TY  - JOUR
AU  - Das, Gourab
AU  - Friedewald, Daniel A. P.
AU  - Tang, Deqi
AU  - Shoyama, Kazutaka
AU  - Creazzo, Fabrizio
AU  - Luber, Sandra
AU  - Wuerthner, Frank
TI  - Secondary Coordination Sphere Effects in Macrocycle-Embedded Mononuclear Ru(bda) Water Oxidation Catalysts
JO  - Inorganic chemistry
VL  - 65
IS  - 8
SN  - 0020-1669
CY  - Washington, DC
PB  - American Chemical Society
M1  - PUBDB-2026-00915
SP  - 4710 - 4720
PY  - 2026
AB  - 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.
LB  - PUB:(DE-HGF)16
DO  - DOI:10.1021/acs.inorgchem.5c05933
UR  - https://bib-pubdb1.desy.de/record/646668
ER  -