Journal Article

PUBDB-2026-00915

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Secondary Coordination Sphere Effects in Macrocycle-Embedded Mononuclear Ru(bda) Water Oxidation Catalysts

Das, G. ; Friedewald, D. A. P. ; Tang, D. ; Shoyama, K.Extern* ; Creazzo, F. ; Luber, S. (Corresponding author) ; Wuerthner, F. (Corresponding author)Extern*

2026
American Chemical Society Washington, DC

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Please use a persistent id in citations: doi:10.1021/acs.inorgchem.5c05933  doi:10.3204/PUBDB-2026-00915

Abstract: Integration of Ru(bda) [bda = (2,2’-bipyridine)-6,6’-dicarboxylate] water oxidation catalysts together with dibenzofuran, dibenzothiophene, or carbazole heterocycles within macrocycles 1-3 affords structures with different conformational preferences. The latter are dictated by noncovalent interactions of the bda oxygens with NH (hydrogen bond) or S (chalcogen bond). The different orientations afford changes in the secondary coordination sphere, thereby influencing the rate and mechanism of photocatalytic water oxidation for the three mononuclear Ru(bda)-based catalysts, with the dibenzothiophene- and carbazole-based ones favoring the unimolecular pathway (first-order kinetics), typically related to water nucleophilic attack (WNA), and the dibenzofuran one operating via a bimolecular pathway (second-order kinetics), typically related to the interaction of two metal-oxo species (I2M). NMR and single crystal X-ray analyses provided insight into the conformational preferences of the precursor macrocycles in the Ru(II) state. Photocatalytic studies including the H/D kinetic isotope effect (KIE) in deuterated water together with theoretical studies on the orientation angle-dependent energy profile for macrocycles in the Ru(V) state afforded a structure–property relationship that explains the outcome of the water oxidation experiments.

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Contributing Institute(s):

1. DOOR-User (DOOR ; HAS-User)

Research Program(s):

1. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)
2. FS-Proposal: I-20220939 (I-20220939) (I-20220939)
3. FS-Proposal: I-20230262 (I-20230262) (I-20230262)
4. SUPRAWOC - Supramolecular Architectures for Ruthenium Water Oxidation Catalysis (787937) (787937)

Experiment(s):

1. PETRA Beamline P11 (PETRA III)

Appears in the scientific report 2026

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Database coverage:
; ; ; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; Ebsco Academic Search ; Essential Science Indicators ; IF < 5 ; JCR ; Nationallizenz ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

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