Kinetics and mechanism of the reaction of photoinduced 9-aryloxy-1,10-anthraquinones with alcohols

Klimenko, L. S.; Gritsan, Nina P.; Fokin, E. P.

doi:10.1007/bf00960658

Cited by 5 publications

(5 citation statements)

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“…Depending on the reaction time, intermediates 33 and 35 could be isolated in case of anthraquinone PAQs. [97] On contrary, the primary adducts of ana-PAQ with primary aliphatic and aromatic amines 36 are thermodynamically unstable and spontaneously eliminate phenol (Scheme 6C). The resulting species exists as a mixture of two tautomeric forms: enaminoquinoid 31 and oxy-imine 32.…”

Section: Reactivity Of Ana-isomersmentioning

confidence: 99%

“…According to calculations, this process is the exergonic one [96] . The selectivity of the nucleophilic attack at position 4 (Scheme 6) may be rationalized in terms of the charge distribution [97] or the largest coefficient in the LUMO of the ana ‐PAQ molecule [98] . The next step of the reaction, i. e., phenol (ArOH) elimination, is strongly dictated by the structure of the primary adduct [96,99] .…”

Section: Photochromic Performancementioning

confidence: 99%

“…After elimination of phenol, the second alcohol molecule can add to intermediate 34 and form acetals 35 . Depending on the reaction time, intermediates 33 and 35 could be isolated in case of anthraquinone PAQs [97] …”

Section: Photochromic Performancementioning

confidence: 99%

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Revisiting Peri‐Aryloxyquinones: From a Forgotten Photochromic System to a Promising Tool for Emerging Applications

Lvov,

Klimenko,

Bykov

et al. 2023

Chemistry A European J

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Emerging applications of photochromic compounds demand new molecular designs that can be inspired by some long‐known yet currently forgotten classes of photoswitches. In the present review, we remind the community about Peri‐AryloxyQuinones (PAQs) and their unique photoswitching behavior originally discovered more than 50 years ago. At the heart of this phenomenon is the light‐induced migration of an aromatic moiety (arylotropy) in peri‐aryloxy‐substituted quinones resulting in ana‐quinones. PAQs feature absorbance of both isomers in the visible spectral region, photochromism in the amorphous and crystalline state, and thermal stability of the photogenerated ana‐isomer. Particularly noticeable is the high sensitivity of the ana‐isomer towards nucleophiles in solution. In addition to the mechanism of molecular photochromism and the underlaying structure‐switch relationships, we analyze potential applications and prospects of aryloxyquinones in optically switchable materials and devices. Due to their ability to efficiently photoswitch in the solid state, PAQs are indeed attractive candidates for such materials and devices, including electronics (optically controllable circuits, switches, transistors, memories, and displays), porous crystalline materials, crystalline actuators, photoactivated sensors, and many more. This review is intended to serve as a guide for researchers who wish to use photoswitchable PAQs in the development of new photocontrollable materials, devices, and processes.

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Section: Reactivity Of Ana-isomersmentioning

confidence: 99%

Section: Photochromic Performancementioning

confidence: 99%

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Revisiting Peri‐Aryloxyquinones: From a Forgotten Photochromic System to a Promising Tool for Emerging Applications

Lvov,

Klimenko,

Bykov

et al. 2023

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…According to calculations, this process is the exergonic one. [96] The selectivity of the nucleophilic attack at position 4 (Scheme 6) may be rationalized in terms of the charge distribution [97] or the largest coefficient in the LUMO of the ana-PAQ molecule. [98] The next step of the reaction, i. e., phenol (ArOH) elimination, is strongly dictated by the structure of the primary adduct.…”

Section: Reactivity Of Ana-isomersmentioning

confidence: 99%

Revisiting peri-aryloxyquinones: From a forgotten photochromic system to a promising tool for emerging applications

Lvov,

Klimenko,

Bykov

et al. 2023

Preprint

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Emerging applications of photochromic compounds demand new molecular designs that can be inspired by some long-known yet currently forgotten classes of photoswitches. In the present review, we would like to remind the community about Peri-AryloxyQuinones (PAQs) and their unique photoswitching behavior originally discovered by Gerasimenko more than 50 years ago. At the heart of this phenomenon is the light-induced migration of an aromatic moiety (arylotropy) in peri-aryloxy-substituted quinones resulting in ana-quinones. PAQs feature absorbance of both isomers in the visible spectral region, photochromism in the amorphous and crystalline state, and thermal stability of the photogenerated ana-isomer. Particularly noticeable is the high sensitivity of the ana-isomer towards nucleophiles in solution. In addition to the mechanism of molecular photochromism and the underlaying structure-switch relationships, we analyze potential applications and prospects of aryloxyquinones in optically switchable materials and devices. Due to their ability to efficiently photoswitch in the solid state, PAQs are indeed attractive candidates for such materials and devices, including electronics (optically controllable circuits, switches, transistors, memories, and displays), porous crystalline materials, crystalline actuators, photoactivated sensors, and many more. This review is intended to serve as a guide for researchers who wish to use photoswitchable PAQs in the development of new photocontrollable materials, devices, and processes.

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“…We assumed that the addition of 4-( tert -butyl)phenol ( TBP ) to ana - 2 would lead to HDA adduct 3 with two equal aryloxy groups (Figure A). In contrast to the reactions of photogenerated ana -quinones with amines and alcohols, , this process should not lead to irreversible loss of switchable properties because back elimination would lead exclusively to ana - 2 (for example, adducts with alcohols eliminate the phenols with loss of photochromism). Indeed, irradiation of para - 2 done in the presence of 1 equiv of TBP gave a mixture of ana - 2 and adduct 3 according to NMR spectroscopy (Figure B).…”

mentioning

confidence: 99%

Activation of Anthraquinone’s Electrophilicity by Light for a Dynamic C–O Bond

Bykov,

Ukhanev,

Ushakov

et al. 2024

J. Am. Chem. Soc.

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Coupling of photoswitching with dynamic covalent chemistry enables control of the formation and cleavage of covalent bonds by light irradiation. peri-Aryloxyanthraquinones feature an exclusive ability to switch electrophilicity by interconversion between para-and ana-quinone isomers, which was used for the first time for the implementation of a dynamic C−O bond. Photogenerated ana-isomers undergo a concerted oxa-Michael addition of phenols to give hitherto unknown 4-hydroxy-10,10-diaryloxyanthracen-9-ones. These species were found to be in equilibrium with the corresponding ana-quinones, thus forming a dynamic covalent system of a new type. Withdrawal of the colored ana-quinones from the equilibria by visible light irradiation resulted in two para-quinones with "locked" aryloxy groups.

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Kinetics and mechanism of the reaction of photoinduced 9-aryloxy-1,10-anthraquinones with alcohols

Cited by 5 publications

References 1 publication

Revisiting Peri‐Aryloxyquinones: From a Forgotten Photochromic System to a Promising Tool for Emerging Applications

Revisiting Peri‐Aryloxyquinones: From a Forgotten Photochromic System to a Promising Tool for Emerging Applications

Revisiting peri-aryloxyquinones: From a forgotten photochromic system to a promising tool for emerging applications

Activation of Anthraquinone’s Electrophilicity by Light for a Dynamic C–O Bond

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