The 2016 Nobel Prize in Chemistry has been jointly awarded to Professors Jean-Pierre Sauvage (University of Strasbourg, France), Sir J. Fraser Stoddart (Northwestern University, Evanston, IL, USA) and Ben L. Feringa (University of Groningen, The Netherlands) “for the design and synthesis of molecular machines.” Sir Fraser is a member of the editorial boards of Chemistry–A European Journal, ChemPlusChem (both owned by ChemPubSoc Europe), Chinese Journal of Chemistry, and Macromolecular Rapid Communications. He was a member of the international advisory board of Angewandte Chemie 1995–2013 (owned by the German chemical society GDCh). He is among the most prolific authors in history for Angewandte with over 125 articles since
1974. He co-edited, among others, Stimulating Concepts in Chemistry and wrote The Nature of the Mechanical Bond. Feringa is a member of the editorial boards of Advanced Synthesis & Catalysis, ChemPhotoChem (ChemPubSoc Europe) and Israel Journal of Chemistry. He co-edited Molecular Switches. Sauvage edited Perspectives in Supramolecular Chemistry: Transition Metals in Supramolecular Chemistry, Volume 5 and co-edited From Non-Covalent Assemblies to Molecular Machines, and Molecular Catenanes, Rotaxanes and Knots.
In the beginning…: The Nobel Prize in Chemistry 2016 goes to three of the pioneers of the field of synthetic molecular machines, Jean-Pierre Sauvage, Sir J. Fraser Stoddart, and Ben L. Feringa. Their work has led from the reliable synthesis of rotaxanes and catenanes (see picture) to molecular rotary motors, shuttles, muscles, and other devices.
Angew. Chem. Int. Ed. 10.1002/anie.201609841 [Highlight]
In this virtual issue, we feature a selection of papers by the Nobel Laureates on molecular machines that have been published in Wiley-VCH journals. The selected articles include both recent contributions and classic reports on the discoveries that led to the Nobel Prize.
Articles by J. F. Stoddart
Modulating the Binding of Polycyclic Aromatic Hydrocarbons Inside a Hexacationic Cage by Anion–π Interactions
Nema Hafezi, James M. Holcroft, Karel J. Hartlieb, Edward J. Dale, Nicolaas A. Vermeulen, Charlotte L. Stern, Amy A. Sarjeant, J. Fraser Stoddart*
The ins and outs: A hexacationic macrobicyclic receptor comprised of pyridinium units fused together by electron-poor triazine rings has been shown to be a good receptor for polycyclic aromatic hydrocarbons. The lower than expected association constant for the PF6− salt with pyrene is attributed to the PF6− counterions fleetingly occupying the cavity. X-ray crystallography confirmed the presence of a PF6− ion in its cavity.
Angew. Chem. Int. Ed. 2015, 54, No. 2, 456–461 [Communication]
J. Fraser Stoddart*
Angew. Chem. Int. Ed. 2014, 53, No. 42, 11102–11104 [Editorial]
Yu-Long Sun, Ying-Wei Yang*, Dai-Xiong Chen, Guan Wang, Yue Zhou, Chun-Yu Wang, J. Fraser Stoddart*
Mechanized silica nanoparticles, equipped with pillararene-pseudorotaxane nanovalves, operate in biological media to trap cargos within their nanopores, but release them when the pH is lowered or a competitive binding agent is added. Although cargo size plays an important role in cargo loading, cargo charge-type does not appear to have any significant influence on the amount of cargo loading or its release. These findings open up the possibility of using pillar[n]arene and its derivatives for the formation of robust and dynamic nanosystems that are capable of performing useful functions.
Small 2013, 9, No. 19, 3224–3229 [Communication]
Chuancheng Jia, Hao Li, Jiaolong Jiang, Jindong Wang, Hongliang Chen, Dennis Cao, J. Fraser Stoddart*, Xuefeng Guo*
The use of high-quality graphene as a local probe in combination with photo excitation helps to establish a deep mechanistic understanding of charge generation/quenching processes under lying the graphene/environment interface. By combining a non-destructive bottom-up assembly technique with sensitive graphene-based transistors, a bistable rotaxane-graphene hybrid device, which exhibits a symmetric mirror-image photoswitching effect with logic capabilities, is produced.
Adv. Mater. 2013, 25, No. 46, 6752–6759 [Communication]
Albert C. Fahrenbach, Scott C. Warren, Jared T. Incorvati, Alyssa-Jennifer Avestro, Jonathan C. Barnes, J. Fraser Stoddart*, Bartosz A. Grzybowski*
The impact of all-organic switches on the properties of surfaces emphasizes the considerable promise these systems possess and paints a bright picture for future applications in molecular electronic and therapeutic applications as well as artificial molecular machine technologies.
Adv. Mater. 2013, 25, No. 3, 331–348 [Progress Report]
Gokhan Barin, Ali Coskun, Moustafa M. G. Fouda, J. Fraser Stoddart*
π–π Stacks come in threes: This Review focuses on recent progress made in the assembly of mechanically interlocked molecules utilizing aromatic π–π interactions in various forms as depicted in the illustration. A variety of synthetic strategies and recognition motifs, as well as new directions in their preparation, are highlighted.
ChemPlusChem 2012, 77, No. 3, 159–185 [Review]
Lei Fang, Cheng Wang, Albert C. Fahrenbach, Ali Trabolsi, Youssry Y. Botros, J. Fraser Stoddart*
The controllable mechanical movement of either the polyether macrocycle or the tetracationic cyclophane in a doubly bistable water-soluble catenane can be accomplished by using orthogonal external stimuli—redox and amine/acid, respectively—in aqueous media (see picture).
Angew. Chem. Int. Ed. 2011, 50, No. 8, 1805–1809 [Communication]
Cari D. Meyer, Ross S. Forgan, Kelly S. Chichak, Andrea J. Peters, Nicholas Tangchaivang, Gareth W. V. Cave, Saeed I. Khan, Stuart J. Cantrill, J. Fraser Stoddart
One thing one minute and another the next: The dynamic solution equilibria between molecular Borromean rings and Solomon knots (see figure) are examined with respect to synthetic conditions, choice of metal template, and crystallization protocols in the self-assembly of these topologically complex mechanically interlocked architectures.
Chem. Eur. J. 2010, 16, No. 42, 12570–12581 [Full Paper]
Pyrenecyclodextrin‐Decorated Single‐Walled Carbon Nanotube Field‐Effect Transistors as Chemical Sensors
Yan-Li Zhao, Liangbing Hu, J. Fraser Stoddart*, George Grüner*
Sensing Device: A pyrenecyclodextrin-decorated single-walled carbon nanotube field-effect transistor acts as a chemical sensor to detect organic molecules selectively in aqueous solution, based on their molecular recognition with β-cyclodextrin.
Adv. Mater. 2008, 20, No. 10, 1910–1915 [Communication]
S. Angelos, E. Johansson, J. F. Stoddart, J. I. Zink
Mesostructured silica is a transparent, easily synthesized framework that can be derivatized with active molecules to produce desired functions. Silica with a 2D hexagonal array of pores has been used as the support for nano-impellers and nanovalves (see figure).
Adv. Funct. Mater. 2007, 17, No. 14, 2261–2271 [Feature Article]
T. D. Nguyen, K. C.-F. Leung, M. Liong, Y. Liu, J. F. Stoddart, J. I. Zink
A supramolecular nanovalve controls the 2 nm diameter openings to pores in silica particles. It traps and releases luminescent molecules in the pores on command (see figure). It is activated by chemical reducing agents and by illumination of built-in photo-reducing agents.
Adv. Funct. Mater. 2007, 17, No. 13, 2101–2110 [Full Paper]
S. Saha, K. C.-F. Leung, T. D. Nguyen, J. F. Stoddart, J. I. Zink
Interlocked molecular and supramolecular actuators based on rotaxanes can act as gatekeepers at the entrances to nanopores in silica, into which guest dye molecules can be uploaded and then released on demand. Such actuators, or nanovalves (shown in the figure), can be operated using a wide range of stimuli, and can be regarded as the prototypes of highly controllable drug-delivery systems.
Adv. Funct. Mater. 2007, 17, No. 5, 685–693 [Feature Article]
Peter R. Ashton, Roberto Ballardini, Vincenzo Balzani, Alberto Credi, Klaus Ruprecht Dress, Eléna Ishow, Cornelis J. Kleverlaan, Oldrich Kocian, Jon A. Preece, Neil Spencer, J. Fraser Stoddart, Margherita Venturi, Sabine Wenger
Chem. Eur. J. 2000, 6, No. 19, 3558–3574 [Molecular Meccano, Part 61 : Full Paper]
Vincenzo Balzani, Alberto Credi, Françisco M. Raymo, J. Fraser Stoddart
The construction of molecular machinery is firing the imaginations of chemists of all persuasions these days. Just as dyes came to the fore and brightened up our lives in the 19th century and drugs came onto the scene and made our lives longer and more bearable in the 20th century, so the 21st century will be dominated by devices (see picture) that will transform the way we live our lives beyond our wildest dreams. The current surge of research activity on artificial molecular machines serves to remind us that fresh concepts continue to instill new life into chemistry as a discipline.
Angew. Chem. Int. Ed. 2000, 39, No. 19, 3348–3391 [Review]
Masumi Asakawa, Peter R. Ashton, Vincenzo Balzani, Alberto Credi, Christoph Hamers, Gunter Mattersteig, Marco Montalti, Andrew N. Shipway, Neil Spencer, J. Fraser Stoddart, Malcolm S. Tolley, Margherita Venturi, Andrew J. P. White, David J. Williams
Angew. Chem. Int. Ed. 1998, 37, No. 3, 333–337 [Communication]
Xiaoqiang Sun, David B. Amabilino, Peter R. Ashton, Ian W. Parsons, J. Fraser Stoddart, Malcolm S. Tolley
Macromol. Symp. 1994, 77, No. 1, 191–207 [Article]
Roberto Ballardini*, Vincenzo Balzani*, Maria Teresa Gandolfi, Luca Prodi, Margherita Venturi, Douglas Philp, Howard G. Ricketts, J. Fraser Stoddart
The unthreading and rethreading of pseudorotaxane 1, which contains two p-phenylene spacers linking two bipyridinium units and a central 1, 5-naphthalenediyl unit, is reversible when an initially oxygen-free solution of 1 in water also containing 9-anthracenecarboxylic acid as a photosensitizes and triethanolamine as a “sacrificial” reluctant is irradiated and then aerated. The absorption and emission spectra of the solution provide conclusive evidence.
Angew. Chem. Int. Ed. 1993, 32, No. 9, 1301–1303 [Communication]
Peter R. Ashton, Timothy T. Goodnow, Angel E. Kaifer, Mark V. Reddington, Alexandra M. Z. Slawin, Neil Spencer, J. Fraser Stoddart*, Cristina Vicent, David J. Williams
A template-controlled, one-pot reaction afforded the catenane 1 in 70% yield. Compound 1 consists of π-electron-rich decaoxa[13.13]paracyclophane (empty circles) and an electron-deficient macrocycle made up of two paraquat p-phenylene units (filled circles). Dynamic 1 H NMR spectroscopy and cyclovoltammetry showed that 1 is highly ordered not only in the solid state but also in solution.
Angew. Chem. Int. Ed. 1989, 28, No. 10, 1396–1399 [Communication]
Articles by J. F. Stoddart and J.-P. Sauvage
Ali Coskun, Mohamad Hmadeh, Gokhan Barin, Felipe Gándara, Qiaowei Li, Eunwoo Choi, Nathan L. Strutt, David B. Cordes, Alexandra M. Z. Slawin, J. Fraser Stoddart*, Jean-Pierre Sauvage*, Omar M. Yaghi*
MOFs on the move: A copper-coordinated pseudorotaxanate which reacts with zinc nitrate to form threefold interpenetrated networks retains most of its solution-state chemistry, including its ability to undergo electronic switching of some of the copper(I) ions under redox control.
Angew. Chem. Int. Ed. 2012, 51, No. 9, 2160–2163 [Communication]
Hao Li, Albert C. Fahrenbach, Ali Coskun, Zhixue Zhu, Gokhan Barin, Yan-Li Zhao, Youssry Y. Botros, Jean-Pierre Sauvage*, J. Fraser Stoddart*
A redox-controllable bistable rotaxane has been synthesized using templation and click chemistry. With assistance from a sacrificial electron donor, light-triggered switching through numerous cycles can be initiated by radical-pairing interactions between the reduced forms of the cyclophane and the bipyridinium unit in aqueous solution in the absence of air. In the presence of air (O2), the interactions are reset by donor–acceptor charge transfer.
Angew. Chem. Int. Ed. 2011, 50, No. 30, 6782–6788 [Communication]
Articles by J.-P. Sauvage
Frédéric Niess, Vincent Duplan, Christian S. Diercks, Jean-Pierre Sauvage*
Forced to twist: Two large rings, 66- and 78-membered, each one incorporating two pairs of transition-metal-complexing units, have been prepared. Both macrocycles form molecular figures-of-eight in the presence of iron(II) (see figure). The larger ring can accommodate a four-coordinate copper(I) center to form a highly twisted figure-of-eight backbone, whereas the smaller ring is too small for coordination.
Chem. Eur. J. 2015, 21, No. 41, 14393–14400 [Full Paper]
A Flexible Copper(I)‐Complexed Rotaxane Containing Two Face‐to‐Face Porphyrinic Plates that Behaves as a Distensible Receptor
Cécile Roche, Angélique Sour*, Jean-Pierre Sauvage*
Accommodating and flexible! A new cyclic rotaxane composed of two flexible bis-macrocycles and two rigid axles is described (see figure). The rotaxane acts as a host for ditopic guest substrates. It shows remarkable flexibility, and is able to adjust its conformation to the guest size. It can be distended and accommodate rod-like guests of up to 15.8 Å in length.
Chem. Eur. J. 2012, 18, No. 27, 8366–8376 [Full Paper]
Jean-Paul Collin*, Stéphanie Durot*, Michel Keller, Jean-Pierre Sauvage*, Yann Trolez, Mario Cetina, Kari Rissanen
Chemical tidying: A new example of a linear rotaxane has been synthesized in good yield (see figure). The external fragments and the central core of the system contain tri- and bidentate chelating units, respectively. Such a situation enables the system to tidy four metal centres consisting of two different metallic ions, Li+ and Zn2+, and to localize them in well-defined positions.
Chem. Eur. J. 2011, 17, No. 3, 947–957 [Full Paper]
A Cyclic rotaxane that Behaves as a Switchable Molecular Receptor: Formation of a Rigid Scaffold from a Collapsed Structure by Complexation with Copper(I) Ions
Jean-Paul Collin*, Fabien Durola, Valérie Heitz*, Felipe Reviriego, Jean-Pierre Sauvage*, Yann Trolez
Total collapse: A porphyrinic rotaxane collapses completely after demetalation. The metal-free compound does not act as a receptor whereas the copper(I)-complexed compound is a selective receptor for diamine and dipyridyl substrates (see picture). The recognition process can thus be switched on and off by complexing the free ligand to four CuI ions or demetalating the metal-complexed species, respectively.
Angew. Chem. Int. Ed. 2010, 49, No. 52, 10172–10175 [Communication]
S. Bonnet, J.-P. Collin, M. Koizumi, P. Mobian, J.-P. Sauvage
Transition metal-containing catenanes and rotaxanes are ideally suited to building “molecular machines”. This review describes some examples of prototypes elaborated in Strasbourg, focusing on light-driven systems using ruthenium(II) complexes. An electrochemically driven system and a linear rotaxane dimer whose behavior is reminiscent of that of muscles (see figure) are also presented.
Adv. Mater. 2006, 18, No. 10, 1239–1250 [Progress Report]
Laure-Emmanuelle Perret-Aebi, Alexander von Zelewsky, Christiane Dietrich-Buchecker, Jean-Pierre Sauvage
Tying nice neat knots is demonstrated on a molecular level with the stereoselective synthesis of a trefoil knot. The key reaction was the completely stereoselective formation of a double-stranded helical precursor from two pinene–bipyridine threads around two CuI centers (the pinene moieties contain stereogenic centers). The helix was then transformed through several steps into 1; demetallation of the complex 1 yielded the configurationally predetermined free trefoil knot.
Angew. Chem. Int. Ed. 2004, 43, No. 34, 4482–4485 [Communication]
Jean-Claude Chambron, Jean-Paul Collin, Valérie Heitz, Damien Jouvenot, Jean-Marc Kern, Pierre Mobian, Didier Pomeranc, Jean-Pierre Sauvage
Eur. J. Org. Chem. 2004, No. 8, 1627–1638 [Microreview]
Maria Consuelo Jimenez-Molero, Christiane Dietrich-Buchecker, Jean-Pierre Sauvage
The copper(I)-induced template synthesis of a linear rotaxane dimer (shown here) is described. This multicomponent molecular assembly, which is obtained in a 23 step synthesis, undergoes large comformational changes by means of a simple metal exchange. The reversible contraction and stretching motions, which are shown by extensive NMR studies, are reminiscient, at the molecular level, of those observed in biological muscles.
Chem. Eur. J. 2002, 8, No. 6, 1456–1466 [Full Paper]
M. Consuelo Jiménez, Christiane Dietrich-Buchecker, Jean-Pierre Sauvage
Copper(I)-induced template synthesis produces a linear rotaxane dimer capable of undergoing contraction and stretching motions of large amplitude under the action of a chemical stimulus (see scheme). The process is reminiscent of those observed in natural muscles.
Angew. Chem. Int. Ed. 2000, 39, No. 18, 3284–3287 [Communication]
Jean-Marc Kern*, Jean-Pierre Sauvage*, Gérard Bidan*, Martial Billon, Bernadette Divisia-Blohorn
Polyrotaxane-like structures consisting of macrocycles trapped to form a polymeric network (see Figure) have been synthesized using a pre-assembling principle. The synthesis and electrochemical characterization of thin films are described. In addition to the classical properties of organic conducting polymers, the assemblies exhibit very specific properties arising from the coordinating macrocycles sliding between the nodes of the network.
Adv. Mater. 1996, 8, No. 7, 580–582 [Communication]
Christiane O. Dietrich-Buchecker, Jean-Pierre Sauvage*
Molecular knots have long been the subject of speculation. Now, for the first time, it has been possible to synthesize a “knotted” molecule having the topological chirality of a trefoil knot. Compound 1 was synthesized via a double-helix complex by exploiting the template effect of CuI ions. The chirality of 1 could be demonstrated by 1H NMR spectroscopy. The “unraveled” topological isomer of 1 was also synthesized.
Angew. Chem. Int. Ed. 1989, 28, No. 2, 189–192 [Communication]
Articles by B. L. Feringa
Motion granted: Redox-driven switching between conformational states competes with electrochemical oxidation on the path to a unidirectional redox-driven molecular rotary motor.
ChemPhysChem 2016, 17, No. 12, 1895–1901 [Article]
Thomas van Leeuwen, Jefri Gan, Jos C. M. Kistemaker, Stefano F. Pizzolato, Mu-Chieh Chang, Ben L. Feringa*
Conformational isomerism: A method to obtain new and functionalizable overcrowded alkenes in enantiopure form is presented. The procedure involves a short synthesis of three steps and a solvent-switchable chiral resolution by using a readily available resolving agent (see scheme).
Chem. Eur. J. 2016, 22, No. 21, 7054–7058 [Communication]
Towards Dynamic Control of Wettability by Using Functionalized Altitudinal Molecular Motors on Solid Surfaces
Gábor London, Kuang-Yen Chen, Gregory T. Carroll, Ben L. Feringa*
Get your motor running: To achieve dynamic control over the properties of solid surfaces, molecular motors with hydrophobic and hydrophilic functional groups were synthesized and attached to quartz surfaces (see figure). The functionalized motors preserved their rotary function both in solution and on the surface. The influence of the functional groups on surface wettability is also described.
Chem. Eur. J. 2013, 19, No. 32, 10690–10697 [Full Paper]
Da-Hui Qu, Ben L. Feringa
The key to motion: A second-generation molecular rotary motor, which contains a DB24C8 macrocycle ring incorporated into the lower stator half and a dialkyl ammonium ion attached to the upper rotor half, forms a pseudorotaxane in less polar solvents such as CH2Cl2. In this self-complexing system, acid–base-controlled threading–dethreading movements can be utilized to unlock or lock the molecular motor (see picture).
Angew. Chem. Int. Ed. 2010, 49, No. 6, 1107–1110 [Communication]
Arjen Cnossen, Dirk Pijper, Tibor Kudernac, Michael M. Pollard, Nathalie Katsonis, Ben L. Feringa
Lightning quick! A new ultrafast light-driven molecular motor was developed, which was readily incorporated into a larger trimeric system. The trimer of these motors was studied with STM and at the interface of highly oriented pyrolytic graphite and 1-phenyloctane the molecules form stable arrays in which the chirality of the trimer is expressed on both the molecular and the supramolecular level (see figure).
Chem. Eur. J. 2009, 15, No. 12, 2768–2772 [Communication]
Nicolas Heureux, Filippo Lusitani, Wesley R. Browne, Maxim S. Pshenichnikov, Paul H. M. van Loosdrecht, Ben L. Feringa*
Small 2008, 4, No. 4, 476–480 [Communication]
Auke J. Kronemeijer, Hylke B. Akkerman, Tibor Kudernac, Bart J. van Wees, Ben L. Feringa, Paul W. M. Blom, Bert de Boer*
A reliable and reproducible solid-state molecular electronic device that shows bidirectional conductance switching of molecular origin is demonstrated. The devices are manufactured by conventional processing techniques and are based on a molecular monolayer of photochromic diarylethenes, sandwiched between two electrodes, which switches reversibly and in situ between two conductance states via optical addressing.
Adv. Mater. 2008, 20, No. 8, 1467–1473 [Communication]
Michael M. Pollard, Matthijs K. J. ter Wiel, Richard A. van Delden, Javier Vicario, Nagatoshi Koumura, Coenraad R. van den Brom, Auke Meetsma, Ben L. Feringa
Unidirectional rotation of light-driven rotary motors in solution is preserved when they are grafted to the surface of small gold nanoparticles (see picture), as was demonstrated by 1H and 13C NMR, UV/Vis and CD spectroscopy in combination with 2H- and 13C-labelled motor molecules.
Chem. Eur. J. 2008, 14, No. 36, 11610–11622 [Full Paper]
M. M. Pollard, M. Klok, D. Pijper, B. L. Feringa
Control over the rotary speed of, and, in particular, the means to accelerate, light-driven unidirectional rotary motor systems is the key to their future application. Here, the structural features that influence the rate of rotation of molecular motors that are based on overcrowded alkenes are reviewed. This intriguing and instructive line of research ultimately leads to a motor that is capable of 44 rotations per second—5 × 108 times faster than the original design (see figure).
Adv. Funct. Mater. 2007, 17, No. 5, 718–729 [Feature Article]
Molecular Transmission: Controlling the Twist Sense of a Helical Polymer with a Single Light‐Driven Molecular Motor
Dirk Pijper, Ben L. Feringa
Twisted sisters: Transmission of chirality from a light-driven rotary molecular motor to the macromolecular level of a polyisocyanate allows fully reversible control of the preferred helical sense of the polymer backbone (see picture).
Angew. Chem. Int. Ed. 2007, 46, No. 20, 3693–3696 [Communication]
Michael M. Pollard, Monika Lubomska, Petra Rudolf, Ben L. Feringa
All for one: The relative unidirectional rotary motion of light-driven molecular motors in solution was transformed into controlled rotary motion in a monolayer on quartz. The correlation of the CD spectroscopic behavior of the monolayer with its solution counterpart suggests that the motors retain their function when grafted to the surface.
Angew. Chem. Int. Ed. 2007, 46, No. 8, 1278–1280 [Communication]
N. Katsonis, T. Kudernac, M. Walko, S. J. van der Molen, B. J. van Wees, B. L. Feringa
Light-controlled conductance switching of diarylethenes attached to Au(111) is reported (see figure). First, scanning tunneling microscopy is used to demonstrate reversible photoswitching for individual molecules. Second, reversible switching in self-assembled monolayers is established by means of optical spectroscopy.
Adv. Mater. 2006, 18, No. 11, 1397–1400 [Communication]