and redox activity. It efficiently binds fullerenes and provides insights into the design of supramolecular hosts.
CHEMICAL COMMUNICATIONS
(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, Multidisciplinary
Shenghua Wang, Jun Yuan, Jialin Xie, Zonghuan Lu, Long Jiang, Yingxiao Mu, Yanping Huo, Yoshitaka Tsuchido, Kelong Zhu
Summary: The study successfully synthesized cyclothianthrenes, a series of sulphur-embedded hydrocarbon belts proposed a decade ago, including [6]cyclothianthrene and [8]cyclothianthrene. These molecules exhibit unique features such as prism-like conformations with well-defined tubular cavities and redox activity, enriching the chemistry of heteroatom-doped molecular belts and tubes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Houyang Xu, Meng-Di Lin, Jun Yuan, Baiyang Zhou, Yingxiao Mu, Yanping Huo, Kelong Zhu
Summary: A fluorescent T-shaped benzimidazole was successfully incorporated into a bicyclic macrocycle to form a suitane through supramolecular templated-synthesis, resulting in enhanced fluorescence emission. This method provides a potential pathway for the development of new complex fluorescent materials by taking advantage of mechanical bonding and molecular packing.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Benjamin H. Wilson, Louae M. Abdulla, Robert W. Schurko, Stephen J. Loeb
Summary: In this study, a new [2]rotaxane molecular shuttle linker based on the binding of a 24-crown-8 ether macrocycle at a benzimidazole recognition site was synthesised and characterised. The translational motion of the molecular shuttle was studied both in solution and in the solid state. Incorporation of mesitylene into the pores of UWDM-11 was found to significantly increase the barrier for thermally driven translation of the macrocycle.
Article
Chemistry, Physical
Ghazale Gholami, Benjamin H. Wilson, Kelong Zhu, Christopher A. O'Keefe, Robert W. Schurko, Stephen J. Loeb
Summary: Two Zr(IV) metal-organic frameworks (MOFs) were studied, incorporating a new H-shaped tetracarboxylate linker with [2]rotaxane molecular shuttles. Solid-state NMR and solution NMR spectra confirmed the successful incorporation of the [2]rotaxanes, while the study found that the structure of the linker affects the shuttling rate of the macrocyclic ring.
FARADAY DISCUSSIONS
(2021)
