Detection of photoreversibility of NO2–ONO linkage isomerization in [Co(NH3)5NO2]Cl(NO3 crystals by the photomechanical response method

Мұқаба

Дәйексөз келтіру

Толық мәтін

Ашық рұқсат Ашық рұқсат
Рұқсат жабық Рұқсат берілді
Рұқсат жабық Тек жазылушылар үшін

Аннотация

Linkage isomerization NO2-ONO (nitro-nitrito) in the complex cation [Co(NH3)5NO2]2+ is a well-studied classical reaction. It is believed that the photoisomerization of the nitro form to nitrito in the crystalline phase achieves complete transformation at low temperature, while the reverse transformation proceeds as a first-order thermal intramolecular reaction upon heating of the crystals. To date, there is no information about the possibility of reverse photoisomerization. In this work, photoisomerization in [Co(NH3)5NO2]Cl(NO3) crystals is investigated by the analysis of crystal deformation caused by the transformation at different wavelengths. A change in the lattice parameters during the transformation leads to reliably measurable elongation and bending of acicular crystals. It is shown that the limiting elongation of the crystal under prolonged irradiation depends on the wavelength, which proves the reversibility of photoisomerization. The quantum yield of the reverse reaction is estimated to be 0.04 of the quantum yield of the direct reaction.

Толық мәтін

Рұқсат жабық

Авторлар туралы

S. Chizhik

Institute of Solid State Chemistry and Mechanochemistry Siberian Branch of Russian Academy of Science

Хат алмасуға жауапты Автор.
Email: stas@solid.nsc.ru
Ресей, Novosibirsk

P. Gribov

Institute of Solid State Chemistry and Mechanochemistry Siberian Branch of Russian Academy of Science

Email: stas@solid.nsc.ru
Ресей, Novosibirsk

V. Kovalskii

Institute of Solid State Chemistry and Mechanochemistry Siberian Branch of Russian Academy of Science

Email: stas@solid.nsc.ru
Ресей, Novosibirsk

A. Sidelnikov

Institute of Solid State Chemistry and Mechanochemistry Siberian Branch of Russian Academy of Science

Email: stas@solid.nsc.ru
Ресей, Novosibirsk

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Әрекет
1. JATS XML
2. Fig. 1. Extinction coefficient of isomers [Co(NH3)5NO2]2+ (1) and [Co(NH3)5ONO]2+ (2) in aqueous solution. Data taken from [8].

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3. Fig. 2. Image of the measured crystal (a) and noise of measuring the length and relative deflection of the central part of the crystal without illumination at T = 0 °C (b).

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4. Fig. 3. Kinetics of changes in elongation (a) and curvature (b) of a crystal upon sequential illumination by sources with wavelengths of 425, 350, and 425 nm at T = 0 °C. Insets: enlarged sections of the dependences of changes in the length and curvature of the crystal caused by switching light sources.

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5. Fig. 4. Combined image of the crystal in three successive stages of the process shown in Fig. 3: 1 - initial state, 2 - peak of curvature when illuminated by a source l = 425 nm (t = 103 s), 3 - peak of curvature achieved after switching from a wavelength of 425 to 350 nm (t = 104 s). Image 2 shows the marks used by the crystal shape analysis algorithm. The arrows indicate the direction of crystal illumination.

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6. Fig. 5. Kinetics of changes in elongation (a) and curvature (b) of the [Co(NH3)5NO2]Cl(NO3) crystal caused by switching radiation sources: 1 - 403 → 350 nm, 2 - 403 → 375 nm, 3 - 403 → 425 nm, 4 - 403 → 465 nm, 5 - 425 → 350 nm, 6 - 465 → 350 nm, 7 - 465 → 375 nm, 8 - 465 → 425 nm, 9 - 465 → 491 nm.

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7. Fig. 6. Dependence of the photostationary degree of nitro-nitrite isomerization on wavelength at 0 °C in the [Co(NH3)5NO2]Cl(NO3) crystal (dots) and the model of the Cps(l) dependence, according to equation (3) at Ф2/Ф1 = 0.04 (line).

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8. Fig. 7. Dependence of the residual curvature of the crystal in the photostationary state on the wavelength of the radiation source, calculated from equation (7).

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Ескертпе

Х Международная конференция им. В.В. Воеводского “Физика и химия элементарных химических про­цессов” (сентябрь 2022, Новосибирск, Россия).


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