Syntheses of Dithienylcyclopentene Optical Molecular Switches

Lucas, Linda N.; Jong, Jaap J. D. de; Esch, Jan H. van; Kellogg, Richard M.; Feringa, Bernard

doi:10.1002/1099-0690(200301)2003:1<155::aid-ejoc155>3.0.co;2-s

Cited by 225 publications

(160 citation statements)

References 37 publications

(70 reference statements)

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“…Dimer 4, in which the dithienylethene moiety is connected directly to the secondary rim of the cyclodextrin cavity, was synthesized from b-cyclodextrin amine 1 and 5,5'-(dicarboxydithienyl)cyclopentene [15] (2). 3-amino-3-deoxy-heptakis(6-O-tert-butyldimethylsilyl)-b-cyclodextrin [16] (1) was used as a precursor for dimer 4 to ensure selective and rigid coupling of the dithienylethene unit directly onto the secondary side of the b-cyclodextrin.…”

Section: Resultsmentioning

confidence: 99%

“…The absorption spectrum of dimer 9 ( Figure 1) is very similar to that of dimer 4 [14] and is typical for the type of dithienylethene moiety used for the spacing of the dimers. [15] Aqueous solutions of the open forms of both dimers showed strong absorption in the UV region, with absorption maxima at 267 and 254 nm for dimers 4 a and 9 a, respectively. The colorless aqueous solutions turned red upon irradiation at 313 nm and an absorption band appeared around 344 nm, together with a broad absorption band in the visible region of the absorption spectra with a maximum at 524 nm for both dimer 4 b and 9 b.…”

Section: Resultsmentioning

confidence: 99%

“…The results obtained with dimers 4 and 9 are comparable to those obtained with similar dithienylethene switches and indicate that the coupling and close proximity of the cyclodextrin cavities does not interfere with the switching process and that the characteristics of the dithienylethene tether are maintained in the cyclodextrin dimers. [15] UV/Vis modeling: Modeling of the UV/Vis spectra of a dimer to directly determine the composition of a mixture of its open and closed forms is an easy and practical alternative to the generally used method of integration of the characteristic thiophene proton signals in the 1 H NMR spectra. The UV/Vis spectra were modeled by fitting a set of Gaussians to the absorption bands in the spectra of the open forms of the dimers.…”

Section: Resultsmentioning

confidence: 99%

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Photocontrolled Release and Uptake of a Porphyrin Guest by Dithienylethene‐Tethered β‐Cyclodextrin Host Dimers

Mulder

Juković

Leeuwen

et al. 2004

Chemistry A European J

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Two photoswitchable dithienylethene‐tethered β‐cyclodextrin dimers were synthesized to function as host molecules with an externally controllable binding affinity. The cyclodextrin cavities of these dimers are linked through their secondary sides by a photochromic dithienylethene unit that is connected to the secondary rim either directly (4) or through propyl spacers (9). Irradiation with light switches these dimers between a relatively flexible (open) and a rigid (closed) form. The binding properties of the dimers depend on the configuration of the dithienylethene spacer, as is shown by microcalorimetry performed with tetrakis‐sulfonatophenyl porphyrin (TSPP) as a guest molecule. The differences in binding properties are most pronounced for the more rigid dimer 4, which binds TSPP 35 times more strongly in the open form (4 a) than in the closed form (4 b). The values found for the enthalpy of binding (ΔH°) indicate that this difference in binding is due to the loss of cooperativity between the two β‐cyclodextrin cavities in the closed form. Molecular modeling shows that 4 b is not able to bind TSPP effectively in both cyclodextrin cavities. The open and closed forms of the more flexible dimer 9 show no substantial difference in their binding of TSPP. Thermodynamic values indicative of strong binding of TSPP by two β‐cyclodextrin cavities were measured for both forms of the dimer, and molecular modeling confirms that both are flexible enough to tightly bind TSPP. The binding differences between the forms of dimer 4 allow the photocontrolled release and uptake of TSPP, which renders control of the ratio of complexed to free TSPP in solution possible.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Photocontrolled Release and Uptake of a Porphyrin Guest by Dithienylethene‐Tethered β‐Cyclodextrin Host Dimers

Mulder

Juković

Leeuwen

et al. 2004

Chemistry A European J

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“…DTCP was synthesized in five steps from 2-Methylthiophene following Lucas et al and 7.5 nm oleic acid-capped PbS QDs were obtained according to Weidman et al [12,13]. All materials were processed and characterized under inert conditions in a glovebox.…”

Section: Methodsmentioning

confidence: 99%

Towards Photo-Switchable Transport in Quantum Dot Solids

Schedel

Thalwitzer

Khoshkhoo

et al. 2016

Zeitschrift Für Physikalische Chemie

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Abstract:We use the photochromic organic semiconductor 1,2-Bis(5′-carboxy-2′-methylthien-3′-yl)-cyclopentene (DTCP) to cross-link PbS quantum dots assembled into thin films. The ligand exchange is monitored by means of vibrational spectroscopy (FT-IR) and core-level X-ray photoemission spectroscopy (XPS). Transport measurements in a field-effect transistor (FET) set-up reveal ambipolar behavior with hole and electron mobilities on the order of 10 −4 cm 2 /Vs and 10 −5 cm 2 /Vs, respectively. Exposure to UV light from a 4 W UV lamp does not significantly change the transport properties, indicating that switching of DTCP is hindered in the hybrid film. We find a pronounced photo-conductance with rapid and reversible photo-response on the order of few seconds, which we attribute to (de-)filling of QD trap states. Our results indicate that hybrid, nanostructured networks of PbS QDs cross-linked with DTCP can be obtained by the presented procedure but that switching of the QD-bound DTCP appears to be hindered compared to the pure, unbound molecular species. We discuss future means to address this problem.

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“…1 Herein is described the careful design of a polyphenylene precursor with a strategically positioned 3-thienyl moiety and the formation of a fully cyclised thienyl-hexabenzocoronene along with its 5,5 0 dimer. Although some sulfur containing polycyclic aromatic hydrocarbons have been previously reported, 2 these systems are the first sulfur containing hexabenzocoronenes.…”

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confidence: 99%