Restriction of guest rotation based on the distortion of a cyclodextrin cavity

Chen, Wenhua; Fukudome, Makoto; Yuan, De‐Qi; Fujioka, Toshihiro; Mihashi, Kunihide; Fujita, Kahee

doi:10.1039/a909727i

Cited by 33 publications

(13 citation statements)

References 8 publications

(8 reference statements)

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“…When the reaction was complete, the water phase was extracted with ethyl acetate (3 ϫ 100 mL). The organic phases was combined, dried with anhydrous Na 2 SO 4 , and then concentrated. Synthesis of the Crown Ether 9: K 2 CO 3 (9.66 g, 70.0 mmol) and CH 3 CN (500 mL) were placed in a 1000 mL round-bottomed flask.…”

Section: Methodsmentioning

confidence: 99%

“…The fractions containing the product (TLC monitoring) were combined and concentrated under vacuum to give a residue, which was dissolved in H 2 O. A red solid, the [2]-catenane 4 (113 mg, 68.0 %), was precipitated from this solution by addition of a saturated aqueous NH 4 Supporting Information (see also the footnote on the first page of this article): Characterizations, Job plots, UV/Vis data, and crystal data for 1a 2 ʛ3 and 4.…”

Section: Synthesis Of the Crown Ether 1amentioning

confidence: 99%

“…Leigh et al [3] developed active metal template synthesis in order to construct interlocked structures such as rotaxanes and catenanes, efficiently based on the formation of a pseudorotaxane geometry when a metal ion was incorporated into precisely designed molecule systems, acting as both a template and as a catalyst. Fujita et al [4] observed that the distortion of a cyclodextrin cavity could significantly restrict the guest rotation. Schalley et al [5] found that small structural changes such as the simple exchange of a CH group for an isoelectronic N atom could have unexpectedly large effects on the deslipping reactions of rotaxanes.…”

Section: Introductionmentioning

confidence: 99%

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Improved Pseudorotaxane and Catenane Formation from a Derivative of Bis(m‐phenylene)‐32‐crown‐10

et al. 2010

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Abstract2,2′‐Dihydroxy‐bis(m‐phenylene)‐32‐crown‐10 (2,2′‐dihydroxy‐BMP32C10, 1a) was synthesized and used to prepare the [2]catenane 4 in an unexpected yield of 68 %, three times the corresponding value for the case in which BMP32C10 (1b) was used and close to the corresponding value for the case in which bis(p‐phenylene)‐34‐crown‐10 was used. This indicated that 1a and paraquat derivatives formed pseudorotaxanes rather than the previously reported “taco complexes” between BMP32C10 and paraquat derivatives. Another unique feature of 1a in relation to other previously reported BMP32C10 derivatives was that its binding to paraquat derivatives in solution could be switched off and back on by addition of K+ and then dibenzo‐18‐crown‐6. In the solid state, a 2:1 [3]pseudorotaxane of 1a with a paraquat derivative was formed.

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Section: Methodsmentioning

confidence: 99%

Section: Synthesis Of the Crown Ether 1amentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Improved Pseudorotaxane and Catenane Formation from a Derivative of Bis(m‐phenylene)‐32‐crown‐10

et al. 2010

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“…Previously, we have reported the formation of pseudo [1]rotaxane dimer from the altro-a-CD (altro-a-CD) dimer via tumbling of altro-a-CD, 40,41 which consists of one altropyranose unit and five glucopyranose units. Although some research groups have reported the tumbling of permethylated glucopyranose type CD, [42][43][44][45][46][47] tumbling of the altropyranose unit in altro-CDs has yet to be reported. We have successfully observed the selective emission of PDI-CD 2 s in aqueous solutions and prepared emission films based on PDI-CD 2 s kneaded into polyvinyl alcohol (PVA) films.…”

Section: Introductionmentioning

confidence: 99%

Emission properties of cyclodextrin dimers linked with perylene diimide—effect of cyclodextrin tumbling

Takashima

Otsubo

et al. 2012

Polym J

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Perylene diimide (PDI) derivatives with cyclodextrins (PDI-CD 2 s) exhibit specific emission properties, which depend on the type of CDs in an aqueous solution. Herein we successfully create an emission film-kneaded PDI-CD 2 derivatives via effective tumbling of the altropyranose unit. PDI-6CD 2 s are crosslinked with PDI between 6-amino-CDs. Although the emission intensities of PDI-6CD 2 s in dimethyl sulfoxide are similar regardless of the type of CD, PDI-6cCD 2 has a relatively high emission intensity in aqueous solutions. In contrast, for PDIC 7 -3CD 2 s, which are linked with N,N'-bis(6-carboxylhexyl)perylene-3,4,9,10-tetracarboxyl diimide (BisC 7 -PDI) between 3-amino-CDs, the emission intensity of PDIC 7 -3bCD 2 is stronger than those of PDIC 7 -3aCD 2 , PDIC 7 -3cCD 2 , and PDI-6CD 2 s in aqueous solutions. The selective emission behavior of PDIC 7 -3CD 2 s is due to the formation of the pseudo[1]rotaxane dimer through tumbling of the altropyranose unit in an aqueous solution. PDIC 7 -3bCD 2 in the solid state does not demonstrate a distinctive emission due to self-quenching, whereas PDIC 7 -3bCD 2 kneaded into the polyvinyl alcohol (PVA) film exhibits a bright yellow emission. The order of the emission intensities of PDIC 7 -3CD 2 s kneaded into PVA films is similar to those in aqueous solutions. INTRODUCTIONRecently, supramolecular assemblies with extended aromatic compounds have attracted much attention. 1-4 Perylene diimides (PDIs) derivatives effectively form supramolecular assemblies through p-p stacking interaction. [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] In particular, supramolecular assemblies based on calixarenePDI conjugates show efficient energy and electron transfer properties due to the well-defined rigid and electron-rich scaffolds of calixarenes. [22][23][24][25][26][27] We have prepared PDI derivatives with a high emission property in aqueous solutions.Generally, PDI derivatives have low solubilities in aqueous solutions. Even if PDI derivatives are dissolved in aqueous solutions by introducing a hydrophilic group, the emission of PDI derivatives exhibit self-quenching in aqueous solutions due to the formation of supramolecular assemblies and folders. To create water-soluble and effective emission sensor materials with PDI derivatives, we have introduced CDs into the PDI motif. The CDs are a family of macrocyclic oligosaccharides; the most common are composed of 6 (a), 7 (b), or 8 (g) a-1,4-linked D-glucopyranose units. [28][29][30][31][32][33][34] The introduction of CDs should influence the molecular recognition property and increase the emission intensity. Although supramolecular assemblies based on permethylated CDPDI conjugates have been previously reported, 35-38 the formation of assemblies cannot prevent the decrease in the monomer emission intensity of the PDI units due

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“…The only case of restricted guest rotation in a cyclodextrinbased system being observable using conventional NMR spectroscopy was reported by Fujita and co-workers. [24] In the complex of sodium 2-naphthalenesulfonate with a mono-altro-b-cyclodextrin, which has a significantly distorted annulus, the shielding and deshielding of the proton resonances of the host showed that the guest does not freely rotate.…”

Section: Introductionmentioning

confidence: 99%

Installation of a Ratchet Tooth and Pawl To Restrict Rotation in a Cyclodextrin Rotaxane

Onagi

Blake

Easton

et al. 2003

Chemistry A European J

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Eight new [2]rotaxanes have been prepared, incorporating an alpha-cyclodextrin as the rotor, a stilbene as the axle, and trinitrophenyl substituents as capping groups. Strategies have been devised to elaborate these by linking the rotor to the axle, to produce two new [1]rotaxanes. Rotational motion in a selection of these rotaxanes has been investigated through the application of two-dimensional NMR spectroscopy by performing TOCSY, DQF-COSY, ROESY and HMQC experiments. This has shown that a methoxyl group incorporated on the stilbene and a succinamide joining the stilbene and the cyclodextrin behave analogously to a ratchet tooth and pawl, respectively, to restrict rotation.

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Restriction of guest rotation based on the distortion of a cyclodextrin cavity

Cited by 33 publications

References 8 publications

Improved Pseudorotaxane and Catenane Formation from a Derivative of Bis(m‐phenylene)‐32‐crown‐10

Improved Pseudorotaxane and Catenane Formation from a Derivative of Bis(m‐phenylene)‐32‐crown‐10

Emission properties of cyclodextrin dimers linked with perylene diimide—effect of cyclodextrin tumbling

Installation of a Ratchet Tooth and Pawl To Restrict Rotation in a Cyclodextrin Rotaxane

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