Light controlled dimerization of spiropyran as a tool to achieve dual responsive capture and release system in aqueous media

Kumar, Arvind; Sahoo, Priya Ranjan; Prakash, K. B.; Arya, Yogita; Kumar, Satish

doi:10.1016/j.jelechem.2021.115845

Cited by 12 publications

(8 citation statements)

References 83 publications

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“…To date, most photoswitches, such as azobenzene, spiropyran, and their derivatives, have been used to gate the reactions. [6][7][8][9][10][11][12][13][14][15][16] In this work, we use a different type of photoresponsive molecule called a photobase of two different categories. Brønsted photobases are compounds that are weak bases in their ground state; however, they become strong bases capable of proton capture in their electronically excited state.…”

Section: Introductionmentioning

confidence: 99%

“…In light‐controlled chemical reactions, light acts as an external stimulus on the gate, a substance that undergoes a certain photoreaction, providing remote control over the desired chemical process. To date, most photoswitches, such as azobenzene, spiropyran, and their derivatives, have been used to gate the reactions [6–16] . In this work, we use a different type of photoresponsive molecule called a photobase of two different categories.…”

Section: Introductionmentioning

confidence: 99%

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Controlling pH‐Sensitive Chemical Reactions Pathways with Light ‐ a Tale of Two Photobases: an Arrhenius and a Brønsted

Yucknovsky,

Amdursky

2023

Chemistry A European J

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Light‐gated chemical reactions allow spatial and temporal control of chemical processes. Here, we suggest a new system for controlling pH‐sensitive processes with light using two photobases of Arrhenius and Brønsted types. Only after light excitation do Arrhenius photobases undergo hydroxide ion dissociation, while Brønsted photobases capture a proton. However, none can be used alone to reversibly control pH due to the limitations arising from excessively fast or overly slow photoreaction timescales. We show here that combining the two types of photobases allows light‐triggered and reversible pH control. We show an application of this method in directing the pH‐dependent reaction pathways of the organic dye Alizarin Red S simply by switching between different wavelengths of light, i. e., irradiating each photobase separately. The concept of a light‐controlled system shown here of a sophisticated interplay between two photobases can be integrated into various smart functional and dynamic systems.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Controlling pH‐Sensitive Chemical Reactions Pathways with Light ‐ a Tale of Two Photobases: an Arrhenius and a Brønsted

Yucknovsky,

Amdursky

2023

Chemistry A European J

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“…[5][6][7][12][13][14][15][16][17] Reversibility in structural alteration is an essential criterion for many processes because it increases the usefulness of sensing materials by decreasing their cost. 18,19 Reversibility can be achieved by the application of light, temperature, or the addition of an external additive. 19,20 Additionally, it has been found that, in the presence of an H + donor, the spiro form of the conventional spiropyran shifts toward the merocyanine form.…”

mentioning

confidence: 99%

“…[32][33][34] Moreover, spiropyrans are known for their redox properties under the influence of metal ions and electrochemical input. 18,[35][36][37][38] The indoline unit of spiropyrans is known for its electrochemical and metal ion-induced oxidation followed by C-C coupling to produce dimeric structures. 18,22,36,39,40 The electrochemical oxidation or reduction of electrons causes a change in dipole moment and counter ionic species, which influences the solvation, optical and magnetic characteristics.…”

mentioning

confidence: 99%

“…18,[35][36][37][38] The indoline unit of spiropyrans is known for its electrochemical and metal ion-induced oxidation followed by C-C coupling to produce dimeric structures. 18,22,36,39,40 The electrochemical oxidation or reduction of electrons causes a change in dipole moment and counter ionic species, which influences the solvation, optical and magnetic characteristics. 41,42 Moreover, protonation followed by ring-opening further influences the electrochemical process.…”

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confidence: 99%

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Influence of Acid on Ring-Opening, Fluorescence, Aggregation, Electrochemical Oxidation, and C–C Bond Coupling of Spiropyran Derivatives

Kathuria¹,

Tewatia²,

Kumar³

et al. 2022

J. Electrochem. Soc.

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Two benzothiazolinic spiropyran derivatives differently substituted at phenolic segment were synthesized to study the effect of acid on their ring-opening and electrochemical oxidation properties. Upon protonation, conventional spiropyrans undergo Cspiro-O bond breakage, resulting in the formation of their ring-open protonated cisoid merocyanine form, which rearranges itself to its stable transoid merocyanine. Benzothiazolinic spiropyrans have also displayed pH-controlled photochromism, with the spiro moiety being opened by trifluoroacetic acid and reverted to spiro form on neutralization with triethylamine. It was demonstrated that the increase in the concentration of trifluoroacetic acid (TFA) influences the rate of ring-opening permitting its identification by 1H NMR, 2D NMR, UV Visible spectroscopy, and single-crystal X-ray crystallography. The aggregation-induced emission characteristics of benzothiazolinic spiropyrans were also explored using fluorescence and DLS measurements. Moreover, the thia-indoline segment of spiropyran undergoes electrochemical oxidation followed by C-C coupling due to the presence of electron-rich nitrogen and sulfur atoms. The influence of acid on electrochemical oxidation and substituent was also investigated. Further, the density functional theory (DFT) based studies were performed to study the electrochemical oxidation and acidochromism in benzothiazolinic spiropyrans. Time-dependent DFT estimated variables also provided additional information regarding the acidochromism process.

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Light-controlled receptors for environmentally and biologically relevant anions

Kumar,

Kumar

2023

Chemical Engineering Journal

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Light controlled dimerization of spiropyran as a tool to achieve dual responsive capture and release system in aqueous media

Cited by 12 publications

References 83 publications

Controlling pH‐Sensitive Chemical Reactions Pathways with Light ‐ a Tale of Two Photobases: an Arrhenius and a Brønsted

Controlling pH‐Sensitive Chemical Reactions Pathways with Light ‐ a Tale of Two Photobases: an Arrhenius and a Brønsted

Influence of Acid on Ring-Opening, Fluorescence, Aggregation, Electrochemical Oxidation, and C–C Bond Coupling of Spiropyran Derivatives

Light-controlled receptors for environmentally and biologically relevant anions

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