Search Results (8)

In this work, we report an example of tuning the photophysical properties of a polypyridine ruthenium(II) complex via the coordination of a second cation. A new ruthenium(II) complex contains a thiacrown-ether fragment that allows selective binding of additional metal cations (Ba²⁺, Cd²⁺, Pb²⁺), leading to pronounced changes in the optical and electronic properties of the bimetallic system. Spectroscopic and electrochemical studies reveal that the monoruthenium precursor displays dual excitation pathways involving either intraligand charge transfer (ILCT) or triplet metal-to-ligand charge transfer (³MLCT) excited states. Upon coordination of a second metal ion, the ILCT channel is suppressed, and only the ³MLCT state remains emissive, resulting in a significant increase in phosphorescence quantum yields (up to 22.6% in degassed solutions) for the bimetallic derivative. Time-resolved emission studies confirm the conversion from biexponential to monoexponential luminescence decay upon complexation. Electrochemical analysis and density functional theory (DFT) calculations support the hypothesis that cation binding alters the electron density distribution within the chromophore, stabilizing the MLCT pathway. These results demonstrate that incorporation of a second cation provides an effective strategy to control excited-state dynamics in ruthenium complexes, offering opportunities for the rational design of photosensitizers and photofunctional materials. Full article

This article provides an overview of the development, structure and activity of various metal complexes with anti-cancer activity. Chemical researchers continue to work on the development and synthesis of new molecules that could act as anti-tumor drugs to achieve more favorable therapies. It is therefore important to have information about the various chemotherapeutic substances and their mode of action. This review focuses on metallodrugs that contain a metal as a key structural fragment, with cisplatin paving the way for their chemotherapeutic application. The text also looks at ruthenium complexes, including the therapeutic applications of phosphorescent ruthenium(II) complexes, emphasizing their dual role in therapy and diagnostics. In addition, the antitumor activities of titanium and gold derivatives, their side effects, and ongoing research to improve their efficacy and reduce adverse effects are discussed. Metallization of host defense peptides (HDPs) with various metal ions is also highlighted as a strategy that significantly enhances their anticancer activity by broadening their mechanisms of action. Full article

Selective staining of extracellular vesicles (EVs) is a major challenge for diagnostic and therapeutic applications. Herein, the EV labeling properties of a new class of tetranuclear polypyridylruthenium(II) complexes, Rubb₇-TNL and Rubb₇-TL, as phosphorescent stains are described. These new stains have many advantages over standard stains to detect and characterize EVs, including: high specificity for EV staining versus cell staining; high phosphorescence yields; photostability; and a lack of leaching from EVs until incorporation with target cells. As an example of their utility, large EVs released from control (basal) or lipopolysaccharide (LPS)-stimulated THP-1 monocytic leukemia cells were studied as a model of immune system EVs released during bacterial infection. Key findings from EV staining combined with flow cytometry were as follows: (i) LPS-stimulated THP-1 cells generated significantly larger and more numerous large EVs, as compared with those from unstimulated cells; (ii) EVs retained native EV physical properties after staining; and (iii) the new stains selectively differentiated intact large EVs from artificial liposomes, which are models of cell membrane fragments or other lipid-containing debris, as well as distinguished two distinct subpopulations of monocytic EVs within the same experiment, as a result of biochemical differences between unstimulated and LPS-stimulated monocytes. Comparatively, the staining patterns of A549 epithelial lung carcinoma-derived EVs closely resembled those of THP-1 cell line-derived EVs, which highlighted similarities in their selective staining despite their distinct cellular origins. This is consistent with the hypothesis that these new phosphorescent stains target RNA within the EVs. Full article

The measurement of oxygen consumption is an important element in the understanding of an organism’s metabolic state. Oxygen is also a phosphorescence quencher, which allows the evaluation of phosphorescence emitted by oxygen sensors. Two Ru(II)-based oxygen-sensitive sensors were used to study the effect of chemical compounds [(1) = [CoCl₂(dap)₂]Cl, and (2) = [CoCl₂(en)₂]Cl (AmB = amphotericin B) against reference and clinical strains of Candida albicans. The tris-[(4,7-diphenyl-1,10-phenanthroline)ruthenium(II)] chloride ([Ru(DPP)₃]Cl₂) (Box) adsorbed onto the Davisil^TM silica gel was embedded in the silicone rubber Lactite NuvaSil^® 5091 and the coating on the bottom of 96-well plates. The water-soluble oxygen sensor (BsOx = tris-[(4,7-diphenyl-1,10-phenanthrolinedisulphonic acid disodium)ruthenium(II)] chloride ‘x’ hydrate = {Ru[DPP(SO₃Na)₂]₃}Cl₂ = water molecules were omitted in the BsOx formula) was synthesized and characterized by RP-UHPLC, LCMS, MALDI, elemental analysis, ATR, UV-Vis, ¹H NMR, and TG/IR techniques. The microbiological studies were performed in the environment of RPMI broth and blood serum. Both Ru(II)-based sensors turned out to be useful in the study of the activity of Co(III) complexes and the commercial antifungal drug amphotericin B. In addition, a new activity of the oxygen sensor, the soluble Ru(II) complex BsOx, was demonstrated, which is a mixture with amphotericin B that caused a significant increase in its antifungal activity. Thus, it is also possible to demonstrate the synergistic effect of compounds active against the microorganisms under study. Full article

Improvements in the design of receptors for the detection and quantification of anions are desirable and ongoing in the field of anion chemistry, and remarkable progress has been made in this direction. In this regard, the development of luminescent chemosensors for sensing anions is an imperative and demanding sub-area in supramolecular chemistry. This decade, in particular, witnessed advancements in chemosensors based on ruthenium and iridium complexes for anion sensing by virtue of their modular synthesis and rich chemical and photophysical properties, such as visible excitation wavelength, high quantum efficiency, high luminescence intensity, long lifetimes of phosphorescence, and large Stokes shifts, etc. Thus, this review aims to summarize the recent advances in the development of ruthenium(II) and iridium(III)-based complexes for their application as luminescent chemosensors for anion sensing. In addition, the focus was devoted to designing aspects of polypyridyl complexes of these two transition metals with different recognition motifs, which upon interacting with different inorganic anions, produces desirable quantifiable outputs. Full article

The present review summarizes the work carried out mostly in the last decade on iridium and ruthenium complexes bearing various perylene ligands, of particular interest for bioimaging, photodynamic therapy, and solar energy conversion. In these complexes, the absorption spectra and the electrochemical properties are those of the perylene subunit plus those of the metal moiety. In contrast, the emissions are completely changed with respect to perylenes considered alone. Thus, fully organic perylenes are characterized by a strong fluorescence in the visible region, lifetimes of a few nanoseconds, and luminescence quantum yields approaching 100%, whereas perylene Ir and Ru complexes usually do not emit; however, in few cases, weak phosphorescent emissions, with lifetimes in the range of microseconds and relatively low quantum yields, are reported. This is due to a strong interaction between the perylene core and the heavy metal center, taking place after the excitation. Nevertheless, an important advantage deriving from the presence of the heavy metal center is represented by the ability to generate large amounts of singlet oxygen, which plays a key role in photodynamic therapy. Full article

In this work, we report the synthesis of the nido-carborane-substituted ruthenium complexes and the substituent effects of nido-carboranes on the optical properties. Initially, from the optical measurements, it is shown that deep-red phosphorescence was obtained from the synthesized molecule, and the phosphorescent quantum yields were significantly improved by loading onto a polyethylene glycol film. This result represents that nido-carborane can work as a strong electron donor and should be an effective unit for enhancing the solid-state phosphorescence of ruthenium complexes. Further, it is suggested that the electron-donating properties of the nido-carborane units and subsequently the optical properties can be tuned by controlling the conformation of the nido-carborane units with the steric substituents. We demonstrate in this study the potential of nido-carborane as a building block for constructing optical materials as well as fundamental information regarding electronic interactions with π-conjugated systems. Full article

The complex [Os(btzpy)₂][PF₆]₂ (1, btzpy = 2,6-bis(1-phenyl-1,2,3-triazol-4-yl)pyridine) has been prepared and characterised. Complex 1 exhibits phosphorescence (λ_em = 595 nm, τ = 937 ns, φ_em = 9.3% in degassed acetonitrile) in contrast to its known ruthenium(II) analogue, which is non-emissive at room temperature. The complex undergoes significant oxygen-dependent quenching of emission with a 43-fold reduction in luminescence intensity between degassed and aerated acetonitrile solutions, indicating its potential to act as a singlet oxygen sensitiser. Complex 1 underwent counterion metathesis to yield [Os(btzpy)₂]Cl₂ (1^Cl), which shows near identical optical absorption and emission spectra to those of 1. Direct measurement of the yield of singlet oxygen sensitised by 1^Cl was carried out (φ (¹O₂) = 57%) for air equilibrated acetonitrile solutions. On the basis of these photophysical properties, preliminary cellular uptake and luminescence microscopy imaging studies were conducted. Complex 1^Cl readily entered the cancer cell lines HeLa and U2OS with mitochondrial staining seen and intense emission allowing for imaging at concentrations as low as 1 μM. Long-term toxicity results indicate low toxicity in HeLa cells with LD50 >100 μM. Osmium(II) complexes based on 1 therefore present an excellent platform for the development of novel theranostic agents for anticancer activity. Full article