Efficient Access of Phenyl-Spaced 5,5′-Bridged Dinuclear Ruthenium Metal Complexes and the Effect of Dynamic Ligand Exchange on Catalysis

Lämmle, Martin; Volk, Steffen; Klinkerman, Madelyn; Müßler, Marius; Mengele, Alexander K.; Rau, Sven

doi:10.3390/photochem2040053

Open AccessArticle

Efficient Access of Phenyl-Spaced 5,5′-Bridged Dinuclear Ruthenium Metal Complexes and the Effect of Dynamic Ligand Exchange on Catalysis

by

Martin Lämmle

,

Steffen Volk

,

Madelyn Klinkerman

,

Marius Müßler

,

Alexander K. Mengele

and

Sven Rau

^*

Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm, Germany

^*

Author to whom correspondence should be addressed.

Photochem 2022, 2(4), 831-848; https://doi.org/10.3390/photochem2040053

Submission received: 8 September 2022 / Revised: 29 September 2022 / Accepted: 1 October 2022 / Published: 6 October 2022

(This article belongs to the Special Issue A Themed Issue in Honor of Professor David I. Schuster's Great Contribution)

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Abstract

Herein, we present the synthesis, characterization, and light-driven hydrogen evolution activity of two dinuclear Ru-Pt complexes, Rup(ph)pPtX₂ (X = Cl, I), comprising a new phenyl-spaced 5,5′-bis-phenanthroline p(ph)p bridging ligand. The two complexes only differ in the nature of the halide ligand at the catalytic center. Structural, photophysical, electrochemical, as well as photochemical characterization techniques revealed that the variations of single components of the intramolecular system provide a strong influence on the stability even in non-catalytic conditions. Interestingly, varying electron density at the catalytic center, mainly influenced by the coordinating halide at the catalytic center, as shown by ¹⁹⁵Pt NMR spectroscopy, strongly influences the photocatalytic efficiency. Furthermore, intensive investigations on the potential catalytic mechanism showed that small structural variations (e.g., halide exchange) not only affect catalytic activity but can also switch the main catalytic mechanism from an initially molecular one to a fully heterogeneous, colloid-driven hydrogen evolution.

Keywords: ruthenium; photocatalysis; hydrogen; colloids; ligands

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MDPI and ACS Style

Lämmle, M.; Volk, S.; Klinkerman, M.; Müßler, M.; Mengele, A.K.; Rau, S. Efficient Access of Phenyl-Spaced 5,5′-Bridged Dinuclear Ruthenium Metal Complexes and the Effect of Dynamic Ligand Exchange on Catalysis. Photochem 2022, 2, 831-848. https://doi.org/10.3390/photochem2040053

AMA Style

Lämmle M, Volk S, Klinkerman M, Müßler M, Mengele AK, Rau S. Efficient Access of Phenyl-Spaced 5,5′-Bridged Dinuclear Ruthenium Metal Complexes and the Effect of Dynamic Ligand Exchange on Catalysis. Photochem. 2022; 2(4):831-848. https://doi.org/10.3390/photochem2040053

Chicago/Turabian Style

Lämmle, Martin, Steffen Volk, Madelyn Klinkerman, Marius Müßler, Alexander K. Mengele, and Sven Rau. 2022. "Efficient Access of Phenyl-Spaced 5,5′-Bridged Dinuclear Ruthenium Metal Complexes and the Effect of Dynamic Ligand Exchange on Catalysis" Photochem 2, no. 4: 831-848. https://doi.org/10.3390/photochem2040053

APA Style

Lämmle, M., Volk, S., Klinkerman, M., Müßler, M., Mengele, A. K., & Rau, S. (2022). Efficient Access of Phenyl-Spaced 5,5′-Bridged Dinuclear Ruthenium Metal Complexes and the Effect of Dynamic Ligand Exchange on Catalysis. Photochem, 2(4), 831-848. https://doi.org/10.3390/photochem2040053

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Efficient Access of Phenyl-Spaced 5,5′-Bridged Dinuclear Ruthenium Metal Complexes and the Effect of Dynamic Ligand Exchange on Catalysis

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