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Impact of substituents on molecular properties and catalytic activities of trinuclear Ru macrocycles in water oxidation

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Abstract

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.

Graphical abstract: Impact of substituents on molecular properties and catalytic activities of trinuclear Ru macrocycles in water oxidation

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Supplementary files

Article information


Submitted
24 Feb 2020
Accepted
20 Apr 2020
First published
29 Apr 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020, Advance Article
Article type
Edge Article

Impact of substituents on molecular properties and catalytic activities of trinuclear Ru macrocycles in water oxidation

A. Meza-Chincha, J. O. Lindner, D. Schindler, D. Schmidt, A. Krause, M. I. S. Röhr, R. Mitrić and F. Würthner, Chem. Sci., 2020, Advance Article , DOI: 10.1039/D0SC01097A

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