We demonstrate self-healing of the shuttling dynamics of a molecular machine operating by negative feedback. When zinc(II) was added to the copper(I)-loaded [2]rotaxane shuttle [Cu()], copper(I) was replaced, thereby generating the static zinc(II)-loaded [2]rotaxane [Zn()]. Loss of the dynamics was accompanied by a fluorescence enhancement at λ = 364 nm. Notably, the released copper(I) ions catalyzed the formation of a bis-triazole ligand, which selectively captured zinc(II). As a result, the copper(I) was restored in the rotaxane, and the dynamic shuttling motion of [Cu()] was regained. The healing was conveniently followed by diagnostic fluorescence changes.
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http://dx.doi.org/10.1021/acs.orglett.2c04237 | DOI Listing |
Dalton Trans
December 2024
Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford, OX1 3TA, UK.
Angew Chem Int Ed Engl
October 2024
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC, V6T 1Z1, Canada.
Post-synthetic modification of mechanically interlocked molecules (MIMs) is an attractive avenue to add complexity to already intricate systems. This remains an important, challenging topic that is under-developed. In this paper, we report the synthesis and characterization of a [2]rotaxane molecule featuring a ring appended to an emissive cyclometalated Pt unit.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2024
College of Chemistry, Key Laboratory of Radiation Physics and Technology of Ministry of Education, Sichuan University, Chengdu, Sichuan 610064, China.
Biomolecular machines autonomously convert energy into functions, driving systems away from thermodynamic equilibrium. This energy conversion is achieved by leveraging complex, kinetically asymmetric chemical reaction networks that are challenging to characterize precisely. In contrast, all known synthetic molecular systems in which kinetic asymmetry has been quantified are well described by simple single-cycle networks.
View Article and Find Full Text PDFChemistry
May 2024
Department of Chemistry, University of Oxford Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA, United Kingdom.
The first example of a [2]rotaxane shuttle capable of selective optical sensing of chloride anions over other halides is reported. The rotaxane was synthesised via a chloride ion template-directed cyclisation of an isophthalamide macrocycle around a multi-station axle containing peripheral naphthalene diimide (NDI) stations and a halogen bonding (XB) bis(iodotriazole) based station. Proton NMR studies indicate the macrocycle resides preferentially at the NDI stations in the free rotaxane, where it is stabilised by aromatic donor-acceptor charge transfer interactions between the axle NDI and macrocycle hydroquinone moieties.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
May 2024
Center of Micro and Nanochemistry and (Bio)Technology, School of Science and Technology, Organische Chemie I, University of Siegen, Adolf-Reichwein Str. 2, 57068, Siegen, Germany.
Stepwise dissipative control of two distinct motions, i.e., shuttling and sliding, is demonstrated in a single multicomponent device.
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