TiO2 Nanoparticles Functionalized with Non-innocent Ligands Allow Oxidative Photocyanation of Amines with Visible/Near-Infrared Photons

Publikationstyp:
Zeitschriftenaufsatz
Metadaten:
Autoren
  • Alexander M Nauth
  • Eugen Schechtel
  • Rene Doeren
  • Wolfgang Tremel
  • Till Opatz
Autoren-URL
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000449239700027&DestLinkType=FullRecord&DestApp=WOS_CPL
DOI
10.1021/jacs.8b07539
Externe Identifier
  • Clarivate Analytics Document Solution ID: GZ2SW
  • PubMed Identifier: 30265004
ISSN
0002-7863
Ausgabe der Veröffentlichung
43
Zeitschrift
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Paginierung
14169 - 14177
Datum der Veröffentlichung
2018
Status
Published
Titel
TiO<sub>2</sub> Nanoparticles Functionalized with Non-innocent Ligands Allow Oxidative Photocyanation of Amines with Visible/Near-Infrared Photons
Sub types
  • Article
Ausgabe der Zeitschrift
140

Datenquelle: Web of Science (Lite)

Andere Metadatenquellen:
Autoren
  • Alexander M Nauth
  • Eugen Schechtel
  • René Dören
  • Wolfgang Tremel
  • Till Opatz
DOI
10.1021/jacs.8b07539
eISSN
1520-5126
ISSN
0002-7863
Ausgabe der Veröffentlichung
43
Zeitschrift
Journal of the American Chemical Society
Sprache
en
Online publication date
2018
Paginierung
14169 - 14177
Datum der Veröffentlichung
2018
Status
Published
Herausgeber
American Chemical Society (ACS)
Herausgeber URL
http://dx.doi.org/10.1021/jacs.8b07539
Datum der Datenerfassung
2023
Titel
TiO<sub>2</sub> Nanoparticles Functionalized with Non-innocent Ligands Allow Oxidative Photocyanation of Amines with Visible/Near-Infrared Photons
Ausgabe der Zeitschrift
140

Datenquelle: Crossref

Abstract
Photosynthesis is an efficient mechanism for converting solar light energy into chemical energy. We report on a strategy for the aerobic photocyanation of tertiary amines with visible and near-infrared (NIR) light. Panchromatic sensitization was achieved by functionalizing TiO<sub>2</sub> with a 2-methylisoquinolinium chromophore, which captures essential features of the extended π-system of 2,7-diazapyrenium (DAP<sup>2+</sup>) dications or graphitic carbon nitride. Two phenolic hydroxy groups make this ligand highly redox-active and allow for efficient surface binding and enhanced electron transfer to the TiO<sub>2</sub> surface. Non-innocent ligands have energetically accessible levels that allow redox reactions to change their charge state. Thus, the conduction band is sufficiently high to allow photochemical reduction of molecular oxygen, even with NIR light. The catalytic performance (up to 90% chemical yield for NIR excitation) of this panchromatic photocatalyst is superior to that of all photocatalysts known thus far, enabling oxidative cyanation reactions to the corresponding α-cyanated amines to proceed with high efficiency. The discovery that the surface-binding of redox-active ligands exhibits enhanced light-harvesting in the red and NIR region opens up the way to improve the overall yields in heterogeneous photocatalytic reactions. Thus, this class of functionalized semiconductors provides the basis for the design of new photocatalysts containing non-innocent donor ligands. This should increase the molar extinction coefficient, permitting a reduction of nanoparticle catalyst concentration and an increase of the chemical yields in photocatalytic reactions.
Addresses
  • Institut für Organische Chemie , Johannes Gutenberg-Universität Mainz , Duesbergweg 10-14 , D-55128 Mainz , Germany.
Autoren
  • Alexander M Nauth
  • Eugen Schechtel
  • René Dören
  • Wolfgang Tremel
  • Till Opatz
DOI
10.1021/jacs.8b07539
eISSN
1520-5126
Externe Identifier
  • PubMed Identifier: 30265004
Funding acknowledgements
  • Rhineland-Palatinate Natural Products Research Center:
Open access
false
ISSN
0002-7863
Ausgabe der Veröffentlichung
43
Zeitschrift
Journal of the American Chemical Society
Sprache
eng
Medium
Print-Electronic
Online publication date
2018
Paginierung
14169 - 14177
Datum der Veröffentlichung
2018
Status
Published
Datum der Datenerfassung
2018
Titel
TiO<sub>2</sub> Nanoparticles Functionalized with Non-innocent Ligands Allow Oxidative Photocyanation of Amines with Visible/Near-Infrared Photons.
Sub types
  • Research Support, Non-U.S. Gov't
  • Journal Article
Ausgabe der Zeitschrift
140

Datenquelle: Europe PubMed Central

Abstract
Photosynthesis is an efficient mechanism for converting solar light energy into chemical energy. We report on a strategy for the aerobic photocyanation of tertiary amines with visible and near-infrared (NIR) light. Panchromatic sensitization was achieved by functionalizing TiO2 with a 2-methylisoquinolinium chromophore, which captures essential features of the extended π-system of 2,7-diazapyrenium (DAP2+) dications or graphitic carbon nitride. Two phenolic hydroxy groups make this ligand highly redox-active and allow for efficient surface binding and enhanced electron transfer to the TiO2 surface. Non-innocent ligands have energetically accessible levels that allow redox reactions to change their charge state. Thus, the conduction band is sufficiently high to allow photochemical reduction of molecular oxygen, even with NIR light. The catalytic performance (up to 90% chemical yield for NIR excitation) of this panchromatic photocatalyst is superior to that of all photocatalysts known thus far, enabling oxidative cyanation reactions to the corresponding α-cyanated amines to proceed with high efficiency. The discovery that the surface-binding of redox-active ligands exhibits enhanced light-harvesting in the red and NIR region opens up the way to improve the overall yields in heterogeneous photocatalytic reactions. Thus, this class of functionalized semiconductors provides the basis for the design of new photocatalysts containing non-innocent donor ligands. This should increase the molar extinction coefficient, permitting a reduction of nanoparticle catalyst concentration and an increase of the chemical yields in photocatalytic reactions.
Autoren
  • Alexander M Nauth
  • Eugen Schechtel
  • René Dören
  • Wolfgang Tremel
  • Till Opatz
Autoren-URL
https://www.ncbi.nlm.nih.gov/pubmed/30265004
DOI
10.1021/jacs.8b07539
eISSN
1520-5126
Ausgabe der Veröffentlichung
43
Zeitschrift
J Am Chem Soc
Sprache
eng
Country
United States
Paginierung
14169 - 14177
Datum der Veröffentlichung
2018
Status
Published
Titel
TiO2 Nanoparticles Functionalized with Non-innocent Ligands Allow Oxidative Photocyanation of Amines with Visible/Near-Infrared Photons.
Sub types
  • Journal Article
  • Research Support, Non-U.S. Gov't
Ausgabe der Zeitschrift
140

Datenquelle: PubMed

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