Search results for "Rotaxane"
showing 10 items of 41 documents
A [13]rotaxane assembled via a palladium molecular capsule
2019
Molecules that are the size of small proteins are difficult to make. The most frequently examined route is via self-assembly, and one particular approach involves molecular nanocapsules, where ligands are designed that will enforce the formation of specific polyhedra of metals within the core of the structure. Here we show that this approach can be combined with mechanically interlocking molecules to produce nanocapsules that are decorated on their exterior. This could be a general route to very large molecules, and is exemplified here by the synthesis and structural characterization of a [13]rotaxane, containing 150 metal centres. Small angle X-ray scattering combined with atomistic molecu…
On the formation of inclusion complexes at the solid/liquid interface of anchored temperature-responsive PNIPAAM diblock copolymers with γ-cyclodextr…
2017
The thermal responsive behavior of adsorbed layers of diblock copolymers of poly(N-isopropylacrylamide) (PNIPAAM) and poly((3-acrylamidopropyl)trimethylammonium chloride) (PAMPTMA(+)) with γ-cyclodextrin (γ-CD) at the solid/liquid interface has been investigated using three in situ techniques: null ellipsometry, quartz–crystal microbalance with dissipation monitoring, and neutron reflectometry. The measurements provided information about the adsorbed amounts, the layer thickness, hydration and viscoelastic properties, and the interfacial structure and composition. The copolymers adsorb to silica with the cationic PAMPTMA(+) blocks sitting as anchors in a flat conformation and the PNIPAAM ch…
Ion-Pairing Effects in the Self-Assembly of a Fluorescent Pseudorotaxane
2006
Herein we report on the self-assembly, in a low polarity solvent, of a pseudorotaxane species comprising binaphthyl-26-crown-8 (BN26C8) as the macrocyclic host and anthracenyl-benzylammonium as the threadlike positively charged guest (ABH+). Absorption and luminescence data reveal a very efficient energy transfer process occurring from the binaphthyl to the anthracene singlet excited states. The self-assembly is highly dependent on the nature of the counteranion confirming the crucial role played by it in the competition between the self-assembly process and the formation of ion pairs (ABH+X-). This behavior can be readily evidenced in dilute solutions from the analysis of the luminescence …
[3]Rotaxanes and [3]pseudorotaxanes with a rigid two-bidentate chelate axle threaded through two coordinating rings
2009
New [3]rotaxanes and [3]pseudorotaxanes have been synthesised using the “gathering and threading” effect of copper(I). By using click chemistry as the “stoppering” reaction, a good yield of the [3]rotaxane was obtained, either as a dicopper complex or as a metal-free compound after demetallation. The axle contains a central rigid aromatic block incorporating two bidentate chelates, and the threaded macrocycles are 30-membered rings. A model dicopper(I) [3]pseudorotaxane whose axle was end-functionalised by triisopropylsilyl groups could be crystallised and studied by X-ray diffraction. A particularly attractive structure was obtained showing a “slanted” geometry for the two rings and the ax…
Damming an electronic energy reservoir: ion-regulated electronic energy shuttling in a [2]rotaxane
2021
We demonstrate the first example of bidirectional reversible electronic energy transfer (REET) between the mechanically bonded components of a rotaxane. Our prototypical system was designed such that photoexcitation of a chromophore in the axle results in temporary storage of electronic energy in a quasi-isoenergetic “reservoir” chromophore in the macrocycle. Over time, the emissive state of the axle is repopulated from this reservoir, resulting in long-lived, delayed luminescence. Importantly, we show that cation binding in the cavity formed by the mechanical bond perturbs the axle chromophore energy levels, modulating the REET process, and ultimately providing a luminescence read-out of c…
Fast redox-triggered shuttling motions in a copper rotaxane based on a phenanthroline–terpyridine conjugate
2014
Fast shuttling motions in solution have been observed by cyclic voltammetry in a Cu(I/II)-based [2] rotaxane. In the reported system, the different coordination preferences of both copper oxidation states are exploited to promote the electrochemically-triggered gliding of the ring from a tetra to a pentacoordinated site and vice versa. The thread of this rotaxane consists of a tridentate 2,2':6',2''-terpyridine chelating unit directly bonded through its 5-position to the 3-position of the bidentate 1,10-phenanthroline unit. This distribution reduces to a minimum the distance between the two coordination sites and lessens the congestion around the tetrahedral environment. These two factors h…
Two-Component Hydrogels Formed by Cyclodextrins and Dicationic Imidazolium Salts
2014
In the framework of our recent interest in studying the gelling behaviour of imidazolium salts, we took into account the possibility of obtaining two-component hydrogels by combining cyclodextrins and dicationic imidazolium salts. In particular, we used diimidazolium salts differing in the alkyl chain length and in the size, shape, and coordination ability of the anion, namely the 3,3′-di-n-decyl- and 3,3′-di-n-dodecyl-1,1′-(1,4- phenylenedimethylene)diimidazolium dibromide, and 3,3′-di-n-dodecyl-1, 1′-(1,4-phenylenedimethylene)diimidazolium ditetrafluoroborate and dihexafluorophosphate. As far as cyclodextrins are concerned, to gain information on the effects of different sized cyclic olig…
A modular "toolbox" approach to flexible branched multimacrocyclic hosts as precursors for multiply interlocked architectures.
2008
Tetralactam macrocycles can be functionalized by a variety of cross-coupling reactions. A modular “toolbox” strategy is presented that allows 1) several tetralactam macrocycles to be covalently connected with each other or with a central spacer, 2) the macrocycles to be substituted with or connected to different chromophores, and 3) metal-coordination sites to be attached to the macrocycles. With this approach a series of different oligo-macrocyclic hosts was obtained with great structural diversity and enormous potential for further functionalization. Rotaxanes made on the basis of these macrocycles have been synthesized to demonstrate their utility in building more complex supramolecular …
Pillar[5]arene-Diketopyrrolopyrrole Fluorescent Copolymer: A Promising Recognition and Adsorption Material for Adiponitrile by Selective Formation of…
2017
Conjugated pillar[5]arene-diketopyrrolopyrrole copolymer (P1) is synthesized by the copolymerization of a difunctionalized pillar[5]arene and a diketopyrrolopyrrole-based monomer, which shows large extinction coefficients (1.1 × 104 m-1 cm-1 ) at 519 nm and strong emission at 587 nm. P1 exhibits very strong host-guest binding affinity towards adiponitrile but low binding affinity towards 1,4-dihalobutane and 1,4-bis(imidazol-1-yl)butane. Such an enhanced selectivity is first found in the polypseudorotaxane between pillararene and neutral guests in organic solution and is successfully used for the recognition and adsorption of adiponitrile by the formation of a P1-adiponitrile polypseudorota…
Autonomous artificial nanomotor powered by sunlight
2006
Light excitation powers the reversible shuttling movement of the ring component of a rotaxane between two stations located at a 1.3-nm distance on its dumbbell-shaped component. The photoinduced shuttling movement, which occurs in solution, is based on a “four-stroke” synchronized sequence of electronic and nuclear processes. At room temperature the deactivation time of the high-energy charge-transfer state obtained by light excitation is ≈10 μs, and the time period required for the ring-displacement process is on the order of 100 μs. The rotaxane behaves as an autonomous linear motor and operates with a quantum efficiency up to ≈12%. The investigated system is a unique example of an artif…