Structures of spiropyrans exhibiting photochromic properties in the solid state

Pugachev, A. D.; Ткачев, В. В.; Ozhogin, Ilya V.; Lukyanova, M. B.; Алдошин, С. М.; Муханов, Е. Л.; Metelitsa, Anatoly V.; Stankevich, N. V.; Lukyanov, B. S.

doi:10.1007/s11172-021-3320-2

Cited by 14 publications

(15 citation statements)

References 42 publications

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“…The same bond is 1.496 Å in experimental studies by Zhang et al [ 35 ], 1.456 Å in measurements described by Pugachev et al [ 67 ] and varies from 1.4558 to 1.488 Å, as reported by Seiler and co-workers [ 66 ]. The chemical bond C

–N is 1.472 Å; the experimental values are 1.438 [ 35 ], 1.452 [ 67 ] and from 1.426 to 1.446 Å [ 66 ]. The values reported in theoretical calculations published in the literature [ 49 , 53 , 54 , 56 , 57 ] are closer to the mentioned values evaluated in this work.…”

Section: Resultssupporting

confidence: 71%

“…For example, the C

–O bond has a length of 1.453 Å for SP illustrated in Figure 3 a. The same bond is 1.496 Å in experimental studies by Zhang et al [ 35 ], 1.456 Å in measurements described by Pugachev et al [ 67 ] and varies from 1.4558 to 1.488 Å, as reported by Seiler and co-workers [ 66 ]. The chemical bond C

–N is 1.472 Å; the experimental values are 1.438 [ 35 ], 1.452 [ 67 ] and from 1.426 to 1.446 Å [ 66 ].…”

Section: Resultssupporting

confidence: 67%

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Spiropyran/Merocyanine Amphiphile in Various Solvents: A Joint Experimental–Theoretical Approach to Photophysical Properties and Self-Assembly

Savchenko

Lomadze

Santer

et al. 2022

IJMS

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This joint experimental-theoretical work focuses on molecular and photophysical properties of the spiropyran-containing amphiphilic molecule in organic and aqueous solutions. Being dissolved in tested organic solvents, the system demonstrates positive photochromism, i.e., upon UV stimulus the colorless spiropyran form is transformed into colorful merocyanine isomer. However, the aqueous solution of the amphiphile possesses a negative photochromism: the orange-red merocyanine form becomes thermodynamically more stable in water, and both UV and vis stimuli lead to the partial or complete photobleaching of the solution. The explanation of this phenomenon is given on the basis of density functional theory calculations and classical modeling including thermodynamic integration. The simulations reveal that stabilization of merocyanine in water proceeds with the energy of ca. 70 kJ mol−1, and that the Helmholtz free energy of hydration of merocyanine form is 100 kJ mol−1 lower as compared to the behavior of SP isomer in water. The explanation of such a difference lies in the molecular properties of the merocyanine: after ring-opening reaction this molecule transforms into a zwitterionic form, as evidenced by the electrostatic potential plotted around the opened form. The presence of three charged groups on the periphery of a flat conjugated backbone stimulates the self-assembly of merocyanine molecules in water, ending up with the formation of elongated associates with stack-like building blocks, as shown in molecular dynamics simulations of the aqueous solution with the concentration above critical micelle concentration. Our quantitative evaluation of the hydrophilicity switching in spiropyran/merocyanine containing surfactants may prompt the search for new systems, including colloidal and polymeric ones, aiming at remote tuning of their morphology, which could give new promising shapes and patterns for the needs of modern nanotechnology.

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Section: Resultssupporting

confidence: 71%

“…For example, the C

–N is 1.472 Å; the experimental values are 1.438 [ 35 ], 1.452 [ 67 ] and from 1.426 to 1.446 Å [ 66 ].…”

Section: Resultssupporting

confidence: 67%

Spiropyran/Merocyanine Amphiphile in Various Solvents: A Joint Experimental–Theoretical Approach to Photophysical Properties and Self-Assembly

Savchenko

Lomadze

Santer

et al. 2022

IJMS

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“…For example, the C spiro -O bond has length of 1.453 Å for SP illustrated in Figure 4a. The same bond is 1.496 Å in experimental studies by Zhang et al [43], 1.456 Å in measurements described by Pugachev et al [93] and varies from 1.4558 to 1.488 Å, as reported by Seiler and co-workers [92]. The chemical bond C spiro -N is 1.472 Å; the experimental values are 1.438 [43], 1.452 [93] and from 1.426 to 1.446 Å [92].…”

Section: Molecular Propertiessupporting

confidence: 61%

“…The same bond is 1.496 Å in experimental studies by Zhang et al [43], 1.456 Å in measurements described by Pugachev et al [93] and varies from 1.4558 to 1.488 Å, as reported by Seiler and co-workers [92]. The chemical bond C spiro -N is 1.472 Å; the experimental values are 1.438 [43], 1.452 [93] and from 1.426 to 1.446 Å [92]. The values reported in theoretical calculations published in literature [58,64,65,67,68] are closer to the mentioned values evaluated in this work.…”

Section: Molecular Propertiessupporting

confidence: 60%

“…This property has been calculated for the optimized geometries in implicit water. The analysis of the ESP surfaces is a common approach to describe the ring-opening reaction of spiropyrans [79,98], to calculate the group charges accumulated on the acceptor and donor groups of the MC form as useful indicators to get insight into the charge separated state of the molecule [67,69], to shed light on the polarity of the protonated MC forms upon hydrolysis [70], for studying crystal packings of various spiropyrans [93]. The mentioned properties are assuredly important, but here we would like to emphasize that the charge redistribution appears also as a decisive factor of hydrophobicity change upon light stimulus, that has been anticipated in experiments [27,30,44].…”

Section: Solventmentioning

confidence: 99%

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Spiropyran/Merocyanine Amphiphile in Various Solvents: A Joint Experimental–Theoretical Approach to Photophysical Properties and Self-Assembly

Savchenko¹,

Lomadze²,

Santer³

et al. 2022

Preprint

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This joint experimental-theoretical work focuses on molecular and photophysical properties of the spiropyran-containing amphiphilic molecule in organic and aqueous solutions. Being dissolved in tested organic solvents, the system demonstrates positive photochromism, i.e. upon UV stimulus the colorless spiropyran form is transformed into colorful merocyanine isomer. However, aqueous solution of the amphiphile possesses a negative photochromism: the orange-red merocyanine form turns to be thermodynamically more stable in water, and both UV and vis stimuli lead to the partial or complete photobleaching of the solution. The explanation of this phenomenon is given on the basis of density functional theory calculations and classical modeling including thermodynamic integration. The simulations reveal that stabilization of merocyanine in water proceeds with the energy of ca. 70 kJ mol−1, and that the Helmholtz free energy of hydration of merocyanine form is 100 kJ mol−1 lower as compared to the behavior of SP isomer in water. The explanation of such a difference lies in the molecular properties of the merocyanine: after ring-opening reaction this molecule transforms into a zwitterionic form, as evidenced by the electrostatic potential plotted around the opened form. The presence of three charged groups on the periphery of a flat conjugated backbone stimulates the self-assembly of merocyanine molecules in water, ending up with the formation of elongated associates with stack-like building blocks, as shown in molecular dynamics simulations of the aqueous solution with the concentration above critical micelle concentration. Our quantitative evaluation of the hydrophilicity switching in spiropyran/merocyanine containing surfactants may prompt the search for new systems, including colloidal and polymeric ones, aiming at remote tuning of their morphology, which could give new promising shapes and patterns for the needs of modern nanotechnology.

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Tunable Photochromism of Spirooxazine in the Solid State: A New Design Strategy Based on the Hypochromic Effect

Zhang

Lou

et al. 2023

Advanced Materials

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As an important organic photofunctional material, spirooxazine (SO) usually does not exhibit photochromism in the solid state since the intermolecular π–π stacking impedes photoisomerization. Developing photochromic SO in the solid state is crucial for practical applications but is still full of challenges. Here, a series of spirooxazine derivatives (SO1–SO4) with bulky aromatic substituents at the 4‐ and 7‐positions of the skeleton, which provide them with a large volume with which to undergo solid‐state photochromism under mild conditions, is designed and synthesized. All the compounds SO1–SO4 exhibit tunable solid photochromism without ground colors, excellent fatigue resistance, and high thermal stability. Notably, it takes only 15 s for SO4 to reach the saturation of absorption intensity, thought to represent the fastest solid‐state photoresponse of spirooxazines. X‐ray crystal structures of the intermediate compound SO0 and the products SO1–SO2 as well as computational studies suggest that the bulky aromatic groups can lead to a hypochromic effect, allowing for the photochromism of SO in the solid state. The ideal photochromic properties of these spirooxazines open a new avenue for their applications in UV printing, quick response code, and related fields.

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Structures of spiropyrans exhibiting photochromic properties in the solid state

Cited by 14 publications

References 42 publications

Spiropyran/Merocyanine Amphiphile in Various Solvents: A Joint Experimental–Theoretical Approach to Photophysical Properties and Self-Assembly

Spiropyran/Merocyanine Amphiphile in Various Solvents: A Joint Experimental–Theoretical Approach to Photophysical Properties and Self-Assembly

Spiropyran/Merocyanine Amphiphile in Various Solvents: A Joint Experimental–Theoretical Approach to Photophysical Properties and Self-Assembly

Tunable Photochromism of Spirooxazine in the Solid State: A New Design Strategy Based on the Hypochromic Effect

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