An Electrochemical and Raman Spectroscopy Study of the Surface Behaviour of Mononuclear Ruthenium and Osmium Polypyridyl Complexes Based on Pyridyl‐ and Thiophene‐Based Linkers

Halpin, Yvonne; Logtenberg, Hella; Cleary, Laura; Schenk, Stephan; Schulz, Martin; Draksharapu, Apparao; Browne, Wesley R.; Vos, Johannes G.

doi:10.1002/ejic.201300366

Cited by 7 publications

(4 citation statements)

References 59 publications

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“…or iridium(III) 41 and ruthenium(II) polypyridine 11,31,32,[42][43][44][45][46][47][48][49][50][51] complexes. Surprisingly, as far as the latter are concerned, all examples are limited to one-step reactions, either reduction, 45,46 condensation, 31,45 hydrolysis, 47,49-52 coppercatalyzed azide-alkyne cycloaddition 53,54 (click chemistry) or palladium-catalyzed cross-couplings.…”

Section: Functionalization Of the Dipyrido-quinolino-phenazine Ligand...mentioning

confidence: 99%

Synthesis of three series of ruthenium tris-diimine complexes containing acridine-based π-extended ligands using an efficient “chemistry on the complex” approach

et al. 2016

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The preparation and characterization of three series of novel ruthenium(ii) complexes are reported, each series differing by the nature of the ancillary ligands (2,2'-bipyridine - bpy, 1,10-phenanthroline - phen or 1,4,5,8-tetraazaphenanthrene - TAP). The third ligand was either the heptacyclic heterocycle dipyrido[3,2-a:2',3'-c]quinolino[3,2-h]phenazine (dpqp) substituted at position 12 by an hydroxyl (oxo), 2,2-dimethoxyethylamine (DMEA) or halogeno (Cl or Br) substituent, or the octacyclic dipyrido[3,2-a:2',3'-c]pyrido[2,3,4-de]quinolino[3,2-h]phenazine (dppqp), prepared by a multi-step "chemistry on the complex" strategy from [RuL(oxo-dpqp)](PF). The three steps, halogenation, substitution by a dimethoxyethylamino group and cyclization in trifluoroacetic acid, were performed in reasonable to high yields depending on the nature of the ancillary ligands. Isolation and purification processes were facilitated by the ability to switch the solubility of the complex from aqueous to organic solvents, depending on the counter-ion. All new complexes were fully characterized; in particular their absorption properties were compared by UV-vis spectroscopy. Finally, π-stacking properties induced by these extended ligands were studied by H NMR studies and quantum chemical calculations.

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Section: Functionalization Of the Dipyrido-quinolino-phenazine Ligand...mentioning

confidence: 99%

Synthesis of three series of ruthenium tris-diimine complexes containing acridine-based π-extended ligands using an efficient “chemistry on the complex” approach

et al. 2016

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“…Its SERS spectrum is equivalent to its nonresonant Raman spectrum and so can be used to demonstrate the impact of specific adsorption on Raman spectra (Figure ). , A roughened (SERS-active) electrode was first immersed in a solution of [Ru(bpy) 3 ] 2+ (10 μM in water) and was subsequently removed and immersed in pure water while the Raman scattering intensity from the electrode was monitored over time. The Raman bands of [Ru(bpy) 3 ] 2+ initially decrease in intensity, consistent with desorption of nonspecificially adsorbed species, but the residual signal remains stable for several hours, which is consistent with (specific) adsorption to the electrode.…”

Section: Resultsmentioning

confidence: 99%

Selective Analysis of Redox Processes at the Electrode Interface with Time-Resolved Raman Spectroscopy

2023

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Electrochemistry and electrochemical reactions are increasingly important in the transition to a sustainable chemical industry. The electron transfer that drives such reactions takes place within nanometers of the electrode surface, and follow-up chemical reactions take place within the diffusion layer. Hence, understanding electrochemical reactions requires time-, potential-, and spatially resolved analysis. The confocal nature of Raman spectroscopy provides high spatial resolution, in addition to detailed information on molecular structure. The intrinsic weakness of nonresonant Raman scattering, however, is not sensitive enough for relatively minor changes to the solution resulting from reactions at the electrode interface. Indeed, the limit of detection is typically well above the concentrations used in electrochemical studies. Here, we show that surface-enhanced Raman scattering (SERS) and resonance Raman (rR) spectroscopy allow for spatially and time-resolved analysis of solution composition at (<1–2 nm) and near (within 5 μm) the electrode surface, respectively, in a selective manner for species present at low (<1 mM) concentrations. We show changes in concentration of species at the electrode surface, without the need for labels, specific adsorption, or resonance enhancement, using a SERS-active gold electrode prepared readily by electrochemical surface roughening. A combination of smooth and roughened gold electrodes is used to distinguish between surface and resonance enhancement using the well-known redox couples ferrocene and 2,2’-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS). We discuss the impact of specific adsorption on the spectral analysis with the ruthenium(II) polypyridyl complex, [Ru(bpy)3]2+. The dual function of the electrode (surface enhancement and electron transfer) in the analysis of solution processes is demonstrated with the reversible oxidation of TMA (4,N,N-trimethylaniline), where transient soluble species are identified in real time, with rapid spectral acquisition, making use of localized enhancement. We anticipate that this approach will find use in elucidating electro(catalytic) reactions at electrode interfaces.

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“…The synthetic routes of RuRe-1 and RuRe-2 are shown in Supplementary Figure S1 . Firstly, mononuclear complexes Ru-1 ( Halpin et al, 2013 ) and Re-1 ( Woźna and Kapturkiewicz, 2015 ) were synthesized according to literature methods. Ru-2 was prepared following a similar procedure to that of Ru-1 , except that cis -[Ru(phen) 2 Cl 2 ]·2H 2 O ( Sullivan et al, 1978 ) was used instead of cis -[Ru(bpy) 2 Cl 2 ]·2H 2 O ( Hartshorn and Barton, 1992 ).…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Characterization and Antitumor Mechanism Investigation of Heterometallic Ru(Ⅱ)-Re(Ⅰ) Complexes

Yang

et al. 2022

Front. Chem.

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The development of heteronuclear metal complexes as potent anticancer agents has received increasing attention in recent years. In this study, two new heteronuclear Ru(Ⅱ)-Re(Ⅰ) metal complexes, [Ru(bpy)2LRe(CO)3(DIP)](PF6)3 and [Ru(phen)2LRe(CO)3(DIP)](PF6)3 [RuRe-1 and RuRe-2, L = 2-(4-pyridinyl)imidazolio[4,5-f][1,10]phenanthroline, bpy = 2,2′-bipyridine, DIP = 4,7-diphenyl-1,10-phenanthroline, phen = 1,10-phenanthroline], were synthesized and characterized. Cytotoxicity assay shows that RuRe-1 and RuRe-2 exhibit higher anticancer activity than cisplatin, and exist certain selectivity toward human cancer cells over normal cells. The anticancer mechanistic studies reveal that RuRe-1 and RuRe-2 can induce apoptosis through the regulation of cell cycle, depolarization of mitochondrial membrane potential (MMP), elevation of intracellular reactive oxygen species (ROS), and caspase cascade. Moreover, RuRe-1 and RuRe-2 can effectively inhibit cell migration and colony formation. Taken together, heteronuclear Ru(Ⅱ)-Re(Ⅰ) metal complexes possess the prospect of developing new anticancer agents with high efficacy.

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An Electrochemical and Raman Spectroscopy Study of the Surface Behaviour of Mononuclear Ruthenium and Osmium Polypyridyl Complexes Based on Pyridyl‐ and Thiophene‐Based Linkers

Cited by 7 publications

References 59 publications

Synthesis of three series of ruthenium tris-diimine complexes containing acridine-based π-extended ligands using an efficient “chemistry on the complex” approach

Synthesis of three series of ruthenium tris-diimine complexes containing acridine-based π-extended ligands using an efficient “chemistry on the complex” approach

Selective Analysis of Redox Processes at the Electrode Interface with Time-Resolved Raman Spectroscopy

Synthesis, Characterization and Antitumor Mechanism Investigation of Heterometallic Ru(Ⅱ)-Re(Ⅰ) Complexes

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