New ruthenium(ii) polypyridyl complexes of formulae [RuCl(MeNtrpy)(bpy-OMe)]Cl, 1, and [Ru(MeNtrpy)(bpy-OMe)(OH)](CFSO), 2, with MeNtrpy = 4'-,-dimethylamino-2,2':6',2''-terpyridine and bpy-OMe = 4,4'-dimethoxy-2,2'-bipyridine, were synthetized and characterized by spectroscopic and electrochemical techniques. Besides, [Ru(MeNtrpy)(bpy-OMe)(NCCH)], 3, was obtained and characterized by UV-vis spectroscopy in acetonitrile solution. All experimental results were complemented with DFT and TD-DFT calculations. The complete structure of complex 1 was determined by X-ray diffraction, evidencing that the Ru-N and Ru-Cl bond lengths are longer than those determined in [RuCl(trpy)(bpy)](PF). The strong electron donating properties of the substituents of both bpy and trpy rings in complexes 1 and 2 led to their potential applications for detecting traces of acetonitrile as a contaminant in aqueous solutions of radiopharmaceuticals and to utilization of complex 2 as a promising candidate for catalyzing water oxidation processes.
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http://dx.doi.org/10.1039/d1ra09455f | DOI Listing |
Sensors (Basel)
December 2024
Chemical Optosensors & Applied Photochemistry Group (GSOLFA), Department of Organic Chemistry, Faculty of Chemistry, Complutense University of Madrid, 28040 Madrid, Spain.
Water conductivity sensing relies universally on electrical measurements, which are subject to corrosion of the electrodes and subsequent signal drift in prolonged in situ uses. Furthermore, they cannot provide contactless sensing or remote readout. To this end, a novel device for water conductivity monitoring has been developed by employing a microenvironment-sensitive ruthenium complex, [Ru(2,2'-bipyridine-4,4'-disulfonato)], embedded into a quaternary ammonium functionalized cross-linked polymer support.
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December 2024
Indian Institute of Technology Kanpur, Chemistry, Department of Chemistry, Indian Institute of Technology Kanpur, 208016, Kanpur, INDIA.
Herein, the photophysical, photochemical properties and photogenerated excited state dynamics of two new Ru(II) complexes, viz. [Ru(p-ttp)(bpy)(PTA)]2+ [1]2+, [Ru(p-ttp)(phen)(PTA)]2+ [2]2+ having a phosphorus-based ligand PTA [p-ttp = p-tolyl terpyridine; bpy = 2,2'-bipyridyl; phen = 1,10-phenthroline and PTA = 1,3,5-triaza-7-phosphaadamantane] are reported. Upon excitation with 470 nm LED, [1]2+ and [2]2+ neither undergo ligand release nor exhibit room temperature luminescence/1O2 generation.
View Article and Find Full Text PDFInorg Chem
December 2024
School of Chemistry, University College Dublin, Dublin 4 D04 V1W8, Ireland.
The preparation, electrochemistry and photophysical properties of a heteroleptic chromium(III) polypyridyl complex [Cr(TMP)(dppn)] () containing two 3,4,7,8-tetramethyl-1,10-phenanthroline (TMP) ligands and the π-extended benzodipyrido[3,2-a:2',3'-]phenazine (dppn) ligand are reported. The visible absorption spectrum of reveals distinct bands between 320 and 420 nm characteristic of dppn-based ligand-centered transitions, with found to be nonemissive in aqueous solution but weakly luminescent in aerated acetonitrile solution. Transient visible absorption (TrA) spectroscopy reveals that 400 nm excitation of leads to initial population of a ligand-to-metal charge transfer (LMCT) state which evolves within tens of ps to form a dppn-localized intraligand (IL) state which persists for longer than 7 ns and efficiently sensitizes singlet oxygen.
View Article and Find Full Text PDFChemistry
November 2024
Centre for Advanced Functional Materials, Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Nadia, West Bengal, Mohanpur, 741246, India.
The Warburg effect, which generates increased demand of glucose in cancer cells is a relatively underexplored phenomenon in existing commercial drugs to enhance uptake in cancer cells. Here, we present a chemotherapeutic strategy employing a Ru(II)-bis-bipyridyl-morphocumin complex (2) encapsulated in a self-assembling glucose-functionalized copolymer P(G-EMA-co-MMA) (where G=glucose; MMA=methyl methacrylate; EMA=ethyl methacrylate), designed to exploit this effect for enhanced selectivity in cancer treatment. The P(G-EMA-co-MMA) polymer, synthesized via reversible-addition fragmentation chain transfer (RAFT) polymerization, has a number average molecular weight (M) of 8000 g/mol.
View Article and Find Full Text PDFInorg Chem
December 2024
Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena, Humboldtstr. 10, 07743 Jena, Germany.
In this contribution, the divergent modular synthesis of photoredox-active dyads, triads and a tetrad descending from one ligand precursor is presented by combining "chemistry-on-the-ligand", stepwise complexation and "chemistry-on-the-complex" with minimal synthetic efforts. In the final step, Pd-mediated borylation and subsequent Suzuki-Miyaura cross-coupling was employed to introduce the different (multi)donor moieties at the preassembled P-A dyad subunit. The (spectro-)electrochemical data revealed preserved redox properties of the subunits and minimal driving force for oxidative quenching by the naphthalene diimide-based (NDI) acceptor and, thus, high-energy charge separated (CS) states.
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