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
Andre Seco, Shilin Yu, Arnaud Tron, Nathan D. McClenaghan, Fernando Pina, A. Jorge Parola, Nuno Basilio
Summary: A linear double pyridinium-terminated thread with a central chalcone moiety provides two independent binding sites for cucurbit[7]uril macrocycles in water. The association leads to [2] and [3] pseudorotaxanes, which are pH and photosensitive, with enhanced association upon switching to the cationic flavylium form. Threading the flavylium moiety into CB7 results in a significant increase in fluorescence quantum yield.
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)
Review
Chemistry, Organic
Adrian Saura-Sanmartin
Summary: Rotaxanes are mechanically interlocked molecules consisting of a thread surrounded by a wheel. They are widely used in the research of artificial molecular machines. This review article focuses on recent applications of pseudorotaxanes and rotaxanes, where dethreading processes play a crucial role in achieving the desired function.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yoko Sakata, Ryosuke Nakamura, Toshihiro Hibi, Shigehisa Akine
Summary: Switching between formation and dissociation of rotaxanes is important for controlling the function of rotaxane-based materials. We developed a convenient strategy called accelerator addition to make a static rotaxane dynamic without affecting the chemical structure. By complexing [PdL2](2+) (L=2,3-diaminotriptycene) with 27C9, a metallorotaxane was quantitatively generated, allowing for tuning of formation and dissociation speed. Addition of Br- accelerated rotaxane formation by 27 times, while Cs+ accelerated dissociation, forming the free axle [PdL2](2+) and the 27C9-Cs+ complex.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Emily P. Bacher, Kevin J. Koh, Antonio J. Lepore, Allen G. Oliver, Olaf Wiest, Brandon L. Ashfeld
Summary: A phosphorus(III)-mediated dearomatization of ortho-substituted dianiline squaraine dyes led to the formation of exotic benzofuranone and oxindole scaffolds with a linear side chain comprised of an enol, a phosphorus ylide, and 2,4-disubstituted aniline. Mechanistic evaluation revealed a significant dependence on the acidity of the aniline ortho substituent, with the rearrangement adducts reverting back to the parent squaraine in the presence of a Bronsted acid.
Article
Chemistry, Multidisciplinary
James H. May, Jeff M. Van Raden, Ruth L. Maust, Lev N. Zakharov, Ramesh Jasti
Summary: In this study, a series of mechanically interlocked carbon nanostructures were synthesized using an active-template method. By catalyzing the reactions between a [n]cycloparaphenylene precursor macrocycle and metal ions, fully pi-conjugated catenanes and a [3]rotaxane were obtained. The developed synthetic method of mechanically interlocked carbon nanostructures can contribute to the understanding of the implications of mechanical bonding and provide insights into the structure-property relationships.
Editorial Material
Chemistry, Multidisciplinary
Daehyun Ahn, Nowshin Kabir, Thirumurugan Prakasam, Ali Trabolsi
Summary: The development of analytical tools over the past three decades has enabled the study of increasingly complex mechanically inter-locked molecules. The first synthesis of a [2]catenane by Edel Wasserman in 1960 was controversial due to the lack of experimental evidence. Recently, Leigh et al. re-examined this pioneering synthesis using modern techniques, confirming its structure in the Journal of the American Chemical Society.
Article
Chemistry, Inorganic & Nuclear
Caiyun Liu, Chang Gao, Amir Said, Huihui Niu, Dexin Wang, Chen-Ho Tung, Yifeng Wang
Summary: Catenane, rotaxane, and pseudorotaxane molecules based on a cyclic titanium oxide cluster and cyclic/linear alkylammonium cations were synthesized and shown to remain intact in acidic water, promising for assembling inorganic-organic hybrid supramolecular structures in water.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Grace Turner, Andrew Docker, Paul D. Beer
Summary: A novel halogen bonding (XB) motif has been successfully incorporated into a [2]rotaxane using a discrete chloride anion template directed clipping methodology. Anion titration experiments show that the interlocked host can strongly bind halide and sulfate oxoanions in competitive aqueous-organic solvent mixtures. Compared to a hydrogen bonding rotaxane analogue, the XB rotaxane exhibits a preference towards lighter halides Cl- ≈ Br- > SO42- > I-.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Organic
Gianpiero Cera, Margherita Bazzoni, Leonardo Andreoni, Federica Cester Bonati, Chiara Massera, Serena Silvi, Alberto Credi, Andrea Secchi, Arturo Arduini
Summary: Heteroditopic calix[6]arenes are widely used in synthetic receptors and supramolecular threaded structures, with the introduction of phenylthioureido groups significantly impacting the conformation and properties of the macrocycle. The stability of the complexes is determined by the number of phenylthioureido units in the macrocyclic host and the nature of the counterions of the bipyridinium guest.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
S. Maryamdokht Taimoory, Xiao Yu, Ngong Kodiah Beyeh, Sarah Nasri, John F. Trant
Summary: Mono-(bis)benzimidazoliums were evaluated for their potential as pseudopolyrotaxane axle building blocks through a combination of experimental and computational methods. Their aggregation and photophysical behavior were studied, revealing the potential to form pseudorotaxanes with tunable optical behavior.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jamie T. T. Wilmore, Yuen Cheong Tse, Andrew Docker, Caspar Whitehead, Charlotte K. K. Williams, Paul D. D. Beer
Summary: A series of dynamic metalloporphyrin [2]rotaxane molecular shuttles were synthesized with high yield using active metal template synthetic methodology. The dynamic macrocycle translocation is controlled by an inter-component co-ordination interaction between the macrocycle pyridyl and axle Zn(II) metalloporphyrin. The shuttling behavior can be inhibited by a neutral Lewis base, but can be tuned through rotaxane demetallation or subsequent metallation.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Andrei S. Baluna, Albano Galan, David A. . Leigh, Gareth D. Smith, Justin T. J. Spence, Daniel J. Tetlow, Inigo J. Vitorica-Yrezabal, Min Zhang
Summary: We repeated the earliest claimed catenane synthesis reported by Wasserman over 60 years ago to investigate the formation of mechanically interlocked rings through a nontemplate, statistical synthesis. Using modern synthetic methods, we reconstructed Wasserman's deuterium-labeled macrocycle and other building blocks on a scale necessary to generate approximately 1 mg of catenane. We employed advanced spectroscopic and chemical techniques to detect, isolate, and prove the structure of a putative [2]catenane consisting of a 34-membered cyclic hydrocarbon mechanically linked with a 34-membered cyclic alpha-hydroxyketone.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Sawsen Cherraben, Jeremy Scelle, Bernold Hasenknopf, Guillaume Vives, Matthieu Sollogoub
Summary: A family of cyclodextrins functionalized with different numbers of amines can control the rate of their threading and dethreading on a molecular axle based on pH and substitution pattern. The uniqueness of this system lies in the ability to directly control the switch rate by operating the stimulus on the macrocycle.
Article
Chemistry, Multidisciplinary
Anna J. McConnell
SUPRAMOLECULAR CHEMISTRY
(2018)
Article
Chemistry, Multidisciplinary
Evan N. Keyzer, Alexandru Sava, Tanya K. Ronson, Jonathan R. Nitschke, Anna J. McConnell
CHEMISTRY-A EUROPEAN JOURNAL
(2018)
Article
Chemistry, Multidisciplinary
Marc Lehr, Tobias Paschelke, Eicke Trumpf, Anna-Marlene Vogt, Christian Naether, Frank D. Soennichsen, Anna J. McConnell
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Review
Chemistry, Multidisciplinary
Anna J. McConnell, Andrew Docker, Paul D. Beer
Article
Chemistry, Multidisciplinary
Claudia Caltagirone, Emily R. Draper, Michaele J. Hardie, Cally J. E. Haynes, Jennifer R. Hiscock, Katrina A. Jolliffe, Marion Kieffer, Anna J. McConnell, Jennifer S. Leigh
Summary: This Essay highlights the importance of DEI/EDI in chemistry and the natural sciences, particularly focusing on equality, diversity, and inclusion for women in supramolecular chemistry. Survey data reveals the barriers faced by individuals needing support, such as career breaks and mentorship during the post-PhD stage.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Marc Lehr, Tobias Paschelke, Victoria Bendt, Andre Petersen, Lorenz Pietsch, Patrick Harders, Anna J. McConnell
Summary: The synthesis of ligands for metal-organic cages is often time-consuming and challenging, hindering the discovery and application of new cages. A highly efficient copper-free one-pot Sonogashira-type coupling method has been developed to synthesize symmetric diarylalkyne ligands for Co4L6 cages directly from aryl halide precursors. This method simplifies ligand synthesis and enables the preparation of functionalized ligands for various applications.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Patrick Harders, Thomas Griebenow, Artjom Businski, Anton J. Kaus, Lorenz Pietsch, Christian Naether, Anna J. McConnell
Summary: Amidoboronates were synthesized as a mixture of up to three isomers through reductive coupling of N-aryl iminoboronates with cobaltocene or decamethylcobaltocene in acetonitrile. The interconversion between rac(5) and rac(6) isomers was studied, with the rac(6) isomer predominating when based on pyrocatechol. Catechol exchange altered the rac(5)/rac(6) distribution, with the rac(5) isomer becoming the major isomer following exchange.
Editorial Material
Chemistry, Multidisciplinary
Patrick Harders, Thomas Griebenow, Artjom Businski, Anton J. Kaus, Lorenz Pietsch, Christian Naether, Anna J. McConnell
Editorial Material
Chemistry, Multidisciplinary
Claudia Caltagirone, Emily R. Draper, Jennifer S. Leigh, Cally J. E. Haynes, Jennifer R. Hiscock, Anna J. McConnell
FRONTIERS IN CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Daniel Hugenbusch, Marc Lehr, Jan-Simon von Glasenapp, Anna J. McConnell, Rainer Herges
Summary: We report the photo-switching properties of two regioisomeric diazocine ligands. The self-assembly of these ligands with Co-II ions was studied, and reversible transformation between different ligand configurations and Co-II complexes was achieved through light-controlled switching.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Editorial Material
Chemistry, Multidisciplinary
Jennifer S. Leigh, Nathalie Busschaert, Cally J. E. Haynes, Jennifer R. Hiscock, Kristin M. Hutchins, Larissa K. S. von Krbek, Anna J. McConnell, Anna G. Slater, David K. Smith, Emily R. Draper
Summary: This article is based on interviews with members of the supramolecular chemistry community, including..., whose identities are kept anonymous to protect their privacy.
NATURE REVIEWS CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Tobias Paschelke, Eicke Trumpf, David Grantz, Malte Pankau, Niclas Grocholski, Christian Naether, Frank D. Soennichsen, Anna J. Mcconnell
Summary: In this study, a family of (Fe4L6)-L-II spin-crossover cages based on 2,2'-pyridylbenzimidazoles was reported, and it was found that subtle ligand modifications can lower the spin crossover temperature in CD3CN by up to 186 K. Comparing different pairs of cages, it was observed that CH3 substituents on either the coordination motif or phenylene linker can lower the spin-crossover temperature by different degrees, attributed to electronic effects, steric effects, and a combination of both. The understanding of the interplay between ligand modifications from this study could contribute to the improved rational design of spin-crossover cages.
DALTON TRANSACTIONS
(2023)
Review
Chemistry, Inorganic & Nuclear
Anna J. McConnell
Summary: This Perspective describes how amidoboronates open up new chemical space spanning the areas of BN-heterocycles and dynamic covalent chemistry. BN-containing heterocycles offer the potential to access new properties and reactivity compared to their C-C analogues. Amidoboronates are introduced as a new class of B-N heterocycles that can be synthesised in three isomeric forms (meso(5), rac(5) and rac(6)) from the reductive coupling of N-aryl iminoboronates. Furthermore, initial investigations on the dynamic covalent chemistry of amidoboronates are discussed, such as the reversibility of C-C bond formation following the reductive coupling and tuning the rac(5)/rac(6) ratio via dynamic covalent B-N and B-O bonds.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Marc Lehr, Tjorge Neumann, Christian Naether, Anna J. McConnell
Summary: A new class of CO-releasing molecules, M-CPOnes, was prepared by combining cyclopropenone-based ligands with the modular scaffold of transition metal complexes. These molecules are stable in the dark but undergo light-triggered CO release, allowing the tuning of their photophysical properties. The modularity of M-CPOnes and the potential for further functionalization of the ligand make them appealing for tailored functionality in applications.
DALTON TRANSACTIONS
(2022)
Review
Chemistry, Multidisciplinary
Anna J. McConnell
Summary: This tutorial review introduces the principles for designing metallosupramolecular cages, with a focus on the design of large and lower symmetry cages. The characterization and identification of cages rely on complementary techniques such as NMR spectroscopy, mass spectrometry, X-ray crystallography, and computational methods. Finally, examples of cages are discussed where these design principles and characterization techniques are applied for specific applications or functions of the cages.
CHEMICAL SOCIETY REVIEWS
(2022)
