Experimental and Theoretical Characterization of Ultrafast Water-Soluble Photochromic Photoacids
UV-visible transient absorption spectroscopy and quantum mechanical simulations are combined to elucidate the photochemical mechanism of two metastable merocyanine/spiropyran photoacids, 2-[(E)-2-(2-hydroxyphenyl)ethenyl]-3,3-dimethyl-1-(3-sulfopropyl)-3H-indol-1-ium (phenylhydroxy-MCH) and 2-[(E)-2-(1H-indazol-7-yl)ethenyl]-3-(3-sulfopropyl)-1,3-benzothiazol-3-ium (indazole-MCH). Transient absorption spectra demonstrate that trans-acid isomerization to the cis form results in deprotonation on a picosecond time scale. Ring closure to form spiropyran follows promptly from the appropriate conformation or follows at longer time delays (≫3.5 ns) following a barrier crossing for single-bond isomerization to the appropriate conformation. Consistent with the results of Berton et al. [ Chem. Sci. 2020, 11, 8457-8468] , we find that cis-phenylhydroxy-MCH is a stronger acid than trans-phenylhydroxy-MCH. The decrease in pKa upon isomerization is further investigated to benchmark quantum chemical methods for their accuracy. Calculations were performed with nine levels of theory including continuum solvent models and explicit water. The calculations are not sufficient to describe the ΔpKa following isomerization of these photoacids, and more work is necessary to properly evaluate the physical basis for the acidity of the cis photoacids.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2021 |
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| Erschienen: |
2021 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:125 |
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| Enthalten in: |
The journal of physical chemistry. B - 125(2021), 16 vom: 29. Apr., Seite 4120-4131 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Aldaz, Cody R [VerfasserIn] |
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| Links: |
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| Anmerkungen: |
Date Completed 20.05.2021 Date Revised 20.05.2021 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/acs.jpcb.1c00644 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM324266340 |
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| 245 | 1 | 0 | |a Experimental and Theoretical Characterization of Ultrafast Water-Soluble Photochromic Photoacids |
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| 500 | |a Date Completed 20.05.2021 | ||
| 500 | |a Date Revised 20.05.2021 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a UV-visible transient absorption spectroscopy and quantum mechanical simulations are combined to elucidate the photochemical mechanism of two metastable merocyanine/spiropyran photoacids, 2-[(E)-2-(2-hydroxyphenyl)ethenyl]-3,3-dimethyl-1-(3-sulfopropyl)-3H-indol-1-ium (phenylhydroxy-MCH) and 2-[(E)-2-(1H-indazol-7-yl)ethenyl]-3-(3-sulfopropyl)-1,3-benzothiazol-3-ium (indazole-MCH). Transient absorption spectra demonstrate that trans-acid isomerization to the cis form results in deprotonation on a picosecond time scale. Ring closure to form spiropyran follows promptly from the appropriate conformation or follows at longer time delays (≫3.5 ns) following a barrier crossing for single-bond isomerization to the appropriate conformation. Consistent with the results of Berton et al. [ Chem. Sci. 2020, 11, 8457-8468] , we find that cis-phenylhydroxy-MCH is a stronger acid than trans-phenylhydroxy-MCH. The decrease in pKa upon isomerization is further investigated to benchmark quantum chemical methods for their accuracy. Calculations were performed with nine levels of theory including continuum solvent models and explicit water. The calculations are not sufficient to describe the ΔpKa following isomerization of these photoacids, and more work is necessary to properly evaluate the physical basis for the acidity of the cis photoacids | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Research Support, U.S. Gov't, Non-P.H.S. | |
| 700 | 1 | |a Wiley, Theodore E |e verfasserin |4 aut | |
| 700 | 1 | |a Miller, Nicholas A |e verfasserin |4 aut | |
| 700 | 1 | |a Abeyrathna, Nawodi |e verfasserin |4 aut | |
| 700 | 1 | |a Liao, Yi |e verfasserin |4 aut | |
| 700 | 1 | |a Zimmerman, Paul M |e verfasserin |4 aut | |
| 700 | 1 | |a Sension, Roseanne J |e verfasserin |4 aut | |
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| 856 | 4 | 0 | |u http://dx.doi.org/10.1021/acs.jpcb.1c00644 |3 Volltext |
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