Issue 10, 2017

Cooperative water oxidation catalysis in a series of trinuclear metallosupramolecular ruthenium macrocycles

Abstract

A series of trinuclear metallosupramolecular Ru(bda) macrocycles has been synthesized and the impact of the ring size on the catalytic activity in homogeneous water oxidation has been elucidated (bda = 2,2′-bipyridine-6,6′-dicarboxylate). Kinetic experiments revealed that for all macrocyclic catalysts a proton-coupled oxidation event is rate-determining. Distinct H/D kinetic isotope effects (KIE) have been observed for the individual macrocycles, which follow the same tendency like the catalytic activity where an intermediate ring size exhibits the best performance. To get insight into the different molecular properties, molecular dynamics simulations using a QM/MM approach have been performed for all reaction steps, revealing that the size of the cavity strongly influences the hydrogen-bonded water network inside the macrocyclic structure and thus, important proton-coupled reaction steps of the catalytic cycle. For the most active catalysts, all reactive sites point into the interior of the cavity, which is supported by a single crystal X-ray analysis of the largest macrocycle, and a cooperative effect between the individual Ru(bda) centers facilitating proton abstraction has been substantiated. On the other hand, different structural conformations predominate the smaller macrocycles, which prevent efficient interactions between the Ru(bda) centers.

Graphical abstract: Cooperative water oxidation catalysis in a series of trinuclear metallosupramolecular ruthenium macrocycles

Supplementary files

Article information

Article type
Paper
Submitted
06 জুন 2017
Accepted
25 আগষ্ট 2017
First published
04 চেপ্টে 2017

Energy Environ. Sci., 2017,10, 2137-2153

Cooperative water oxidation catalysis in a series of trinuclear metallosupramolecular ruthenium macrocycles

V. Kunz, J. O. Lindner, M. Schulze, M. I. S. Röhr, D. Schmidt, R. Mitrić and F. Würthner, Energy Environ. Sci., 2017, 10, 2137 DOI: 10.1039/C7EE01557G

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements