Water-Soluble Tris(cyclometalated) Iridium(III) Complexes for Aqueous Electron and Energy Transfer Photochemistry
- Publikationstyp:
- Zeitschriftenaufsatz
- Metadaten:
-
- Autoren
- Mirjam R Schreier
- Xingwei Guo
- Bjorn Pfund
- Yasunori Okamoto
- Thomas R Ward
- Christoph Kerzig
- Oliver S Wenger
- Autoren-URL
- https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000800139900009&DestLinkType=FullRecord&DestApp=WOS_CPL
- DOI
- 10.1021/acs.accounts.2c00075
- eISSN
- 1520-4898
- Externe Identifier
- Clarivate Analytics Document Solution ID: 1M7HY
- PubMed Identifier: 35414170
- ISSN
- 0001-4842
- Ausgabe der Veröffentlichung
- 9
- Zeitschrift
- ACCOUNTS OF CHEMICAL RESEARCH
- Paginierung
- 1290 - 1300
- Datum der Veröffentlichung
- 2022
- Status
- Published
- Titel
- Water-Soluble Tris(cyclometalated) Iridium(III) Complexes for Aqueous Electron and Energy Transfer Photochemistry
- Sub types
- Review
- Ausgabe der Zeitschrift
- 55
Datenquelle: Web of Science (Lite)
- Andere Metadatenquellen:
-
- Autoren
- Mirjam R Schreier
- Xingwei Guo
- Björn Pfund
- Yasunori Okamoto
- Thomas R Ward
- Christoph Kerzig
- Oliver S Wenger
- DOI
- 10.1021/acs.accounts.2c00075
- eISSN
- 1520-4898
- ISSN
- 0001-4842
- Ausgabe der Veröffentlichung
- 9
- Zeitschrift
- Accounts of Chemical Research
- Sprache
- en
- Online publication date
- 2022
- Paginierung
- 1290 - 1300
- Datum der Veröffentlichung
- 2022
- Status
- Published
- Herausgeber
- American Chemical Society (ACS)
- Herausgeber URL
- http://dx.doi.org/10.1021/acs.accounts.2c00075
- Datum der Datenerfassung
- 2023
- Titel
- Water-Soluble Tris(cyclometalated) Iridium(III) Complexes for Aqueous Electron and Energy Transfer Photochemistry
- Ausgabe der Zeitschrift
- 55
Datenquelle: Crossref
- Abstract
- Cyclometalated iridium(III) complexes are frequently employed in organic light emitting diodes, and they are popular photocatalysts for solar energy conversion and synthetic organic chemistry. They luminesce from redox-active excited states that can have high triplet energies and long lifetimes, making them well suited for energy transfer and photoredox catalysis. Homoleptic tris(cyclometalated) iridium(III) complexes are typically very hydrophobic and do not dissolve well in polar solvents, somewhat limiting their application scope. We developed a family of water-soluble sulfonate-decorated variants with tailored redox potentials and excited-state energies to address several key challenges in aqueous photochemistry.First, we aimed at combining enzyme with photoredox catalysis to synthesize enantioenriched products in a cyclic reaction network. Since the employed biocatalyst operates best in aqueous solution, a water-soluble photocatalyst was needed. A new tris(cyclometalated) iridium(III) complex provided enough reducing power for the photochemical reduction of imines to racemic mixtures of amines and furthermore was compatible with monoamine oxidase (MAO-N-9), which deracemized this mixture through a kinetic resolution of the racemic amine via oxidation to the corresponding imine. This process led to the accumulation of the unreactive amine enantiomer over time. In subsequent studies, we discovered that the same iridium(III) complex photoionizes under intense irradiation to give hydrated electrons as a result of consecutive two-photon excitation. With visible light as energy input, hydrated electrons become available in a catalytic fashion, thereby allowing the comparatively mild reduction of substrates that would typically only be reactive under harsher conditions. Finally, we became interested in photochemical upconversion in aqueous solution, for which it was desirable to obtain water-soluble iridium(III) compounds with very high triplet excited-state energies. This goal was achieved through improved ligand design and ultimately enabled sensitized triplet-triplet annihilation upconversion unusually far into the ultraviolet spectral range.Studies of photoredox catalysis, energy transfer catalysis, and photochemical upconversion typically rely on the use of organic solvents. Water could potentially be an attractive alternative in many cases, but photocatalyst development lags somewhat behind for aqueous solution compared to organic solvent. The purpose of this Account is to provide an overview of the breadth of new research perspectives that emerged from the development of water-soluble <i>fac</i>-[Ir(ppy)]<sub>3</sub> complexes (ppy = 2-phenylpyridine) with sulfonated ligands. We hope to inspire the use of some of these or related coordination compounds in aqueous photochemistry and to stimulate further conceptual developments at the interfaces of coordination chemistry, photophysics, biocatalysis, and sustainable chemistry.
- Addresses
- Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland.
- Autoren
- Mirjam R Schreier
- Xingwei Guo
- Björn Pfund
- Yasunori Okamoto
- Thomas R Ward
- Christoph Kerzig
- Oliver S Wenger
- DOI
- 10.1021/acs.accounts.2c00075
- eISSN
- 1520-4898
- Externe Identifier
- PubMed Identifier: 35414170
- PubMed Central ID: PMC9069695
- Funding acknowledgements
- Swiss National Science Foundation: 200021_178760
- Deutsche Akademie der Naturforscher Leopoldina - Nationale Akademie der Wissenschaften: LPDS 201711
- Fonds National de la Recherche Luxembourg: 14583224
- Open access
- true
- ISSN
- 0001-4842
- Ausgabe der Veröffentlichung
- 9
- Zeitschrift
- Accounts of chemical research
- Schlüsselwörter
- Iridium
- Water
- Amines
- Organometallic Compounds
- Ligands
- Solvents
- Energy Transfer
- Photochemistry
- Electrons
- Sprache
- eng
- Medium
- Print-Electronic
- Online publication date
- 2022
- Open access status
- Open Access
- Paginierung
- 1290 - 1300
- Datum der Veröffentlichung
- 2022
- Status
- Published
- Publisher licence
- CC BY-NC-ND
- Datum der Datenerfassung
- 2022
- Titel
- Water-Soluble Tris(cyclometalated) Iridium(III) Complexes for Aqueous Electron and Energy Transfer Photochemistry.
- Sub types
- research-article
- Review
- Journal Article
- Ausgabe der Zeitschrift
- 55
Files
https://europepmc.org/articles/PMC9069695?pdf=render
Datenquelle: Europe PubMed Central
- Abstract
- Cyclometalated iridium(III) complexes are frequently employed in organic light emitting diodes, and they are popular photocatalysts for solar energy conversion and synthetic organic chemistry. They luminesce from redox-active excited states that can have high triplet energies and long lifetimes, making them well suited for energy transfer and photoredox catalysis. Homoleptic tris(cyclometalated) iridium(III) complexes are typically very hydrophobic and do not dissolve well in polar solvents, somewhat limiting their application scope. We developed a family of water-soluble sulfonate-decorated variants with tailored redox potentials and excited-state energies to address several key challenges in aqueous photochemistry.First, we aimed at combining enzyme with photoredox catalysis to synthesize enantioenriched products in a cyclic reaction network. Since the employed biocatalyst operates best in aqueous solution, a water-soluble photocatalyst was needed. A new tris(cyclometalated) iridium(III) complex provided enough reducing power for the photochemical reduction of imines to racemic mixtures of amines and furthermore was compatible with monoamine oxidase (MAO-N-9), which deracemized this mixture through a kinetic resolution of the racemic amine via oxidation to the corresponding imine. This process led to the accumulation of the unreactive amine enantiomer over time. In subsequent studies, we discovered that the same iridium(III) complex photoionizes under intense irradiation to give hydrated electrons as a result of consecutive two-photon excitation. With visible light as energy input, hydrated electrons become available in a catalytic fashion, thereby allowing the comparatively mild reduction of substrates that would typically only be reactive under harsher conditions. Finally, we became interested in photochemical upconversion in aqueous solution, for which it was desirable to obtain water-soluble iridium(III) compounds with very high triplet excited-state energies. This goal was achieved through improved ligand design and ultimately enabled sensitized triplet-triplet annihilation upconversion unusually far into the ultraviolet spectral range.Studies of photoredox catalysis, energy transfer catalysis, and photochemical upconversion typically rely on the use of organic solvents. Water could potentially be an attractive alternative in many cases, but photocatalyst development lags somewhat behind for aqueous solution compared to organic solvent. The purpose of this Account is to provide an overview of the breadth of new research perspectives that emerged from the development of water-soluble fac-[Ir(ppy)]3 complexes (ppy = 2-phenylpyridine) with sulfonated ligands. We hope to inspire the use of some of these or related coordination compounds in aqueous photochemistry and to stimulate further conceptual developments at the interfaces of coordination chemistry, photophysics, biocatalysis, and sustainable chemistry.
- Autoren
- Mirjam R Schreier
- Xingwei Guo
- Björn Pfund
- Yasunori Okamoto
- Thomas R Ward
- Christoph Kerzig
- Oliver S Wenger
- Autoren-URL
- https://www.ncbi.nlm.nih.gov/pubmed/35414170
- DOI
- 10.1021/acs.accounts.2c00075
- eISSN
- 1520-4898
- Externe Identifier
- PubMed Central ID: PMC9069695
- Ausgabe der Veröffentlichung
- 9
- Zeitschrift
- Acc Chem Res
- Schlüsselwörter
- Amines
- Electrons
- Energy Transfer
- Iridium
- Ligands
- Organometallic Compounds
- Photochemistry
- Solvents
- Water
- Sprache
- eng
- Country
- United States
- Paginierung
- 1290 - 1300
- Datum der Veröffentlichung
- 2022
- Status
- Published
- Datum, an dem der Datensatz öffentlich gemacht wurde
- 2022
- Titel
- Water-Soluble Tris(cyclometalated) Iridium(III) Complexes for Aqueous Electron and Energy Transfer Photochemistry.
- Sub types
- Journal Article
- Review
- Ausgabe der Zeitschrift
- 55
Datenquelle: PubMed
- Beziehungen:
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