Gold(II) Porphyrins in Photoinduced Electron Transfer Reactions

Publikationstyp:
Zeitschriftenaufsatz
Metadaten:
Autoren
  • Sebastian Preiss
  • Ayla Paepcke
  • Lukas Burkhardt
  • Luca Grossmann
  • Stefan Lochbrunner
  • Matthias Bauer
  • Till Opatz
  • Katja Heinze
Autoren-URL
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000467184600016&DestLinkType=FullRecord&DestApp=WOS_CPL
DOI
10.1002/chem.201900050
eISSN
1521-3765
Externe Identifier
  • Clarivate Analytics Document Solution ID: HX1WU
  • PubMed Identifier: 30786079
ISSN
0947-6539
Ausgabe der Veröffentlichung
23
Zeitschrift
CHEMISTRY-A EUROPEAN JOURNAL
Schlüsselwörter
  • electron transfer
  • gold
  • paramagnetic NMR spectroscopy
  • photoinduced electron transfer
  • porphyrins
Paginierung
5940 - 5949
Datum der Veröffentlichung
2019
Status
Published
Titel
Gold(II) Porphyrins in Photoinduced Electron Transfer Reactions
Sub types
  • Article
Ausgabe der Zeitschrift
25

Datenquelle: Web of Science (Lite)

Andere Metadatenquellen:
Abstract
<jats:title>Abstract</jats:title><jats:p>In the context of solar‐to‐chemical energy conversion, inspired by natural photosynthesis, the synthesis, electrochemical properties and photoinduced electron‐transfer processes of three novel zinc(II)‐gold(III) bis(porphyrin) dyads [Zn<jats:sup>II</jats:sup>(P)–Au<jats:sup>III</jats:sup>(P)]<jats:sup>+</jats:sup> are presented (P: tetraaryl porphyrin). Time‐resolved spectroscopic studies indicated ultrafast dynamics (<jats:italic>k</jats:italic><jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="graphic/chem201900050-math-0001.png" xlink:title="urn:x-wiley:09476539:media:chem201900050:chem201900050-math-0001" /> &gt;10<jats:sup>10</jats:sup> s<jats:sup>−1</jats:sup>) after visible‐light excitation, which finally yielded a charge‐shifted state [Zn<jats:sup>II</jats:sup>(P<jats:sup><jats:bold>⋅</jats:bold>+</jats:sup>)–Au<jats:sup>II</jats:sup>(P)]<jats:sup>+</jats:sup> featuring a gold(II) center. The lifetime of this excited state is quite long due to a comparably slow charge recombination (<jats:italic>k</jats:italic><jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="graphic/chem201900050-math-0002.png" xlink:title="urn:x-wiley:09476539:media:chem201900050:chem201900050-math-0002" /> ≈3×10<jats:sup>8</jats:sup> s<jats:sup>−1</jats:sup>). The [Zn<jats:sup>II</jats:sup>(P<jats:sup><jats:bold>⋅</jats:bold>+</jats:sup>)–Au<jats:sup>II</jats:sup>(P)]<jats:sup>+</jats:sup> charge‐shifted state is reductively quenched by amines in bimolecular reactions, yielding the neutral zinc(II)–gold(II) bis(porphyrin) Zn<jats:sup>II</jats:sup>(P)–Au<jats:sup>II</jats:sup>(P). The electronic nature of this key gold(II) intermediate, prepared by chemical or photochemical reduction, is elucidated by UV/Vis, X‐band EPR, gold L<jats:sub>3</jats:sub>‐edge X‐ray absorption near edge structure (XANES) and paramagnetic <jats:sup>1</jats:sup>H NMR spectroscopy as well as by quantum chemical calculations. Finally, the gold(II) site in Zn<jats:sup>II</jats:sup>(P)–Au<jats:sup>II</jats:sup>(P) is thermodynamically and kinetically competent to reduce an aryl azide to the corresponding aryl amine, paving the way to catalytic applications of gold(III) porphyrins in photoredox catalysis involving the gold(III/II) redox couple.</jats:p>
Autoren
  • Sebastian Preiß
  • Ayla Päpcke
  • Lukas Burkhardt
  • Luca Großmann
  • Stefan Lochbrunner
  • Matthias Bauer
  • Till Opatz
  • Katja Heinze
DOI
10.1002/chem.201900050
eISSN
1521-3765
ISSN
0947-6539
Ausgabe der Veröffentlichung
23
Zeitschrift
Chemistry – A European Journal
Sprache
en
Online publication date
2019
Paginierung
5940 - 5949
Datum der Veröffentlichung
2019
Status
Published
Herausgeber
Wiley
Herausgeber URL
http://dx.doi.org/10.1002/chem.201900050
Datum der Datenerfassung
2023
Titel
Gold(II) Porphyrins in Photoinduced Electron Transfer Reactions
Ausgabe der Zeitschrift
25

Datenquelle: Crossref

Abstract
In the context of solar-to-chemical energy conversion, inspired by natural photosynthesis, the synthesis, electrochemical properties and photoinduced electron-transfer processes of three novel zinc(II)-gold(III) bis(porphyrin) dyads [Zn<sup>II</sup> (P)-Au<sup>III</sup> (P)]<sup>+</sup> are presented (P: tetraaryl porphyrin). Time-resolved spectroscopic studies indicated ultrafast dynamics (k ET 1 >10<sup>10</sup>  s<sup>-1</sup> ) after visible-light excitation, which finally yielded a charge-shifted state [Zn<sup>II</sup> (P<sup>⋅+</sup> )-Au<sup>II</sup> (P)]<sup>+</sup> featuring a gold(II) center. The lifetime of this excited state is quite long due to a comparably slow charge recombination (k BET 2 ≈3×10<sup>8</sup>  s<sup>-1</sup> ). The [Zn<sup>II</sup> (P<sup>⋅+</sup> )-Au<sup>II</sup> (P)]<sup>+</sup> charge-shifted state is reductively quenched by amines in bimolecular reactions, yielding the neutral zinc(II)-gold(II) bis(porphyrin) Zn<sup>II</sup> (P)-Au<sup>II</sup> (P). The electronic nature of this key gold(II) intermediate, prepared by chemical or photochemical reduction, is elucidated by UV/Vis, X-band EPR, gold L<sub>3</sub> -edge X-ray absorption near edge structure (XANES) and paramagnetic <sup>1</sup> H NMR spectroscopy as well as by quantum chemical calculations. Finally, the gold(II) site in Zn<sup>II</sup> (P)-Au<sup>II</sup> (P) is thermodynamically and kinetically competent to reduce an aryl azide to the corresponding aryl amine, paving the way to catalytic applications of gold(III) porphyrins in photoredox catalysis involving the gold(III/II) redox couple.
Addresses
  • Institute of Inorganic Chemistry and Analytical Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, 55128, Mainz, Germany.
Autoren
  • Sebastian Preiß
  • Ayla Päpcke
  • Lukas Burkhardt
  • Luca Großmann
  • Stefan Lochbrunner
  • Matthias Bauer
  • Till Opatz
  • Katja Heinze
DOI
10.1002/chem.201900050
eISSN
1521-3765
Externe Identifier
  • PubMed Identifier: 30786079
Funding acknowledgements
  • Deutsche Forschungsgemeinschaft: LO 714/11-1
  • Stiftung Rheinland-Pfalz für Innovation: LESSING
  • Stiftung Rheinland-Pfalz für Innovation: CINEMA
Open access
false
ISSN
0947-6539
Ausgabe der Veröffentlichung
23
Zeitschrift
Chemistry (Weinheim an der Bergstrasse, Germany)
Sprache
eng
Medium
Print-Electronic
Online publication date
2019
Paginierung
5940 - 5949
Datum der Veröffentlichung
2019
Status
Published
Datum der Datenerfassung
2019
Titel
Gold(II) Porphyrins in Photoinduced Electron Transfer Reactions.
Sub types
  • Journal Article
Ausgabe der Zeitschrift
25

Datenquelle: Europe PubMed Central

Abstract
In the context of solar-to-chemical energy conversion, inspired by natural photosynthesis, the synthesis, electrochemical properties and photoinduced electron-transfer processes of three novel zinc(II)-gold(III) bis(porphyrin) dyads [ZnII (P)-AuIII (P)]+ are presented (P: tetraaryl porphyrin). Time-resolved spectroscopic studies indicated ultrafast dynamics (k ET 1 >1010  s-1 ) after visible-light excitation, which finally yielded a charge-shifted state [ZnII (P⋅+ )-AuII (P)]+ featuring a gold(II) center. The lifetime of this excited state is quite long due to a comparably slow charge recombination (k BET 2 ≈3×108  s-1 ). The [ZnII (P⋅+ )-AuII (P)]+ charge-shifted state is reductively quenched by amines in bimolecular reactions, yielding the neutral zinc(II)-gold(II) bis(porphyrin) ZnII (P)-AuII (P). The electronic nature of this key gold(II) intermediate, prepared by chemical or photochemical reduction, is elucidated by UV/Vis, X-band EPR, gold L3 -edge X-ray absorption near edge structure (XANES) and paramagnetic 1 H NMR spectroscopy as well as by quantum chemical calculations. Finally, the gold(II) site in ZnII (P)-AuII (P) is thermodynamically and kinetically competent to reduce an aryl azide to the corresponding aryl amine, paving the way to catalytic applications of gold(III) porphyrins in photoredox catalysis involving the gold(III/II) redox couple.
Autoren
  • Sebastian Preiß
  • Ayla Päpcke
  • Lukas Burkhardt
  • Luca Großmann
  • Stefan Lochbrunner
  • Matthias Bauer
  • Till Opatz
  • Katja Heinze
Autoren-URL
https://www.ncbi.nlm.nih.gov/pubmed/30786079
DOI
10.1002/chem.201900050
eISSN
1521-3765
Funding acknowledgements
  • Stiftung Rheinland-Pfalz für Innovation: CINEMA
  • Stiftung Rheinland-Pfalz für Innovation: LESSING
  • Deutsche Forschungsgemeinschaft: LO 714/11-1
Ausgabe der Veröffentlichung
23
Zeitschrift
Chemistry
Schlüsselwörter
  • electron transfer
  • gold
  • paramagnetic NMR spectroscopy
  • photoinduced electron transfer
  • porphyrins
Sprache
eng
Country
Germany
Paginierung
5940 - 5949
Datum der Veröffentlichung
2019
Status
Published
Titel
Gold(II) Porphyrins in Photoinduced Electron Transfer Reactions.
Sub types
  • Journal Article
Ausgabe der Zeitschrift
25

Datenquelle: PubMed

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