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Impact of substituents on molecular properties and catalytic activities of trinuclear Ru macrocycles in water oxidation
Herein we report a broad series of new trinuclear supramolecular Ru(bda) macrocycles bearing different substituents at the axial or equatorial ligands which enabled investigation of substituent effects on the catalytic activities in chemical and photocatalytic water oxidation. Our detailed investiga...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8159484/ https://www.ncbi.nlm.nih.gov/pubmed/34094143 http://dx.doi.org/10.1039/d0sc01097a |
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author | Meza-Chincha, Ana-Lucia Lindner, Joachim O. Schindler, Dorothee Schmidt, David Krause, Ana-Maria Röhr, Merle I. S. Mitrić, Roland Würthner, Frank |
author_facet | Meza-Chincha, Ana-Lucia Lindner, Joachim O. Schindler, Dorothee Schmidt, David Krause, Ana-Maria Röhr, Merle I. S. Mitrić, Roland Würthner, Frank |
author_sort | Meza-Chincha, Ana-Lucia |
collection | PubMed |
description | Herein we report a broad series of new trinuclear supramolecular Ru(bda) macrocycles bearing different substituents at the axial or equatorial ligands which enabled investigation of substituent effects on the catalytic activities in chemical and photocatalytic water oxidation. Our detailed investigations revealed that the activities of these functionalized macrocycles in water oxidation are significantly affected by the position at which the substituents were introduced. Interestingly, this effect could not be explained based on the redox properties of the catalysts since these are not markedly influenced by the functionalization of the ligands. Instead, detailed investigations by X-ray crystal structure analysis and theoretical simulations showed that conformational changes imparted by the substituents are responsible for the variation of catalytic activities of the Ru macrocycles. For the first time, macrocyclic structure of this class of water oxidation catalysts is unequivocally confirmed and experimental indication for a hydrogen-bonded water network present in the cavity of the macrocycles is provided by crystal structure analysis. We ascribe the high catalytic efficiency of our Ru(bda) macrocycles to cooperative proton abstractions facilitated by such a network of preorganized water molecules in their cavity, which is reminiscent of catalytic activities of enzymes at active sites. |
format | Online Article Text |
id | pubmed-8159484 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-81594842021-06-04 Impact of substituents on molecular properties and catalytic activities of trinuclear Ru macrocycles in water oxidation Meza-Chincha, Ana-Lucia Lindner, Joachim O. Schindler, Dorothee Schmidt, David Krause, Ana-Maria Röhr, Merle I. S. Mitrić, Roland Würthner, Frank Chem Sci Chemistry Herein we report a broad series of new trinuclear supramolecular Ru(bda) macrocycles bearing different substituents at the axial or equatorial ligands which enabled investigation of substituent effects on the catalytic activities in chemical and photocatalytic water oxidation. Our detailed investigations revealed that the activities of these functionalized macrocycles in water oxidation are significantly affected by the position at which the substituents were introduced. Interestingly, this effect could not be explained based on the redox properties of the catalysts since these are not markedly influenced by the functionalization of the ligands. Instead, detailed investigations by X-ray crystal structure analysis and theoretical simulations showed that conformational changes imparted by the substituents are responsible for the variation of catalytic activities of the Ru macrocycles. For the first time, macrocyclic structure of this class of water oxidation catalysts is unequivocally confirmed and experimental indication for a hydrogen-bonded water network present in the cavity of the macrocycles is provided by crystal structure analysis. We ascribe the high catalytic efficiency of our Ru(bda) macrocycles to cooperative proton abstractions facilitated by such a network of preorganized water molecules in their cavity, which is reminiscent of catalytic activities of enzymes at active sites. The Royal Society of Chemistry 2020-04-29 /pmc/articles/PMC8159484/ /pubmed/34094143 http://dx.doi.org/10.1039/d0sc01097a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Meza-Chincha, Ana-Lucia Lindner, Joachim O. Schindler, Dorothee Schmidt, David Krause, Ana-Maria Röhr, Merle I. S. Mitrić, Roland Würthner, Frank Impact of substituents on molecular properties and catalytic activities of trinuclear Ru macrocycles in water oxidation |
title | Impact of substituents on molecular properties and catalytic activities of trinuclear Ru macrocycles in water oxidation |
title_full | Impact of substituents on molecular properties and catalytic activities of trinuclear Ru macrocycles in water oxidation |
title_fullStr | Impact of substituents on molecular properties and catalytic activities of trinuclear Ru macrocycles in water oxidation |
title_full_unstemmed | Impact of substituents on molecular properties and catalytic activities of trinuclear Ru macrocycles in water oxidation |
title_short | Impact of substituents on molecular properties and catalytic activities of trinuclear Ru macrocycles in water oxidation |
title_sort | impact of substituents on molecular properties and catalytic activities of trinuclear ru macrocycles in water oxidation |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8159484/ https://www.ncbi.nlm.nih.gov/pubmed/34094143 http://dx.doi.org/10.1039/d0sc01097a |
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