Formation of [2]- and [3]Rotaxanes through Bridging under Kinetic and Thermodynamic Control

Fujino, Takaaki; Naitoh, Hirotake; Miyagawa, Shinobu; Kimura, Masaki; Kawasaki, Tsuneomi; Yoshida, Kazuyuki; Inoue, Hajime; Takagawa, Hiroaki; Tokunaga, Yuji

doi:10.1021/acs.orglett.7b03615

Cited by 8 publications

(16 citation statements)

References 83 publications

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“…The synthetic routes of M1 and M2 were presented in Scheme S1. M1, M2 and their precursors were characterized by 1 H NMR spectroscopy, 13 C NMR spectroscopy as well as highresolution mass spectrometry (Figure S1-S13). For preparing stock solutions, M1 (0.983 g, 400 mM) and M2 (1.38 mg, 400 mM) were dissolved in CDCl 3 /CD 3 CN (v/v = 1/1).…”

Section: Resultsmentioning

confidence: 99%

“…However, even if the incipient host-guest interactions were damaged, the depolymerization behaviors would not occur on account of the resulting interlocked conformation. [13] These above-mentioned movements were both reversible when D 2 O [15] and AgPF 6 [14] were being contributed respectively. Generally, this supramolecular polymer had presented a motion pattern towards different orientations, for which it showed a close moving trend to natural muscle.…”

Section: Introductionmentioning

confidence: 96%

“…In this way, on the occasion of high concentrations, SPs could be formed through self-assembly of M1 and M2 through host-guest interactions from a large macrocycle and two secondary ammonium ions. [13] Upon the addition of N 2 H 4 , dynamic covalent bonds were generated via two aldehyde moieties reacting with hydrazine, in which azine was able to be bridged. Consequently, the initial large macrocycle proceeded ring shrinking with production of two smaller macrocyclic rings.…”

Section: Introductionmentioning

confidence: 99%

“…Consequently, the initial large macrocycle proceeded ring shrinking with production of two smaller macrocyclic rings. [13] The positioned M2 was terminated with two 3,5-di-tertbutylphenyl groups owning the larger size than that of cavity, which made itself not thread through the macrocycle, affording mechanically interlocked structures. In this way, the original diastolic state of SPs turned into vertical shrinkage condition.…”

Section: Introductionmentioning

confidence: 99%

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Muscle‐Like Supramolecular Polymers with Dual Motion Patterns

2023

Chemistry A European J

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Benefiting from the features like polymeric linear structures, stimuli‐responsiveness and dynamic adaptiveness, supramolecular polymers (SPs) are favored as exploiting muscle‐like materials, allowing for imitating the muscle functions. However, a substantial part of these materials barely owned an unitary motion orientation while it was obviously known that muscle movements involved distinct orientations. Herein, M1 holding the structure of 44‐membered macrocycle with two aldehyde groups was designed, meanwhile, M2 comprising of secondary ammonium ions, 3,5‐di‐tert‐butylphenyl groups as well as the alkyl chains was fabricated, for which it could be assembled with M1 to generate SPs based on host–guest interactions from a large macrocycle and two secondary ammonium ions. SPs underwent vertical compression upon the addition of N2H4 owing to the forming dynamic covalent bonds, notably, mechanically interlocked structures were also generated. Afterwards, the vertically compressed SPs experienced horizontal shrinkage when tetrabutylammonium chloride was contributed due to the destruction of host–guest interactions.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Muscle‐Like Supramolecular Polymers with Dual Motion Patterns

2023

Chemistry A European J

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“…The biphenyl 1 , [13] the ditosylate 2 a , [17b] the ammonium salt 4 a , [19b] and 3,5‐di‐ tert ‐butylaniline 5 b [20] were prepared according to previously reported procedures. The dichloride 2 b [18] was prepared using the method described in the Supporting Information.…”

Section: Methodsmentioning

confidence: 99%

Locking the Dynamic Axial Chirality of Biphenyl Crown Ethers through Threading

Kimura

Miyagawa

Takaya

et al. 2020

Chemistry An Asian Journal

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This paper describes the syntheses of [2]rotaxanes comprising 23-and 26-membered biphenyl crown ethers as the macrocyclic components and secondary ammonium ions as the dumbbell-shaped components, and the locking of the dynamic axial chirality of the biphenyl moieties in these structures. Chiral high-performance liquid chromatography (HPLC) revealed that our [2]rotaxane featuring the 26membered crown ether racemized at room temperature, but the racemization of the [2]rotaxane featuring the 23-mem-bered crown ether did not proceed at room temperature over a period of three days. After separation of the enantiomers of the [2]rotaxane incorporating the 23-membered crown ether through chiral HPLC, we studied its racemization at elevated temperature. The rate of stereoinversion in dimethylsulfoxide (a polar solvent) was faster than that in o-dichlorobenzene (a nonpolar solvent), and herein we discuss these kinetic parameters.

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Macrocyclic Dinuclear Palladium Complex as a Novel Doubly Threaded [3]Rotaxane Scaffold and Its Application as a Rotaxane Cross‐Linker

et al. 2020

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A dinuclear PdII complex possessing a cyclic ligand was developed as a novel doubly threaded [3]rotaxane scaffold and applied as a rotaxane cross‐linker reagent. The dinuclear complex (PdMC)2 was prepared by one‐step macrocyclization followed by the double palladation reaction. 1H NMR analysis and UV/Vis measurements revealed the formation of a doubly threaded pseudo[3]rotaxane by the complexation of (PdMC)2 with 2 equivalents of 2,6‐disubstituted pyridine 3 through double metal coordination. The treatment of (PdMC)2 with 2 equivalents of 4‐vinylpyridine (VP) afforded a doubly threaded [3]rotaxane cross‐linker (PdMC‐VP)2. Radical co‐polymerization of VP and t‐butylstyrene in the presence of (PdMC‐VP)2 afforded a stable rotaxane cross‐linked polymer (RCP). An elastic RCP was also prepared by using n‐butyl acrylate as a monomer. The obtained RCPs exhibited higher swelling ability and higher mechanical toughness compared with the corresponding covalent cross‐linked polymers.

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Formation of [2]- and [3]Rotaxanes through Bridging under Kinetic and Thermodynamic Control

Cited by 8 publications

References 83 publications

Muscle‐Like Supramolecular Polymers with Dual Motion Patterns

Muscle‐Like Supramolecular Polymers with Dual Motion Patterns

Locking the Dynamic Axial Chirality of Biphenyl Crown Ethers through Threading

Macrocyclic Dinuclear Palladium Complex as a Novel Doubly Threaded [3]Rotaxane Scaffold and Its Application as a Rotaxane Cross‐Linker

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