View in EDS

Tuning the Thermal Isomerization of Phenylazoindole Photoswitches from Days to Nanoseconds.

Saved in:
Bibliographic Details
Title: Tuning the Thermal Isomerization of Phenylazoindole Photoswitches from Days to Nanoseconds.
Authors: Simeth, Nadja A.1, Crespi, Stefano1, König, Burkhard1, Fagnoni, Maurizio2
Source: Journal of the American Chemical Society. 2/28/2018, Vol. 140 Issue 8, p2940-2946. 7p.
Subjects: Isomerization, Photochemical oxidants, Methylation, Fluorescence, Magnetization
Abstract: The growing interest in light-driven molecular switches and optical oscillators led to the development of molecules that are able to interconvert from a stable to a metastable configuration upon photochemical triggering and to return to the thermodynamically stable form as soon as the light stimulus is removed. Controlling a wide range of back-isomerization lifetimes in the dark is a crucial goal for potential application of these compounds such as molecular machines. We herein present a novel class of easily synthesizable azo photoswitches based on the arylazoindole core. Most notably, minimal modifications of the core, such as methylation, dramatically change the Z-to-E thermal isomerization rate from days (Me in position 1) to the nanosecond range (Me in position 2). Moreover, fine-tuning of the Z-to-E lifetimes can be achieved choosing a proper dimethyl sulfoxide -- water (or buffered water) solvent mixture. The photochemical and thermal mechanisms have been elucidated by a thorough computational and spectroscopic analysis. This allowed to detect three different pathways of thermal isomerization and to identify the hydrazone tautomer of the phenylazoindole as the major actor in the fast Z -- E thermal isomerization of the NH-substituted switch in protic media. [ABSTRACT FROM AUTHOR]
Copyright of Journal of the American Chemical Society is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
Database: Engineering Source
FullText Text:
  Availability: 0
Header DbId: egs
DbLabel: Engineering Source
An: 128315295
AccessLevel: 6
PubType: Academic Journal
PubTypeId: academicJournal
PreciseRelevancyScore: 0
IllustrationInfo
Items – Name: Title
  Label: Title
  Group: Ti
  Data: Tuning the Thermal Isomerization of Phenylazoindole Photoswitches from Days to Nanoseconds.
– Name: Author
  Label: Authors
  Group: Au
  Data: <searchLink fieldCode="AR" term="%22Simeth%2C+Nadja+A%2E%22">Simeth, Nadja A.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Crespi%2C+Stefano%22">Crespi, Stefano</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22König%2C+Burkhard%22">König, Burkhard</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Fagnoni%2C+Maurizio%22">Fagnoni, Maurizio</searchLink><relatesTo>2</relatesTo>
– Name: TitleSource
  Label: Source
  Group: Src
  Data: <searchLink fieldCode="JN" term="%22Journal+of+the+American+Chemical+Society%22">Journal of the American Chemical Society</searchLink>. 2/28/2018, Vol. 140 Issue 8, p2940-2946. 7p.
– Name: Subject
  Label: Subjects
  Group: Su
  Data: <searchLink fieldCode="DE" term="%22Isomerization%22">Isomerization</searchLink><br /><searchLink fieldCode="DE" term="%22Photochemical+oxidants%22">Photochemical oxidants</searchLink><br /><searchLink fieldCode="DE" term="%22Methylation%22">Methylation</searchLink><br /><searchLink fieldCode="DE" term="%22Fluorescence%22">Fluorescence</searchLink><br /><searchLink fieldCode="DE" term="%22Magnetization%22">Magnetization</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: The growing interest in light-driven molecular switches and optical oscillators led to the development of molecules that are able to interconvert from a stable to a metastable configuration upon photochemical triggering and to return to the thermodynamically stable form as soon as the light stimulus is removed. Controlling a wide range of back-isomerization lifetimes in the dark is a crucial goal for potential application of these compounds such as molecular machines. We herein present a novel class of easily synthesizable azo photoswitches based on the arylazoindole core. Most notably, minimal modifications of the core, such as methylation, dramatically change the Z-to-E thermal isomerization rate from days (Me in position 1) to the nanosecond range (Me in position 2). Moreover, fine-tuning of the Z-to-E lifetimes can be achieved choosing a proper dimethyl sulfoxide -- water (or buffered water) solvent mixture. The photochemical and thermal mechanisms have been elucidated by a thorough computational and spectroscopic analysis. This allowed to detect three different pathways of thermal isomerization and to identify the hydrazone tautomer of the phenylazoindole as the major actor in the fast Z -- E thermal isomerization of the NH-substituted switch in protic media. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Journal of the American Chemical Society is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
PLink https://search.ebscohost.com/login.aspx?direct=true&site=eds-live&db=egs&AN=128315295
RecordInfo BibRecord:
  BibEntity:
    Identifiers:
      – Type: doi
        Value: 10.1021/jacs.7b12871
    Languages:
      – Code: eng
        Text: English
    PhysicalDescription:
      Pagination:
        PageCount: 7
        StartPage: 2940
    Subjects:
      – SubjectFull: Isomerization
        Type: general
      – SubjectFull: Photochemical oxidants
        Type: general
      – SubjectFull: Methylation
        Type: general
      – SubjectFull: Fluorescence
        Type: general
      – SubjectFull: Magnetization
        Type: general
    Titles:
      – TitleFull: Tuning the Thermal Isomerization of Phenylazoindole Photoswitches from Days to Nanoseconds.
        Type: main
  BibRelationships:
    HasContributorRelationships:
      – PersonEntity:
          Name:
            NameFull: Simeth, Nadja A.
      – PersonEntity:
          Name:
            NameFull: Crespi, Stefano
      – PersonEntity:
          Name:
            NameFull: König, Burkhard
      – PersonEntity:
          Name:
            NameFull: Fagnoni, Maurizio
    IsPartOfRelationships:
      – BibEntity:
          Dates:
            – D: 28
              M: 02
              Text: 2/28/2018
              Type: published
              Y: 2018
          Identifiers:
            – Type: issn-print
              Value: 00027863
          Numbering:
            – Type: volume
              Value: 140
            – Type: issue
              Value: 8
          Titles:
            – TitleFull: Journal of the American Chemical Society
              Type: main
ResultId 1