Ring Closure Reaction Pathway of a Diarylethene in Solution Using Femtosecond Time‐resolved Fluorescence Spectra

Seo, Kiho; Eom, Intae; Shim, Sangdeok; Kim, Chul Hoon; Joo, Taiha

doi:10.1002/bkcs.11689

Cited by 6 publications

(2 citation statements)

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“…[16,17] To overpass such limitation some researchers focused their efforts on exploring purposed-designed synthetic approach [18][19][20][21] or specific excited-state reactivity. [22,23] Indeed, the rationalization of complex excited state mechanisms are highly desired to still improve photochromic performances and so considerable investigations have been devoted worldwide to explore the excited state topologies of DTEs (or DAEs) via advanced optical spectroscopies [24][25][26][27] and/or computational chemistry. [28][29][30] In this perspective, our group has actively investigated the spectrokinetic features on the series of bridged DAEs, [31] bridged DTEs [29,32,33] or DTEs dedicated to supramolecular chemistry [34] using ultrafast spectroscopies combined with (TD)-DFT calculations.…”

Section: Introductionmentioning

confidence: 99%

Cyclization Dynamics and Competitive Processes of Photochromic Perfluorocyclopentene Dithienylethylene in Solution

et al. 2020

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This article is dedicated to the memory of Dr. Olivier Poizat, CNRS researcher at LASIR laboratory, who passed away much too soon. Olivier Poizat led the "photochemistry" team at LASIR for many years with great involvement, kindness and modesty. He was able to unite energies around numerous fundamental research projects dealing with photochemistry, photophysics and spectroscopy. He was at the origin of many research themes and of the development of time-resolved spectroscopy experiments in the laboratory. Throughout his career, he has participated in the training of many PhD students, post-doctorants and junior researchers. The authors of this paper are infinitely grateful to him for his unfailing support in the development of researches on the elucidation of reaction mechanisms of photochromic molecules and for the many fruitful discussions they had with him on this subject and many others. Rest in peace Olivier. Time-resolved absorption spectroscopy measurements were performed to study the dynamics of photochromic 1,2-Bis(2,4dimethylthiophene-3-yl)perfluoro-cyclopentene (DMTPF) in chloroform, including antiparallel conformer ring-closure reaction and parallel conformer photophysics. All characteristic times are given, discussed and compared to a previous publication concerning the close molecule substituted with phenyl rings. (Hamdi et al., PCCP, 2016). Apart from the expected photocyclization process, condensed ring by-product formation is observed and hypotheses concerning the origin of this by-product are presented.

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Section: Introductionmentioning

confidence: 99%

Cyclization Dynamics and Competitive Processes of Photochromic Perfluorocyclopentene Dithienylethylene in Solution

et al. 2020

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“…However, NMR, isothermal titration calorimetry, and thermogravimetry are challenging to obtain the dynamic changes during confined reaction at micromolar concentrations (5 × 10 −6 m) relative to conventional reactions, which is due to its complex multimolecular interactions, [10] and the poor solubility results in concentrations in the solution below the detection range of conventional methods. [11] The test methods that can detect the reactants in micromolar concentration include fluorescence spectra and SERS, but fluorescence spectra need to be labeled with fluorescent groups, [12] and SERS requires substrates. [13] Therefore, the application of the above methods in micromolar concentration chemical reaction tracking is still lacking in universality.…”

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confidence: 99%

Tracking Confined Reaction Based on Host–Guest Interaction Using Single‐Molecule Conductance Measurement

Yuán

Qian

Zhou

et al. 2021

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the reaction dynamics of confined reaction in millimolar concentration scale efficiently. However, NMR, isothermal titration calorimetry, and thermogravimetry are challenging to obtain the dynamic changes during confined reaction at micromolar concentrations (5 × 10 −6 m) relative to conventional reactions, which is due to its complex multimolecular interactions, [10] and the poor solubility results in concentrations in the solution below the detection range of conventional methods. [11] The test methods that can detect the reactants in micromolar concentration include fluorescence spectra and SERS, but fluorescence spectra need to be labeled with fluorescent groups, [12] and SERS requires substrates. [13] Therefore, the application of the above methods in micromolar concentration chemical reaction tracking is still lacking in universality. The single-molecule conductance measurement technique is based on the repeated opening and closing of metal electrodes to form a large number of single-molecule junctions. The electrode forms a nanometer gap during the stretching process, thus achieving the capture of single molecules. [14][15][16] Break junction techniques offer the opportunity to detect the single-molecule electrical signals of the reactants at the singlemolecule scale. [17][18][19][20][21][22][23] Although mass spectrometry can be used to study reactions at low concentrations, this technique cannot reach single-molecule level. Moreover, the high energy of mass spectrometry will affect the weak interaction and reaction. While, this observation based on scanning tunneling microscope-break junction (STM-BJ) technique is lossless and low consumption. Therefore we choose STM-BJ technique to track the confined reaction based on host-guest interaction.The single-molecule conductance measurement of reaction can provide direct evidence for reaction kinetics [24,25] and reaction mechanisms from the molecular level. Recent advances suggested that the single-molecule techniques can track reactions such as Diels-Alder reaction, [26,27] ring cleavage and ring closure reaction, [28,29] cleavage of alkoxyamines, [30] isomerization reactions of cumulenes, [31] aniline coupling, [32] photoswitches of photochromic molecules, [33] and supramolecular interactions are also detected in molecular junctions includeThe host-guest interaction acts as an essential part of supramolecular chemistry, which can be applied in confined reaction. However, it is challenging to obtain the dynamic process during confined reactions below micromolar concentrations. In this work, a new method is provided to characterize the dimerization process of the guest 1,2-bis(4-pyridinyl) ethylene in host cucurbit[8]curil using scanning tunneling microscope-break junction (STM-BJ) technique. The guest reaction kinetics is quantitatively by nuclear magnetic resonance (NMR) and in situ single-molecule junctions. It is found that in the single-molecule conductance measurements, the electrical signals of the reactants with a concentration as low as 5 × 10 −6 m a...

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Geometrical Evolution and Formation of the Photoproduct in the Cycloreversion Reaction of a Diarylethene Derivative Probed by Vibrational Spectroscopy

et al. 2020

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The geometrical evolution of the reactant and formation of the photoproduct in the cycloreversion reaction of a diarylethene derivative were probed using time‐resolved absorption spectroscopies in the visible to near‐infrared and mid‐infrared regions. The time‐domain vibrational data in the visible region show that the initially formed Franck‐Condon state is geometrically relaxed into the minimum in the excited state potential energy surface, concomitantly with the low‐frequency coherent vibrations. Theoretical calculations indicate that the nuclear displacement in this coherent vibration is nearly parallel to that in the geometrical relaxation. Time‐resolved mid‐infrared spectroscopy directly detected the formation of the open‐ring isomer with the same time constant as the decrease of the closed‐ring isomer in the excited state minimum. This observation reveals that no detectable intermediate, in which the population is accumulated, is present between the excited closed‐ring isomer and the open‐ring isomer in the ground state.

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Ring Closure Reaction Pathway of a Diarylethene in Solution Using Femtosecond Time‐resolved Fluorescence Spectra

Cited by 6 publications

References 39 publications

Cyclization Dynamics and Competitive Processes of Photochromic Perfluorocyclopentene Dithienylethylene in Solution

Cyclization Dynamics and Competitive Processes of Photochromic Perfluorocyclopentene Dithienylethylene in Solution

Tracking Confined Reaction Based on Host–Guest Interaction Using Single‐Molecule Conductance Measurement

Geometrical Evolution and Formation of the Photoproduct in the Cycloreversion Reaction of a Diarylethene Derivative Probed by Vibrational Spectroscopy

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