Synthesis, Photochromic Properties, and Crystal Structures of Salts Containing a Pyridinium-Fused Spiropyran: Positive and Negative Photochromism in the Solution and Solid State

Funasako, Yusuke; Miyazaki, Haruka; Sasaki, Tomoya; Goshima, Kenta; Inokuchi, Makoto

doi:10.1021/acs.jpcb.0c04994

Cited by 15 publications

(10 citation statements)

References 33 publications

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“…Upon irradiation with UV light or after dissolution in water, the TMAB-C3-SP form is transformed into the opened TMAB-C3-MC form, accompanied by a solution color change. The visualization of the excitations in MC isomer (Figure 9b) illustrates delocalized conjugated nature of the molecule, which is supported by the majority of theoretical studies [67,77,79,97,110]. The excitations at 504-516nm are attributed to the π − π * transition of the opened form [43].…”

Section: Photophysical Propertiessupporting

confidence: 62%

“…However, the data in Table 2 clearly reveal that the merocyanine isomer represents thermodynamically more stable form, as compared to the spiro-compound. There is a few spiropyrans known from literature, especially those with OH, COOH, NH 2 , and NR 3 groups exhibiting the so-called negative photochromism [26,[94][95][96][97]. Thus, deeply-colored MC solution spontaneously formed by mixing a photochrome with a polar solvent is photo-bleached under visible light.…”

Section: Molecular Propertiesmentioning

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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Section: Photophysical Propertiessupporting

confidence: 62%

Section: Molecular Propertiesmentioning

confidence: 99%

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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“…Few materials showed the opposite which is known as negative photochromism. [34,35] SD coated photo chromic thin films based on D1 show the first report of negative photochromic behavior of this dye. SD coating a purple solution (10 mg mL −1 in MeOH) leads to yellow color thin films that switch to colorless after UV exposure (Figure 2a).…”

Section: Sd Coating Of Photochromic Filmsmentioning

confidence: 88%

Slot‐Die Coated Organic UV Indicators and Filters Processed from Green Solvents

Farahat

Welch

2021

Advanced Sustainable Systems

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Many attempts to fabricate rapid and inexpensive UV indicators have been introduced. [9][10][11][12][13][14][15][16][17][18][19] Among them, wearable and flexible devices have emerged as the ideal practical candidate. [20] However, most of them are based on electronic devices employing inorganic semiconductors generating current under UV radiations. For these types, external electronic devices (e.g., smart phones) are required to read and process the collected data. [21,22] In addition mass production and large area fabrication often require expensive high-tech processes, e.g., thermal deposition. Therefore, for affordable and rapid personal day-to-day UV indicators, according to Zou et al. they should offer "FLIP" features where FLIP refers to: i) Flexible-to ensure the mechanical robustness during movement; ii) Low-powered or even self-powered-to avoid large power supply units; iii) Instant response-to provide real-time detection; and iv) be portable-to offer comfortable user experience. [20] These criteria are highly applicable to photochromic or photodegradable organic dyes/polymers as cost-effective and easy-processable UV active layers. [3,10,15,18,19,23,24] Photochromic dyes have been widely employed as sensitive active layers for various sensing applications such as pH, metal ions, gas and vapor, temperature, and UV light. [9] For UV sensing applications as the topic of the current study, Zheng et al. reported a wearable UV indicator based on electrospun spiropyran photochromic dyed fibers and a step toward textile based wearable UV indicators. [17] Butterfield et al. have demonstrated a long-term (months to years) intradermal tattoo based on spirooxazine photochromic nanocapsules, a step toward skin-intergrade UV indicators. [3] Although ink formulation and film preparation for these systems are unique and innovative, the working UV indicator fabrication process is sophisticated. UVR (λ < 356 nm) is representing 5% of the total solar flux. [25] Organic electronic devices such as OPVs are exposed to quantities of UVR enough to dramatically reduce their operational long-term stability. Numerous studies have used commercially available inorganic UVA and/or UVB long pass filters to minimize the UV amount absorbed by the OPVs devices to increase their stability. [5][6][7]26] Recently Chen et al. reported using high quality thermally evaporated semitransparent inorganic CsPbBr 3 perovskite as a dual functional layer acting as UV filter and light absorbing material. By integration with OPVs in tandem structure, they achieved PCEs > 14% with excellent photostability. [27] Kimura et al. used 1.3 µm thick transparent This work reports the use of the slot-die (SD) coating solution processing method to fabricate large-area organic thin films composed of photochromic dyes as UV indicators and UV light absorbers as UV filters on polyethylene terephthalate flexible substrates. This is the first demonstration of large-area SD coated organic photochromic films and UV filters. Impressively, highly uniform photochromic fil...

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“…В процессе синтеза индолиновых спиро-пиранов, содержащих сопряженные катионные винил-3Н-индолиновые фрагменты и их аналогов с формильным заместителем в 2Н-хроменовом фрагменте получено соединение СП 23, проявляющее отрицательный фотохромизм под действием УФ излучения [19]. Пиридиний-содержащий спиропиран СП 24 проявляет отрицательный фотохромизм в растворах и положительный фотохромизм в кристаллическом состоянии [20].…”

Section: сп 22unclassified

Отрицательный Фотохромизм: Последние Достижения

Barachevsky¹

2021

РХЖ

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Представлен анализ последних достижений в исследовании явления отрицательного фотохромизма органических соединений из классов спиропиранов, Стенхаус и нитрил-содержащих соединений, бииимидазолильных радикальныых комплексов, дигидропиранов, цианиновых красителей, азуленов и гидразонов. Установлены зависимости спектрально-кинетических свойств от их структуры и природы заместителей. Рассмотрены возможности применения фотохромных систем на их основе в создании покрытий с фотоадаптивными свойствами и в биомедицинских технологиях.

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Synthesis, Photochromic Properties, and Crystal Structures of Salts Containing a Pyridinium-Fused Spiropyran: Positive and Negative Photochromism in the Solution and Solid State

Cited by 15 publications

References 33 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

Slot‐Die Coated Organic UV Indicators and Filters Processed from Green Solvents

Отрицательный Фотохромизм: Последние Достижения

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