- Fast redox-triggered shuttling motions in a copper rotaxane based on a phenanthroline-terpyridine conjugate
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Fast shuttling motions in solution have been observed by cyclic voltammetry in a CuI/II-based [2] rotaxane. In the reported system, the different coordination preferences of both copper oxidation states are exploited to promote the electrochemi
- Coronado, Eugenio,Gavia, Pablo,Ponce, Julia,Tatay, Sergio
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- Fast pirouetting motion in a pyridine bisamine-containing copper-complexed rotaxane
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The present work reports the introduction of pyridine bisamine terdentate ligands in the structure of a pirouetting copper rotaxane. Rotaxane 2[PF 6] constitutes the first example of the incorporation of imine-based dynamic covalent chemistry in the synthesis of switchable copper-complexed interlocked systems. In this rotaxane, the substitution of the classical terpyridine terdentate unit by a pyridine bisamine moiety has led to a significant stabilization of the pentacoordinated site. That fact has been evidenced by EPR spectroscopy and cyclic voltammetry. Regarding the tetracoordinated site, the congestion around the coordination sphere has been reduced to accelerate the typically slow reorganization of the CuII. Ethynyl-3,8-substitution on the axis phenanthroline along with the 2,9-diphenyl-1,10-phenanthroline (dpp) present in the macrocycle afforded a very stable coordination environment for CuI, which is at the same time labile upon oxidation. In summary, the incorporation of a pyridine bisamine unit as a terdentate ligand and the optimization of the bidentate ligand of the axle not only has led to a simplification of the synthetic procedures, but it has also given rise to a bistable systems with an enhanced energetic separation between states and an acceleration of the reorganization processes. Thus far, rotaxane 2[PF6] presents the fastest switching cycle reported to date in copper-interlocked dynamic systems.
- Coronado, Eugenio,Gavina, Pablo,Ponce, Julia,Tatay, Sergio
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p. 6939 - 6950
(2014/06/09)
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- A neutral naphthalene diimide [2]rotaxane
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A neutral donor-acceptor [2]rotaxane, which has been synthesized using click chemistry, has had its solid-state structure and superstructure elucidated by X-ray crystallography. Both dynamic 1H NMR spectroscopy and electrochemical investigations have been employed in an attempt to shed light on both geometrical reorganization and redox-switching processes that are occurring or can be induced within the [2]rotaxane.
- Jacquot De Rouville, Henri-Pierre,Iehl, Julien,Bruns, Carson J.,McGrier, Psaras L.,Frasconi, Marco,Sarjeant, Amy A.,Stoddart, J. Fraser
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supporting information
p. 5188 - 5191
(2013/01/15)
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- Modular synthesis of bipyridinium oligomers and corresponding donor-acceptor oligorotaxanes with crown ethers
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Donor-acceptor [4]- and [6]rotaxanes have been prepared from bipyridinium (BIPY2+) oligomers and 1,5-dinaphtho[38]crown-10 (DN38C10) by a threading-followed-by-stoppering protocol employing click chemistry. An efficient, straightforward route to the BIPY2+ oligomers has been developed that requires little to no chromatographic purification. Unlike most donor-acceptor oligorotaxanes that have been reported to date, 100% of the recognition sites on the dumbbells are occupied by rings.
- Gothard, Chris M.,Bruns, Carson J.,Gothard, Nosheen A.,Grzybowski, Bartosz A.,Stoddart, J. Fraser
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supporting information
p. 5066 - 5069,4
(2020/09/15)
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