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Unravelling the Relaxation Pathway and Excited State Dynamics of Ruthenium(II) Polypyridyl Complexes Incorporating Phosphorus-Based Monodentate Ligands.
Chemistry
December 2024
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016, Uttar Pradesh, India.
Article Synopsis
- The study investigates two new Ru(II) complexes containing a phosphorus-based ligand (PTA) and analyzes their photophysical, photochemical properties, and excited state dynamics.
- Excitation at 470 nm does not trigger ligand release or noticeable luminescence at room temperature, but luminescence is detected at 77 K when excited near the MLCT bands.
- The complexes show non-cytotoxic behavior in cancer cells, linked to their stability and failure to produce reactive oxygen species, including findings from MTT assays and ICP-MS analyses.
Near-infrared phosphorescence in a ruthenium(II) complex equipped with a pyridyl-1,2-azaborine ligand.
Dalton Trans
January 2025
Institute for Organic Synthesis and Photoreactivity (ISOF), National Research Council of Italy (CNR), Via Piero Gobetti 101, 40129 Bologna, Italy.
The 4-methyl-2-(pyridin-2-yl)-2,1-borazaronaphthalene molecule Hazab-py has been successfully used, for the first time, as a ligand in a ruthenium(II) polypyridine complex A (with the formula [Ru(dtbbpy)(azab-py)], where dtbbpy = 4,4'-di--butyl-2,2'-bipyridine). This compound was characterized by NMR spectroscopy and high-resolution mass spectrometry (MS), and its electrochemical and photophysical properties were fully investigated and compared to those of its homoleptic analogue [Ru(dtbbpy)] (B), an archetypical mono-cationic cyclometalated complex C (with the formula [Ru(dtbbpy)(ppy)], where Hppy = 2-phenylpyridine), and the more structurally similar analogue [Ru(dtbbpy)(naft-py)] (D), where the B-N unit of the azaborine ligand is replaced by a standard CC one, resulting in the 2-(naphthalen-2-yl)pyridine ligand (Hnaft-py). The presence of the novel 1,2-azaborine ligand induces a 0.
View Article and Find Full Text PDFCyrene™ as a green alternative to ,'-dimethylformamide (DMF) in the synthesis of MLCT-emissive ruthenium(II) polypyridyl complexes for biological applications.
Dalton Trans
November 2024
Department of Chemistry, Faculty of Science and Engineering, Swansea University, Swansea, UK.
Ruthenium(II) polypyridyl complexes (RPCs) that emit from triplet metal-to-ligand charge transfer (MLCT) states find a wide variety of uses ranging from luminophores to potential anti-cancer or anti-bacterial therapeutics. Herein we describe a greener, microwave-assisted synthetic pathway for the preparation of homoleptic [Ru(N^N)] and bis-heteroleptic [Ru(N^N)(N'^N')] type complexes. This employs the bio-renewable solvent Cyrene™, dihydrolevoglucosenone, as a green alternative to ,'-dimethylformamide (DMF) in the synthesis of Ru(N^N)Cl intermediate complexes, obtaining comparable yields for N^N = 2,2'-bipyridine, 1,10-phenanthroline and methylated derivatives.
View Article and Find Full Text PDFSonoinduced Tumor Therapy and Metastasis Inhibition by a Ruthenium Complex with Dual Action: Superoxide Anion Sensitization and Ligand Fracture.
J Am Chem Soc
September 2024
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, Dalian University of Technology, Dalian 116024, China.
Photoresponsive ruthenium(II) complexes have recently emerged as a promising tool for synergistic photodynamic therapy and chemotherapy in oncology, as well as for antimicrobial applications. However, the limited penetration power of photons prevents the treatment of deep-seated lesions. In this study, we introduce a sonoresponsive ruthenium complex capable of generating superoxide anion (O) via type I process and initiating a ligand fracture process upon ultrasound triggering.
View Article and Find Full Text PDFDual Photoreactive Ternary Ruthenium(II) Terpyridyl Complexes: A Comparative Study on Visible-Light-Induced Single-Step Dissociation of Bidentate Ligands and Generation of Singlet Oxygen.
Inorg Chem
August 2024
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh 208016, India.
The versatile and tunable ligand-exchange dynamics in ruthenium(II)-polypyridyl complexes imposed by the modulation of the steric and electronic effects of the coordinated ligands provide an unlimited scope for developing phototherapeutic agents. The photorelease of a bidentate ligand from the Ru-center is better suited for potent Ru(II)-based photocytotoxic agents with two available labile sites for cross-linking with biological targets augmented with possible phototriggered O generation. Herein, we introduced a phenyl-terpyridine (ptpy) ligand in the octahedral Ru(II) core of [Ru(ptpy)(L-L)Cl] to induce structural distortion for the possible photorelease of electronically distinct bidentate ligands (L-L).
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