Gold(III) tetraarylporphyrin amino acid derivatives: ligand or metal centred redox chemistry?
- Publikationstyp:
- Zeitschriftenaufsatz
- Metadaten:
-
- Autoren
- Sebastian Preiss
- Jascha Melomedov
- Anica Wuensche von Leupoldt
- Katja Heinze
- Autoren-URL
- https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000366826900072&DestLinkType=FullRecord&DestApp=WOS_CPL
- DOI
- 10.1039/c5sc03429a
- eISSN
- 2041-6539
- Externe Identifier
- Clarivate Analytics Document Solution ID: CZ0WL
- PubMed Identifier: 29896349
- ISSN
- 2041-6520
- Ausgabe der Veröffentlichung
- 1
- Zeitschrift
- CHEMICAL SCIENCE
- Paginierung
- 596 - 610
- Datum der Veröffentlichung
- 2016
- Status
- Published
- Titel
- Gold(III) tetraarylporphyrin amino acid derivatives: ligand or metal centred redox chemistry?
- Sub types
- Article
- Ausgabe der Zeitschrift
- 7
Datenquelle: Web of Science (Lite)
- Andere Metadatenquellen:
-
- Abstract
- <p>EPR spectroscopy and DFT calculations show that the site of reduction of porphyrinato gold(<sc>iii</sc>) complexes depends on the counterions X, the<italic>meso</italic>substituents R and the solvent.</p>
- Autoren
- Sebastian Preiß
- Jascha Melomedov
- Anica Wünsche von Leupoldt
- Katja Heinze
- DOI
- 10.1039/c5sc03429a
- eISSN
- 2041-6539
- ISSN
- 2041-6520
- Ausgabe der Veröffentlichung
- 1
- Zeitschrift
- Chemical Science
- Sprache
- en
- Online publication date
- 2016
- Paginierung
- 596 - 610
- Status
- Published online
- Herausgeber
- Royal Society of Chemistry (RSC)
- Herausgeber URL
- http://dx.doi.org/10.1039/c5sc03429a
- Datum der Datenerfassung
- 2024
- Titel
- Gold(<scp>iii</scp>) tetraarylporphyrin amino acid derivatives: ligand or metal centred redox chemistry?
- Ausgabe der Zeitschrift
- 7
Datenquelle: Crossref
- Abstract
- <i>Meso</i> tetraarylporphyrinato gold(iii) cations bearing different substituents at the aryl substituents (COOMe, COOH, NO<sub>2</sub>, NH<sub>2</sub>, NHAc, H, O <sup><i>n</i></sup> Bu, CF<sub>3</sub>) were prepared and characterised. Their reversible one-electron reductions were studied by (spectro)electrochemical means as well as by selective chemical one-electron reduction using cobaltocene. The preferred location of the spin density, namely gold centred or porphyrin centred, was probed by electron paramagnetic resonance spectroscopy (<i>g</i> values, <sup>197</sup>Au hyperfine coupling) as well as by density functional theory calculations (spin densities). In all cases studied experimentally and theoretically, the gold(ii) valence isomer (5d<sup>9</sup> electron configuration) is preferred over the porphyrin π radical anion. In the hexafluorophosphate salt of the nitro derivative a further nitro π radical anion valence isomeric species is significantly populated. In the presence of chloride ions this nitro π radical anion/Au<sup>II</sup> valence isomeric equilibrium evolves towards the porphyrin π radical anion. The electronic structures of the nitro π radical and the Au<sup>II</sup> σ radical valence isomers (5d <sub><i>x</i><sup>2</sup>-<i>y</i><sup>2</sup></sub> orbital) could be calculated by DFT methods. The electron transfer pathway between the nitro π radical anion and the Au<sup>II</sup> valence isomer is well described by the location of the hexfluorophosphate counterion, the Au-N distances (corresponding to the totally symmetric stretching vibration), the symmetric stretching mode of the NO<sub>2</sub> substituent and a <i>meso</i>-nitrophenyl rotation. The specific geometric and electronic properties of the favoured gold(ii) σ radical valence isomer, namely counterion dislocation and σ symmetry of the redox orbital, might stabilise charge-shifted states [(gold(ii) porphyrin)-donor˙<sup>+</sup>] by retarding the back electron transfer to give the ground state (gold(iii) porphyrin)-donor. This will guide the design of (photo-induced) electron transfer pathways with tetraarylporphyrinato gold(iii) complexes as electron acceptors.
- Addresses
- Institute of Inorganic Chemistry and Analytical Chemistry , Johannes Gutenberg-University of Mainz , Duesbergweg 10-14 , 55128 Mainz , Germany . Email: katja.heinze@uni-Mainz.de ; ; Tel: +49-6131-39-25886.
- Autoren
- Sebastian Preiß
- Jascha Melomedov
- Anica Wünsche von Leupoldt
- Katja Heinze
- DOI
- 10.1039/c5sc03429a
- eISSN
- 2041-6539
- Externe Identifier
- PubMed Identifier: 29896349
- PubMed Central ID: PMC5952892
- Open access
- true
- ISSN
- 2041-6520
- Ausgabe der Veröffentlichung
- 1
- Zeitschrift
- Chemical science
- Sprache
- eng
- Medium
- Print-Electronic
- Online publication date
- 2015
- Open access status
- Open Access
- Paginierung
- 596 - 610
- Datum der Veröffentlichung
- 2016
- Status
- Published
- Publisher licence
- CC BY
- Datum der Datenerfassung
- 2018
- Titel
- Gold(iii) tetraarylporphyrin amino acid derivatives: ligand or metal centred redox chemistry?
- Sub types
- research-article
- Journal Article
- Ausgabe der Zeitschrift
- 7
Files
https://pubs.rsc.org/en/content/articlepdf/2016/sc/c5sc03429a https://europepmc.org/articles/PMC5952892?pdf=render
Datenquelle: Europe PubMed Central
- Abstract
- Meso tetraarylporphyrinato gold(iii) cations bearing different substituents at the aryl substituents (COOMe, COOH, NO2, NH2, NHAc, H, O n Bu, CF3) were prepared and characterised. Their reversible one-electron reductions were studied by (spectro)electrochemical means as well as by selective chemical one-electron reduction using cobaltocene. The preferred location of the spin density, namely gold centred or porphyrin centred, was probed by electron paramagnetic resonance spectroscopy (g values, 197Au hyperfine coupling) as well as by density functional theory calculations (spin densities). In all cases studied experimentally and theoretically, the gold(ii) valence isomer (5d9 electron configuration) is preferred over the porphyrin π radical anion. In the hexafluorophosphate salt of the nitro derivative a further nitro π radical anion valence isomeric species is significantly populated. In the presence of chloride ions this nitro π radical anion/AuII valence isomeric equilibrium evolves towards the porphyrin π radical anion. The electronic structures of the nitro π radical and the AuII σ radical valence isomers (5d x2-y2 orbital) could be calculated by DFT methods. The electron transfer pathway between the nitro π radical anion and the AuII valence isomer is well described by the location of the hexfluorophosphate counterion, the Au-N distances (corresponding to the totally symmetric stretching vibration), the symmetric stretching mode of the NO2 substituent and a meso-nitrophenyl rotation. The specific geometric and electronic properties of the favoured gold(ii) σ radical valence isomer, namely counterion dislocation and σ symmetry of the redox orbital, might stabilise charge-shifted states [(gold(ii) porphyrin)-donor˙+] by retarding the back electron transfer to give the ground state (gold(iii) porphyrin)-donor. This will guide the design of (photo-induced) electron transfer pathways with tetraarylporphyrinato gold(iii) complexes as electron acceptors.
- Date of acceptance
- 2015
- Autoren
- Sebastian Preiß
- Jascha Melomedov
- Anica Wünsche von Leupoldt
- Katja Heinze
- Autoren-URL
- https://www.ncbi.nlm.nih.gov/pubmed/29896349
- DOI
- 10.1039/c5sc03429a
- Externe Identifier
- PubMed Central ID: PMC5952892
- ISSN
- 2041-6520
- Ausgabe der Veröffentlichung
- 1
- Zeitschrift
- Chem Sci
- Sprache
- eng
- Country
- England
- Paginierung
- 596 - 610
- PII
- c5sc03429a
- Datum der Veröffentlichung
- 2016
- Status
- Published
- Titel
- Gold(iii) tetraarylporphyrin amino acid derivatives: ligand or metal centred redox chemistry?
- Sub types
- Journal Article
- Ausgabe der Zeitschrift
- 7
Datenquelle: PubMed
- Beziehungen:
-