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Ru(II) complexes were synthesized with π-expanding (phenyl, fluorenyl, phenanthrenyl, naphthalen-1-yl, naphthalene-2-yl, anthryl and pyrenyl groups) attached at a 1H-imidazo[4,5-f][1,10]phenanthroline ligand and 4,4'-dimethyl-2,2'-bipyridine (4,4'-dmb) coligands. These Ru(II) complexes were characterized by 1D and 2D NMR, and mass spectroscopy, and studied for visible light and dark toxicity to human malignant melanoma SK-MEL-28 cells. In the SK-MEL-28 cells, the Ru(II) complexes are highly phototoxic (EC = 0.2-0.5 µm) and have low dark toxicity (EC = 58-230 µm). The highest phototherapeutic index (PI) of the series was found with the Ru(II) complex bearing the 2-(pyren-1-yl)-1H-imidazo[4,5-f][1,10]phenanthroline ligand. This high PI is in part attributed to the π-rich character added by the pyrenyl group, and a possible low-lying and longer-lived IL state due to equilibration with the MLCT state. While this pyrenyl Ru(II) complex possessed a relatively high quantum yield for singlet oxygen formation (Φ = 0.84), contributions from type-I processes (oxygen radicals and radical ions) are competitive with the type-II ( O ) process based on effects of added sodium azide and solvent deuteration.
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http://dx.doi.org/10.1111/php.13177 | DOI Listing |
Dalton Trans
September 2025
Department of Chemistry and Protein Research Center for Bio-Industry, Hankuk University of Foreign Studies, Yongin 17035, Republic of Korea.
The nanoscale environment within the void spaces of metal-organic frameworks (MOFs) can significantly influence the photoredox catalytic activity of encapsulated visible-light photoredox catalysts (PCs). To compare two isostructural PC@In-MOF systems, three cationic Ru(II) polypyridine complexes were successfully encapsulated within the mesoscale channels of the anionic framework of InTATB (HTATB = 4,4',4''--triazine-2,4,6-triyltribenzoic acid), which features a doubly interpenetrated framework structure. This encapsulation yielded three heterogenized visible-light PCs, RuL@InTATB, where L = 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen), or 2,2'-bipyrazine (bpz).
View Article and Find Full Text PDFEur J Pharm Sci
September 2025
Department of Organic Chemistry, University of Debrecen, P.O. Box 400, H-4002 Debrecen, Hungary. Electronic address:
Half-sandwich complexes of platinum-group metals are a widely studied subgroup of organometallic compounds with promising anticancer and antimicrobial properties. Recently, we have published a set of polyhapto arene/arenyl Ru(II), Os(II), Ir(III) and Rh(III) complexes with hetaryl-substituted 1-N-glucopyranosyl-1,2,3-triazole and C-glycopyranosyl-1,3,4- and -1,2,4-oxadiazole-type N,N-bidentate ligands, several of which exhibited (sub)micromolar antineoplastic and bacteriostatic potencies. The structure-activity relationships of these series indicated that the nature of the azole ring and its way of connection to the pyranoid sugar unit played crucial roles in the biological activity of such complexes.
View Article and Find Full Text PDFChemistry
September 2025
Department of Chemistry and the Manitoba Institute for Materials, University of Manitoba, Winnipeg, Manitoba, R3T 2N2, Canada.
The coordination chemistry of the planar, doubly π-extended bipyridine analog, 6,6',7,7'-biphenanthridine (p-biphe), is presented. The phenanthridine units in p-biphe are fused together at the 6- and 7- positions, and the resulting rigid ligand is compared with the more flexible parent "biphe" fused only at the 6-positions. p-Biphe is intensely fluorescent in solution with a much higher quantum yield, but, unlike biphe, at 77 K the fluorescence is not accompanied by any significant phosphorescence.
View Article and Find Full Text PDFOrganometallics
August 2025
Department of Chemistry and Biochemistry, University of California Santa Cruz, Santa Cruz, California 95064, United States.
Despite the widespread occurrence of CO poisoning and the number of people left underserved by current treatment options, there are no clinically employed CO poisoning antidotes. Current efforts to develop candidate antidotes have focused on Fe-(II) complexes with a high binding affinity for CO, with small-molecule Fe-(II) porphyrin complexes demonstrating promising potential in this role. The well-established organometallic chemistry of group 8 metals suggests that Ru-(II) and Os-(II) analogs should be able to form even more stable carbonyl adducts than their Fe-(II) congeners.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology, 5-16-1 Omiya, Asahi Ward, Osaka, 535-8585, Japan.
We report a reversible ON-OFF proton-coupled electron transfer (PCET) switch based on ruthenium(II) polypyridyl complexes, triggered by both light and redox stimuli. Upon photoirradiation, a carboxylate-ligated Ru(II) complex undergoes photosubstitution to generate a metastable, PCET-active aqua complex. This metastable complex exhibits redox-induced conformational change, regenerating the original carboxylate complex.
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