Photochromism of peri-aryloxy-p-quinones. Determination of molar extinction coefficients of 6-phenoxy-5,11-naphthacenequinones

Gerasimenko, Yu. E.; Parshutkin, A. A.; Poteleshchenko, N. T.; Poteleshchenko, V. P.; Romanov, V. V.

doi:10.1007/bf00608442

Cited by 4 publications

(7 citation statements)

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“…Standard electrophilic substitution of pyrene produces a mixture of 1,8-, 1,6-, and 1,3-disubstituted products and they react at the undesirable 6 and 8 positions and 2,7-disubstituted tetrahydropyrenes can be prepared by intramolecular coupling of m -cyclophanes and can then be aromatized to pyrenes. , However, these routes did not seem likely to meet our needs.…”

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confidence: 95%

“…5 2-Substituted pyrenes are difficult to obtain, 6 and they react at the undesirable 6 and 8 positions. 7 A few 2,7disubstituted pyrenes are known: for example, bis tertbutylation of pyrene gives the 2,7-disubstituted product for steric reasons, 8 and 2,7-disubstituted tetrahydropyrenes can be prepared by intramolecular coupling of m-cyclophanes 9 and can then be aromatized to pyrenes. 10,11 However, these routes did not seem likely to meet our needs.…”

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confidence: 99%

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7-Amino-2-pyrenecarboxylic Acid

et al. 1996

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Pyrenes undergo initial electrophilic substitution in the 1 position; a second substitution typically occurs in the 3, 6, or 8 positions. We sought a pyrene with synthetically useful handles in the unusual 2,7 substitution pattern. To that end, 7-amino-2-pyrenecarboxylic acid was prepared by partial reduction of pyrene to 4,5,9,10-tetrahydropyrene, Friedel−Crafts acylation in the 2 position, and conversion to 2-carbethoxytetrahydropyrene through the haloform reaction and esterification. Nitration of the ester proceeded in the 7 position; rearomatization, reduction of the nitro group, and saponification gave the title compound.

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confidence: 95%

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confidence: 99%

7-Amino-2-pyrenecarboxylic Acid

et al. 1996

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“…At the same time, substituents on the migrating aryl group only weakly affect the maxima of absorption bands of both para-as well as ana-isomers. [50][51][52] In general, PAQ photoswitches exhibit a significant band separation of their para-and ana-isomers as a result of the fully aromatic π-system in the para-isomers formally consisting of two benzene rings while the ana-isomers consists of only one benzene ring and a system of conjugated double bonds.…”

Section: Spectral Propertiesmentioning

confidence: 99%

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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“…In fact, the simple electrophilic dibromination of pyrene produces a mixture of 1,6‐ and 1,8‐dibromopyrenes, not 1,3‐dibromopyrene (Figure 1c). [7] 1,3‐Dibromopyrene can be synthesized in low yield (<10 %) from the expensive 2‐pyrenecarboxylic acid [18] . Our group found that long‐axially symmetric pyrene derivatives may exhibit photophysical properties [14] and intracellular localization behaviors [19] considerably different from those of their isomers.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of 1,3‐Dibromopyrene as Precursor of 1‐, 3‐, 6‐, and 8‐Substituted Long‐Axially Symmetric Pyrene Derivatives

Ruto,

Seki,

Osaki

et al. 2024

Chemistry A European J

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Pyrene derivatives bearing substituents at positions 1, 3, 6, and 8 find numerous applications, as exemplified by their use in lasers, sensors, and bioimaging probes. However, these derivatives typically have point‐symmetric or short‐axially symmetric structures, whereas long‐axially symmetric derivatives remain underexplored because of the difficulty in obtaining their precursor, 1,3‐dibromopyrene. To address this problem, we herein synthesized 1,3‐dibromopyrene from 1‐methoxypyrene in an overall yield (71% over four steps) considerably exceeding those of existing methods. 1,3‐Dibromopyrene was converted into 13OPA, a long‐axially symmetric pyrene dye with electron‐donor (alkoxy) groups at positions 1 and 3 and electron‐acceptor (formyl) groups at positions 6 and 8. 13OPA exhibited photophysical properties distinct from those of its point‐symmetric and short‐axially symmetric isomers, featuring a broad and strongly redshifted absorption, strong fluorescence with reduced sensitivity to protic solvents, and small dipole moment change upon photoexcitation. The derivatization of 13OPA into a Schiff base and its functionalization via Lewis acid–base pairing were also demonstrated. Thus, our work expands the design scope of pyrene‐based molecules, particularly those used as emitters.

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Photochromism of peri-aryloxy-p-quinones. Determination of molar extinction coefficients of 6-phenoxy-5,11-naphthacenequinones

Cited by 4 publications

References 0 publications

7-Amino-2-pyrenecarboxylic Acid

7-Amino-2-pyrenecarboxylic Acid

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

Synthesis of 1,3‐Dibromopyrene as Precursor of 1‐, 3‐, 6‐, and 8‐Substituted Long‐Axially Symmetric Pyrene Derivatives

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