A Neutral Naphthalene Diimide [2]Rotaxane

Rouville, Henri Pierre Jacquot De; Iehl, Julien; Bruns, Carson J.; McGrier, Psaras L.; Frasconi, Marco; Sarjeant, Amy A.

doi:10.1021/ol3022963

Cited by 35 publications

(25 citation statements)

References 47 publications

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“…30 The product was characterized to satisfaction by 1 H and 13 C NMR spectroscopy and high-resolution ESI-MS (See Supporting Information). The dumbbell-shaped molecule, which constitutes the second part of the rotaxane, contains an electron-poor 1,4,5,8-naphthalenetetracarboxylic diimide (NpI) [31][32][33][34] as a matching quencher and two tetraphenyl methane units featuring three tertbutyl groups as stoppers. [35][36][37] The emitter and one of stopper groups were equipped with hydroxyl-groups in order to covalently incorporate the mechanophore into polymers.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Mechanoresponsive Behavior of a Polymer-Embedded Red-Light Emitting Rotaxane Mechanophore

Muramatsu

Sagara

Traeger

et al. 2019

ACS Appl. Mater. Interfaces

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A red-light-emitting photoluminescent supramolecular mechanophore based on an interlocked molecular motif is presented. The rotaxane-based mechanophore contains a cyclic compound featuring a π-extended 4,4-difluoro-4bora-3a,4a-diaza-s-indacene (BODIPY) dye as a red emitter that was threaded onto a dumbbell-shaped molecule containing an electron-poor 1,4,5,8-naphthalenetetracarboxylic diimide quencher at its center. Through two aliphatic hydroxyl groups attached to the dumbbell and the cycle, the mechanophore was covalently embedded into the backbone of a thermoplastic polyurethane elastomer. The mechanophore is only weakly photoluminescent in solution, indicating that the BODIPY's emission is efficiently quenched. Solution-cast films of the rotaxane-containing polymer, by contrast, show an appreciable photoluminescence, which suggests that during film formation some of the emitting cycles are trapped in positions away from the quencher. Interestingly, the emission intensity could be significantly reduced by swelling the films with an organic solvent and the emission increased again upon drying, suggesting that such solvent plasticization causes a reversible rearrangement. In both, dry and solvent-swollen films, uniaxial deformation caused a significant, reversible increase of the emission intensity, on account of mechanically induced shuttling of the emitters away from and back to the quenchers. It is shown that the properties of the polymer can be tuned by the solvent, and that such plasticizing extends the small palette of approaches that allow modification of the activation stress of a given materials system.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Mechanoresponsive Behavior of a Polymer-Embedded Red-Light Emitting Rotaxane Mechanophore

Muramatsu

Sagara

Traeger

et al. 2019

ACS Appl. Mater. Interfaces

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“…The rotaxane-based mechanoluminophore 1 ( Figure 2 a) was inspired by works of Sanders and Stoddart, who pioneered neutral donor–acceptor catenanes 29 and rotaxanes 30 based on electron-rich 1,5-disubstituted naphthalene crown ethers and the electron-poor 1,4,5,8-naphthalenetetracarboxylic diimide (NpI) motif. The latter was expected to quench the emission of 4,7-bis(phenylethynyl)-2,1,3-benzothiadiazole (BTH).…”

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confidence: 99%

Rotaxanes as Mechanochromic Fluorescent Force Transducers in Polymers

et al. 2018

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The integration of mechanophores, motifs that transduce mechanical forces into chemical reactions, allows creating materials with stress-dependent properties. Typical mechanophores are activated by cleaving weak covalent bonds, but these reactions can also be triggered by other stimuli, and this renders the behavior unspecific. Here we show that this problem can be overcome by extending the molecular-shuttle function of rotaxanes to mechanical activation. A mechanically interlocked mechanophore composed of a fluorophore-carrying macrocycle and a dumbbell-shaped molecule containing a matching quencher was integrated into a polyurethane elastomer. Deformation of this polymer causes a fluorescence turn-on, due to the spatial separation of fluorophore and quencher. This process is specific, efficient, instantly reversible, and elicits an easily detectable optical signal that correlates with the applied force.

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“…We have shown previously13b–c that electrochemical reduction of the NDI unit eliminates its affinity for aromatic crown‐10 ethers, constituting a basis for operating a redox switch. We have used cyclic voltammetry (Figure 4) at 298 K in Ar‐purged CH 2 Cl 2 with 0.1 M NBu 4 PF 6 as a supporting electrolyte to elucidate the redox‐controlled switching mechanism of 2 at a concentration of 1 m M .…”

Section: Methodsmentioning

confidence: 99%

An Electrochemically and Thermally Switchable Donor–Acceptor [c2]Daisy Chain Rotaxane

Bruns

Frasconi

et al. 2014

Angewandte Chemie

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Although motor proteins are essential cellular components that carry out biological processes by converting chemical energy into mechanical motion, their functions have been difficult to mimic in artificial synthetic systems. Daisy chains are a class of rotaxanes which have been targeted to serve as artificial molecular machines because their mechanically interlocked architectures enable them to contract and expand linearly, in a manner that is reminiscent of the sarcomeres of muscle tissue. The scope of external stimuli that can be used to control the musclelike motions of daisy chains remains limited, however, because of the narrow range of supramolecular motifs that have been utilized in their templated synthesis. Reported herein is a cyclic daisy chain dimer based on p-associated donor-acceptor interactions, which can be actuated with either thermal or electrochemical stimuli. Molecular dynamics simulations have shown the daisy chains mechanism of extension/contraction in the ground state in atomistic detail.

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A Neutral Naphthalene Diimide [2]Rotaxane

Cited by 35 publications

References 47 publications

Mechanoresponsive Behavior of a Polymer-Embedded Red-Light Emitting Rotaxane Mechanophore

Mechanoresponsive Behavior of a Polymer-Embedded Red-Light Emitting Rotaxane Mechanophore

Rotaxanes as Mechanochromic Fluorescent Force Transducers in Polymers

An Electrochemically and Thermally Switchable Donor–Acceptor [c2]Daisy Chain Rotaxane

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