Triggering a [2]Rotaxane Molecular Shuttle by a Photochemical Bond-Cleavage Strategy.

The successful triggering of ring-shuttling motion between two stations in a [2]rotaxane is demonstrated by employing a photochemical bond-cleavage strategy. A photolabile bulk barrier is covalently introduced into two identical stations of the thread to prevent dynamic shuttling of the macrocycle, resulting in a "gated" state. Irradiation of UV light (λ = 365 nm) results in the complete removal of the bulk barrier and the balanced shuttling motion of the macrocycle, indicating an "open" state of the rotaxane. In addition, the process from the "open" rotaxane to the "gated" rotaxane was executed by a chemical-rebonding method.

[1]  Euan R. Kay,et al.  A Reversible Synthetic Rotary Molecular Motor , 2004, Science.

[2]  M. Alajarin,et al.  Versatile control of the submolecular motion of di(acylamino)pyridine-based [2]rotaxanes , 2015, Chemical science.

[3]  Wiktor Szymanski,et al.  Wavelength-selective cleavage of photoprotecting groups: strategies and applications in dynamic systems. , 2015, Chemical Society reviews.

[4]  J. Barltrop,et al.  Photosensitive Protecting Groups , 1962 .

[5]  Francesco Zerbetto,et al.  A generic basis for some simple light-operated mechanical molecular machines. , 2004, Journal of the American Chemical Society.

[6]  Hao Li,et al.  Photoinduced memory effect in a redox controllable bistable mechanical molecular switch. , 2012, Angewandte Chemie.

[7]  R. Woodward,et al.  Photosensitive protecting groups , 1970 .

[8]  D. Qu,et al.  A fluorescent bistable [2]rotaxane molecular switch on SiO₂ nanoparticles. , 2015, Chemical communications.

[9]  A. Credi,et al.  Solvent- and light-controlled unidirectional transit of a nonsymmetric molecular axle through a nonsymmetric molecular wheel. , 2012, Chemistry.

[10]  Euan R. Kay,et al.  A molecular information ratchet , 2007, Nature.

[11]  J. F. Stoddart,et al.  Interface‐Engineered Bistable [2]Rotaxane‐Graphene Hybrids with Logic Capabilities , 2013, Advanced materials.

[12]  H. Tian,et al.  Bright functional rotaxanes. , 2010, Chemical Society reviews.

[13]  H. Lusic,et al.  Photocleavable polyethylene glycol for the light-regulation of protein function. , 2010, Bioconjugate chemistry.

[14]  T. Furuta,et al.  Coumarin-4-ylmethoxycarbonyls as phototriggers for alcohols and phenols. , 2003, Organic letters.

[15]  H. Ågren,et al.  A switchable bis-branched [1]rotaxane featuring dual-mode molecular motions and tunable molecular aggregation. , 2014, ACS applied materials & interfaces.

[16]  M. Baroncini,et al.  Organic Nanofibers Embedding Stimuli-Responsive Threaded Molecular Components , 2014, Journal of the American Chemical Society.

[17]  David A Leigh,et al.  Catenanes: Fifty Years of Molecular Links , 2015, Angewandte Chemie.

[18]  M. Baroncini,et al.  Photoactivated directionally controlled transit of a non-symmetric molecular axle through a macrocycle. , 2012, Angewandte Chemie.

[19]  D. Leigh,et al.  An autonomous chemically fuelled small-molecule motor , 2016, Nature.

[20]  R. Givens,et al.  Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy , 2012, Chemical reviews.

[21]  Mark Peplow,et al.  The tiniest Lego: a tale of nanoscale motors, rotors, switches and pumps , 2015, Nature.

[22]  Douglas C. Friedman,et al.  A light-gated STOP-GO molecular shuttle. , 2009, Journal of the American Chemical Society.

[23]  Severin T. Schneebeli,et al.  Redox switchable daisy chain rotaxanes driven by radical-radical interactions. , 2014, Journal of the American Chemical Society.

[24]  Keiji Hirose,et al.  A shuttling molecular machine with reversible brake function. , 2008, Chemistry.

[25]  Euan R Kay,et al.  Rise of the Molecular Machines , 2015, Angewandte Chemie.

[26]  N. Harada,et al.  Light-driven monodirectional molecular rotor , 2022 .

[27]  D. Philp,et al.  Orthogonal Recognition Processes Drive the Assembly and Replication of a [2]Rotaxane. , 2015, Journal of the American Chemical Society.

[28]  Alberto Credi,et al.  Light-powered autonomous and directional molecular motion of a dissipative self-assembling system. , 2015, Nature nanotechnology.

[29]  D. Qu,et al.  One-pot synthesis of a [c2]daisy-chain-containing hetero[4]rotaxane via a self-sorting strategy† †Electronic supplementary information (ESI) available: Full experimental procedures and characterization data for all compounds. See DOI: 10.1039/c5sc04844c Click here for additional data file. , 2016, Chemical science.

[30]  A. Credi,et al.  Light to investigate (read) and operate (write) molecular devices and machines. , 2014, Chemical Society reviews.

[31]  Linyong Zhu,et al.  Light and reductive dual stimuli-responsive PEI nanoparticles: "AND" logic response and controllable release. , 2014, Journal of materials chemistry. B.

[32]  Xiang Ma,et al.  Photoresponsive Host-Guest Functional Systems. , 2015, Chemical reviews.

[33]  Belén Ferrer,et al.  Autonomous artificial nanomotor powered by sunlight , 2006, Proceedings of the National Academy of Sciences of the United States of America.

[34]  D. Qu,et al.  An acid/base responsive side-chain polyrotaxane system with a fluorescent signal , 2016 .

[35]  J. F. Stoddart,et al.  Rotaxane-based molecular muscles. , 2014, Accounts of chemical research.

[36]  Feihe Huang,et al.  Development of Pseudorotaxanes and Rotaxanes: From Synthesis to Stimuli-Responsive Motions to Applications. , 2015, Chemical reviews.

[37]  Vincenzo Balzani,et al.  Light powered molecular machines. , 2009, Chemical Society reviews.

[38]  H. Zhang,et al.  Mechanically selflocked chiral gemini-catenanes , 2015, Nature Communications.

[39]  A. Slawin,et al.  A chemically-driven molecular information ratchet. , 2008, Journal of the American Chemical Society.

[40]  J. F. Stoddart,et al.  Solution-phase counterion effects in supramolecular and mechanostereochemical systems. , 2011, Chemical Society reviews.

[41]  Hao Li,et al.  An artificial molecular pump. , 2015, Nature nanotechnology.

[42]  Sundus Erbas-Cakmak,et al.  Artificial Molecular Machines , 2015, Chemical reviews.

[43]  Ying-Wei Yang,et al.  Molecular and supramolecular switches on mesoporous silica nanoparticles. , 2015, Chemical Society reviews.

[44]  D. Leigh,et al.  A three-compartment chemically-driven molecular information ratchet. , 2012, Journal of the American Chemical Society.

[45]  Alberto Credi,et al.  A simple molecular machine operated by photoinduced proton transfer. , 2007, Journal of the American Chemical Society.

[46]  J. F. Stoddart,et al.  Putting mechanically interlocked molecules (MIMs) to work in tomorrow's world. , 2014, Angewandte Chemie.

[47]  M. Baroncini,et al.  Reversible photoswitching of rotaxane character and interplay of thermodynamic stability and kinetic lability in a self-assembling ring-axle molecular system. , 2010, Chemistry.

[48]  Hui Zhao,et al.  o-Nitrobenzyl Alcohol Derivatives: Opportunities in Polymer and Materials Science , 2012 .

[49]  David A. Leigh,et al.  Pick-up, transport and release of a molecular cargo using a small-molecule robotic arm. , 2016, Nature chemistry.

[50]  D. Qu,et al.  Fluorescence modulation in tribranched switchable [4]rotaxanes. , 2013, Chemistry.

[51]  Junzo Otera,et al.  Intermittent molecular shuttle as a binary switch. , 2004, Angewandte Chemie.

[52]  Arne Lützen,et al.  Controlling the rate of shuttling motions in [2]rotaxanes by electrostatic interactions: a cation as solvent-tunable brake. , 2005, Organic & biomolecular chemistry.

[53]  Feihe Huang,et al.  A pillar[6]arene-based UV-responsive supra-amphiphile: synthesis, self-assembly, and application in dispersion of multiwalled carbon nanotubes in water. , 2014, Chemical communications.

[54]  Da-Hui Qu,et al.  Recent advances in new-type molecular switches , 2015, Science China Chemistry.

[55]  D. Qu,et al.  Dual-mode operation of a bistable [1]rotaxane with a fluorescence signal. , 2013, Organic letters.

[56]  J. F. Stoddart,et al.  Electrostatic barriers in rotaxanes and pseudorotaxanes. , 2011, Chemistry.

[57]  J. Berná,et al.  Small-molecule recognition for controlling molecular motion in hydrogen-bond-assembled rotaxanes. , 2014, Angewandte Chemie.

[58]  S. Woutersen,et al.  Water lubricates hydrogen-bonded molecular machines. , 2013, Nature chemistry.

[59]  D. Qu,et al.  A half adder based on a photochemically driven [2]rotaxane. , 2005, Angewandte Chemie.

[60]  S. J. Loeb,et al.  Rotaxanes as ligands: from molecules to materials. , 2007, Chemical Society reviews.

[61]  H. Mootz,et al.  Photocontrol of protein activity mediated by the cleavage reaction of a split intein. , 2011, Angewandte Chemie.

[62]  D. Qu,et al.  Phototriggered supramolecular polymerization of a [c2]daisy chain rotaxane , 2016 .

[63]  D. Qu,et al.  Dual-mode control of PET process in a ferrocene-functionalized [2]rotaxane with high-contrast fluorescence output. , 2012, Organic letters.

[64]  David A. Leigh,et al.  Peptide-Based Molecular Shuttles , 1997 .

[65]  Francesco Zerbetto,et al.  Unidirectional rotation in a mechanically interlocked molecular rotor , 2003, Nature.