Coordination complexes of precious metals with the d valence electron configuration such as Ru(II), Os(II) and Ir(III) are used for lighting applications, solar energy conversion and photocatalysis. Until now, d complexes made from abundant first-row transition metals with competitive photophysical and photochemical properties have been elusive. While previous research efforts focused mostly on Fe(II), we disclose that isoelectronic Cr(0) gives access to higher photoluminescence quantum yields and excited-state lifetimes when compared with any other first-row d metal complex reported so far. The luminescence behaviour of the metal-to-ligand charge transfer excited states of these Cr(0) complexes is competitive with Os(II) polypyridines. With these Cr(0) complexes, the metal-to-ligand charge transfer states of first-row d metal complexes become exploitable in photoredox catalysis, and benchmark chemical reductions proceed efficiently under low-energy red illumination. Here we demonstrate that appropriate molecular design strategies open up new perspectives for photophysics and photochemistry with abundant first-row d metals.
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http://dx.doi.org/10.1038/s41557-023-01297-9 | DOI Listing |
Chemistry
October 2024
IMDEA Nanociencia, Faraday 9, 28049, Madrid, Spain.
Half-sandwich Ru(II)- and Os(II)-arene complexes have great potential for catalytic and biological applications. The possibility of fine-tuning their chemical reactivity by including modifications in the ligands around the metal adds to their many advantages. However, structural modifications at the η-bound arene have had significant synthetic limitations, particularly in the design of Os(II)-tethered complexes.
View Article and Find Full Text PDFJ Am Chem Soc
August 2024
Molecular Chemistry, Materials and Catalysis (MOST), UCLouvain, Institut de la Matière Condensée et des Nanosciences (IMCN), Place Louis Pasteur 1/L4.01.02, B-1348 Louvain-la-Neuve, Belgium.
The cage escape yield, i.e., the separation of the geminate radical pair formed immediately after bimolecular excited-state electron transfer, was studied in 11 solvents using six Fe(III), Ru(II), and Ir(III) photosensitizers and tri--tolylamine as the electron donor.
View Article and Find Full Text PDFDalton Trans
June 2024
UCLouvain, Institut de la Matière Condensée et des Nanosciences (IMCN), Molecular Chemistry, Materials and Catalysis (MOST), Place Louis Pasteur 1/L4.01.02, B-1348 Louvain-la-Neuve, Belgium.
The synthesis of eight Ru(II) and Os(II) photosensitizers bearing a common 9,10-disubstituted-1,4,5,8-tetraazaphenanthrene backbone is reported. With Os(II) photosensitizers, the 9,10-diNH-1,4,5,8-tetraazaphenanthrene could be directly chelated onto the metal center the heteroaromatic moiety, whereas similar conditions using Ru(II) resulted in the formation of an -quinonediimine derivative. Hence, an alternative route, proceeding the chelation of 9-NH-10-NO-1,4,5,8-tetraazaphenanthrene and subsequent ligand reduction of the corresponding photosensitizers was developed.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
July 2024
Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, School of Pharmacy, Yunnan University, East Outer Ring Road, Kunming, 650500, P. R. China.
A planar conjugated ligand functionalized with bithiophene and its Ru(II), Os(II), and Ir(III) complexes have been constructed as single-molecule platform for synergistic photodynamic, photothermal, and chemotherapy. The complexes have significant two-photon absorption at 808 nm and remarkable singlet oxygen and superoxide anion production in aqueous solution and cells when exposed to 808 nm infrared irradiation. The most potent Ru(II) complex Ru7 enters tumor cells via the rare macropinocytosis, locates in both nuclei and mitochondria, and regulates DNA-related chemotherapeutic mechanisms intranuclearly including DNA topoisomerase and RNA polymerase inhibition and their synergistic effects with photoactivated apoptosis, ferroptosis and DNA cleavage.
View Article and Find Full Text PDFDalton Trans
April 2024
Laboratory of Inorganic Chemistry, Department of Chemistry, University of Ioannina, 45110, Greece.
The reaction mechanisms of the photocatalytic reduction of CO to CO catalyzed by [(en)M(CO)Cl] complexes (M = Ru, Os, en = ethylenediamine) in the presence of triethanolamine (TEOA), RN (R = -CHCHOH), in DCM and DMF solvents, were studied by means of DFT/TDDFT electronic structure calculations. The geometric and free energy reaction profiles for two possible reaction pathways were calculated. Both reaction pathways studied, start with the 17e, catalytically active intermediate, [(en)M(CO)]˙ generated from the first triplet excited state, T upon reductive quenching by TEOA which acts as a sacrificial electron donor.
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