A DFT study of magnetic interactions in photoswitchable systems

Bousquet, Diane; Peltier, Cyril; Masselin, Charles; Jacquemin, Denis; Adamo, Carlo; Ciofini, Ilaria

doi:10.1016/j.cplett.2012.05.040

Cited by 13 publications

(7 citation statements)

References 44 publications

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“…In the closed-ring isomer strong antiferromagnetic interaction is expected to operate, while the magnetic interaction in the open-ring isomer should be very small. On the basis of this principle, switching of magnetic interaction has been demonstrated. − …”

Section: Switchesmentioning

confidence: 99%

Photochromism of Diarylethene Molecules and Crystals: Memories, Switches, and Actuators

et al. 2014

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Section: Switchesmentioning

confidence: 99%

Photochromism of Diarylethene Molecules and Crystals: Memories, Switches, and Actuators

et al. 2014

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“…26 The theoretical calculation of the switching of exchange interaction J has also been reported. 27 …”

Section: ■ Introductionmentioning

confidence: 97%

“…26 The theoretical calculation of the switching of exchange interaction J has also been reported. 27 In terms of the practical application, it is important to establish a design principle for the highly efficient switching molecule. Although the switching phenomenon itself is observed in various DAEs, the insight into the SE has not been investigated systematically for different DAEs.…”

Section: ■ Introductionmentioning

confidence: 99%

“…After these reports, many groups, including our group, have reported switching of exchange interaction J − and molecular conductance G − based on the photochromism of DAE. The SEs of G , defined as the ratio of conductance G between the open- and the closed-ring isomers, G closed / G open , were reported to be about 1 to 3 orders of magnitude. − The switching of G and J based on the photochromism of DAE has also been investigated theoretically. − For example, Yoshizawa et al showed that molecular conductance G switches about 1000 times between the two isomers of 3-thienyl DAE using nonequilibrium Green’s function density functional theory (NEGF-DFT) . The theoretical calculation of the switching of exchange interaction J has also been reported …”

Section: Introductionmentioning

confidence: 99%

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Computational Investigation into Photoswitching Efficiency of Diarylethene Derivatives: An Insight Based on the Decay Constant of Electron Tunneling

2015

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The switching efficiency (SE) of the intramolecular exchange interaction J between the open-and the closed-ring isomers of diarylethenes (DAEs) was investigated using DFT calculations of DAE biradicals with different core structures: DAEs with 3-thienyl, thiophene-S,S-dioxide-3-yl, 2-thienyl, or thiophene-S,S-dioxide-2-yl rings. The SE of DAE with a 3-thienyl ring is calculated to be around 400-fold, which is the largest among the four calculated DAEs. The decay constant β of the exchange interaction J for the DAE molecular wires was evaluated by calculating J for biradicals with different lengths of wires. For the wires of the closed-ring isomers of DAE with 3-thienyl-and thiophene-S,Sdioxide-3-yl rings, which are supposed to take a quinoid structure, allyl nitronyl nitroxide radical was successfully employed. The calculated β values showed a significant difference between the open-and the closedring isomers, and this difference of β is considered to be the origin of photoswitching of J. The difference of β upon isomerization, Δβ, is in good agreement with SE, and the largest Δβ was obtained for the DAE with a 3-thienyl ring. We can understand the switching of J as the switching of electron tunneling efficiency β between the open-and the closed-ring isomers. ■ INTRODUCTIONRecently molecular electronics has drawn considerable attention in the fields of chemistry and applied physics because of the potential application to single-molecule electronic devices. 1−4 Among these molecular electronic devices, the molecular switch is an essential material to a construct molecular circuit. 5 Diarylethene (DAE) is one of the renowned photochromic molecules which shows reversible photoisomerization between the open-and the closed-ring isomers by irradiation with UV and visible light. 6,7 One of the authors (K.M.) has reported the photoswitching of intramolecular exchange interaction J between the open-and the closed-ring isomers of a 3-thienyl DAE in which nitronyl nitroxide (NN) was connected at each end. 8 The ratio of switching, that is switching efficiency (SE), defined as the ratio of the exchange interaction J between the open-and the closed-ring isomers, J closed /J open , has been reported to be more than 150-fold. In addition, it has also been reported that the switching of J of a 2-thienyl DAE shows the opposite direction of 3-thienyl DAE. 9 After these reports, many groups, including our group, have reported switching of exchange interaction J 10−12 and molecular conductance G 13−23 based on the photochromism of DAE. The SEs of G, defined as the ratio of conductance G between the open-and the closedring isomers, G closed /G open , were reported to be about 1 to 3 orders of magnitude. 13−20 The switching of G and J based on the photochromism of DAE has also been investigated theoretically. 24−27 For example, Yoshizawa et al. showed that molecular conductance G switches about 1000 times between the two isomers of 3-thienyl DAE using nonequilibrium Green's function density functional theory (NEGF-DFT). 26 The theoret...

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“…Besides the above experimental investigations and simple theoretical model studies, abundant theoretical efforts have also achieved . Still, they mainly focused on the thiophene‐based diarylethene derivatives and their properties.…”

Section: Introductionmentioning

confidence: 99%

Theoretical insights into the effect of heterocycles of the molecular framework on photochromic magnetic properties of diarylethene compounds

Huang

Wang

et al. 2019

J of Physical Organic Chem

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Considering the effect of heterocycles on photochromic magnetic properties, we presented a comparative study among series of closed-and open-ring isomers of benzothiophene-, benzofuran-, and 1-methylindole-based diarylperfluorocyclopentenes or diarylmaleic anhydrides bearing nitronyl nitroxide diradicals. Owing to the better itinerant exchange of the unpaired electrons for the closed-ring isomers than for the open-ring ones, the former have ferromagnetic coupling interactions, while the later are antiferromagnetic. This difference indicates that the interconversion between them is switchable. In the molecular framework of the diarylethene, the participation of benzofuran group(s) can increase J ab value and contributes to thermal stability, while that of 1-methylindole group(s) can increase J ab value and has block effect on thermal stability. Still, the later can lead to red-shift of the maximum absorption wavelength, which is benefit for the requirement of the application to optical memory media. It is the better choice for perfluorocyclopentenes than for maleic anhydrides as the bridging group in construction of photochromic magnetic molecular switch of diarylethene compound.

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A DFT study of magnetic interactions in photoswitchable systems

Cited by 13 publications

References 44 publications

Photochromism of Diarylethene Molecules and Crystals: Memories, Switches, and Actuators

Photochromism of Diarylethene Molecules and Crystals: Memories, Switches, and Actuators

Computational Investigation into Photoswitching Efficiency of Diarylethene Derivatives: An Insight Based on the Decay Constant of Electron Tunneling

Theoretical insights into the effect of heterocycles of the molecular framework on photochromic magnetic properties of diarylethene compounds

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