A5013585457- Magnetism in coordination complexes
- Metal complexes synthesis and properties
- Photochemistry and Electron Transfer Studies
- Crystallization and Solubility Studies
- Molecular Junctions and Nanostructures
- Organometallic Complex Synthesis and Catalysis
- X-ray Diffraction in Crystallography
- Metal-Catalyzed Oxygenation Mechanisms
- Advanced biosensing and bioanalysis techniques
- Chemical Synthesis and Reactions
- Porphyrin and Phthalocyanine Chemistry
- Chemical Reaction Mechanisms
- Advanced Nanomaterials in Catalysis
- Sulfur Compounds in Biology
- Inorganic and Organometallic Chemistry
- Electrochemical Analysis and Applications
- Coenzyme Q10 studies and effects
- Nanocluster Synthesis and Applications
- Enzyme Catalysis and Immobilization
- Ferrocene Chemistry and Applications
- Sirtuins and Resveratrol in Medicine
- Organoselenium and organotellurium chemistry
- Catalytic Cross-Coupling Reactions
- Electronic and Structural Properties of Oxides
- Metal-Organic Frameworks: Synthesis and Applications
University of Buenos Aires
2014-2025
Consejo Nacional de Investigaciones Científicas y Técnicas
2013-2025
Donostia International Physics Center
2023-2025
Instituto de Química y Fisicoquímica Biológicas
2019-2025
Fundación Ciencias Exactas y Naturales
2013-2024
Cyclopentadienyl (Cp) Ru(IV) quinoline complexes are known for their role in bioorthogonal catalysis within cellular environments, where they use endogenous GSH to deprotect profluorescent and prodrug substrates. However, reactivity toward potential redox-mediated therapies remain underexplored. This study presents RuQ-TARF, a Cp-Ru(IV) complex with ligand linked 2',3',4',5'-tetraacetylriboflavin (TARF) as redox-active moiety. Its catalytic activity oxidizing activating Pt(IV) of oxaliplatin...
The NIR and IR spectroscopic properties of the cyanide-bridged complex, trans-[Ru(dmap)4 {(μ-CN)Ru(py)4 Cl}2 ](3+) (py=pyridine, dmap=4-dimethylaminopyridine) provide strong evidence that this trimetallic ion behaves as a Class III mixed-valence species, first example reported system. This has been accomplished by tuning energy fragments in complex to compensate for intrinsic asymmetry cyanide bridge. Moreover, (TD)DFT calculations accurately predict spectra confirms its delocalized nature.
In this article, we report the structural, spectroscopic, and electrochemical properties of cyanide-bridged complex salts trans-[(NC)Ru(II)(L)4(μ-CN)Ru(II)(py)4Cl]PF6 trans-[Ru(II)(L)4{(μ-CN)Ru(II)(py)4Cl}2](PF6)2 (L = pyridine or 4-methoxypyridine). The mixed-valence forms these compounds show a variety metal-to-metal charge-transfer bands, including one arising from charge transfer between remote ruthenium units. latter is more intense when L 4-methoxypyridine points to role bridging unit...
Clear spectroscopic signatures of ligand field states in the MLCT decay cascade of<italic>trans</italic>-[Ru(L)<sub>4</sub>(NCS)<sub>2</sub>] (L = pyridine or 4-methoxypyridine) were found. (TD)DFT calculations reveal presence both and LMCT transient absorption bands.
Cyclopentadienyl (Cp) Ru(IV) quinoline complexes are known for their role in bioorthogonal catalysis within cellular environments, where they use endogenous GSH to deprotect profluorescent and prodrug substrates. However, reactivity toward potential redox-mediated therapies remain underexplored. This study presents RuQ-TARF, a Cp-Ru(IV) complex with ligand linked 2',3',4',5'-tetraacetylriboflavin (TARF) as redox-active moiety. Its catalytic activity oxidizing activating Pt(IV) of oxaliplatin...
In this study, cyclometallated gold(III) compounds were evaluated for their capability to promote C-Se coupling reactions under biocompatible conditions, and chemoselectivity towards selenium-containing substrates compared sulfur-containing analogs. The exhibited varying degrees of selectivity compounds, with [Au(bnopy)Cl₂] showing rapid bond formation. Competitive selenium sulfur highlighted the preference selenium, especially [Au(Mephpy)Cl₂], even in presence excess substrates. This was...
We report here the spectroscopic properties of four very closely related mixed-valence cyanide-bridged bimetallic complexes, trans-[Ru(T)(bpy)(μ-NC)Ru(L)4(CN)]3+ (T = tris(1-pyrazolyl)methane (tpm, a) or 2,2′;6′,2″-terpyridine, (tpy, b), and L pyridine (py, 1) 4-methoxypyridine (MeOpy, 2)). In acetonitrile all complexes present intervalence charge transfer (IVCT) transitions in NIR region, but their intensities are widely different, with intensity transition observed for 1a–b3+ around times...
The excited-state version of the Creutz-Taube ion was prepared via visible light excitation [(NH3 )5 RuII (μ-pz)RuII (NH3 ]4+ . resulting excited state is a mixed valence {RuIII-δ (μ-pz⋅- )RuII+δ } transient species, which characterized using femtosecond absorption spectroscopy with vis-NIR detection. Very intense photoinduced intervalence charge transfers were observed at 7500 cm-1 , revealing an electronic coupling element HDA =3750 DFT calculations confirm strongly delocalized state. A...
Abstract The NIR and IR spectroscopic properties of the cyanide‐bridged complex, tran s‐[Ru(dmap) 4 {(μ‐CN)Ru(py) Cl} 2 ] 3+ (py=pyridine, dmap=4‐dimethylaminopyridine) provide strong evidence that this trimetallic ion behaves as a Class III mixed‐valence species, first example reported system. This has been accomplished by tuning energy fragments in complex to compensate for intrinsic asymmetry cyanide bridge. Moreover, (TD)DFT calculations accurately predict spectra confirms its delocalized nature.
The mechanism for the photocatalytic activation of Pt(IV) anticancer prodrugs by riboflavin in presence NADH has been investigated DFT. In first step reaction, oxidation kinetics to afford catalytically active hydroquinone is dramatically favoured generation flavin triplet excited state. triplet, formation a π-π stacked adduct promotes hydride transfer from with an almost barrierless pathway (2.7 kcal mol-1). singlet channel, conversely, process endergonic and requires overcoming higher...
Modification of the ligand L in mixed-valence cyanide-bridged complexes [Ru(tpy)(bpy)(μ-CN)Ru(bpy)<sub>2</sub>(L)]<sup>3+/4+</sup> (L= Cl<sup>−</sup> (<bold>1</bold><sup>2+</sup>), NCS<sup>−</sup> (<bold>2</bold><sup>3+</sup>), 4-dimethylaminopyridine (<bold>3</bold><sup>4+</sup>) or acetonitrile (<bold>4</bold><sup>4+</sup>)) reduces difference between redox potentials ruthenium ions and leads to a transition from localized delocalized configuration.
In vitro biosynthetic pathways that condense and reduce molecules through coenzyme A (CoASH) activation demand energy redox power in the form of ATP NAD(P)H, respectively. These coenzymes must be orthogonally recycled by ancillary reactions consume chemicals, electricity, or light, impacting atom economy and/or consumption biosystem. this work, we have exploited vinyl esters as dual acyl electron donor substrates to synthesize β-hydroxy acids a non-decarboxylating Claisen condensation,...
Flavin-like ligands (L-1 and L-2) with extended π-conjugation were synthesized using microwave-assisted techniques. An N,N-chelating fragment was integrated into alloxazine units, providing binding sites for metal ions while retaining redox activity. The complexation capability of L-1 L-2 two prototypical Ru-scaffolds examined to design Ru(II) complexes (M-1 M-2), whose electronic properties studied compared their corresponding via absorption emission spectroscopy, computational analysis...
Bimetallic trans-[RuII(tpm)(bpy)(μNC)RuII(L)4(CN)]2+, where bpy is 2,2′-bipyridine, tpm tris(1-pyrazolyl)methane and L = 4-methoxypyridine (MeOpy) or pyridine (py), was examined using ultrafast vis-NIR transient absorption spectroscopy. Of great relevance are the longest-lived excited states in form of strongly coupled photoinduced mixed-valence systems, which exhibit intense absorptions NIR freely tunable by judicious choice coordination spheres metallic ions. Using latter strategy, we...
Photoexcitation of [Ru(tpy)(bpy)(μ-CN)Ru(py)4Cl]2+ ([RuRu]2+) at 387 nm results in the population two 3MLCT excited states different symmetry that coexist on nanosecond scale. Common to both is an electron a tpy-based orbital. Their configuration differs position hole. In one state, 3MLCTz, hole sits orbital parallel intermetallic axis allowing for strong metal–metal electronic interaction. As result, 3MLCTz highly delocalized over metal centers and shows intense photoinduced intervalence...
The picosecond excited state dynamics of [Ru(tpm)(bpy)(NCS)]<sup>+</sup> (<bold>RubNCS+</bold>) and [Ru(tpm)(bpy)(CN)]<sup>+</sup> (<bold>RubCN+</bold>) (tpm = tris(1-pyrazolyl)methane, bpy 2,2′-bipyridine) reveal an intermediate MLCT living in the 300 ps timescale.
Catalysis-based approaches offer versatile strategies for activating anticancer prodrugs, potentially allowing precise control over drug release and localization within tumor tissues, while reducing systemic toxicity. In this study, we explore the role of phenothiazine dye methylene blue (MB+) as a photocatalyst in conjunction with biologically relevant electron donors to facilitate red-light conversion two Pt(IV) complexes, denoted cis,cis,trans-[PtCl2(NH3)2(O2CCH2CH2COOH)2] (1)...
Flavin-like ligands (L-1 and L-2) with extended π-conjugation were synthesized using microwave-assisted techniques. An N,N-chelating fragment was integrated into alloxazine units, providing binding sites for metal ions while retaining redox activity. The complexation capability of L-1 L-2 two prototypical Ru-scaffolds examined to design Ru(II) complexes (M-1 M-2), whose electronic properties studied compared their corresponding via absorption emission spectroscopy, computational analysis...
Catalysis-based approaches offer versatile strategies for activating anticancer prodrugs, potentially allowing precise control over drug release and localization within tumor tissues, while reducing systemic toxicity. In this study, we explore the role of phenothiazine dye methylene blue (MB+) as a photocatalyst in conjunction with biologically relevant electron donors to facilitate red-light conversion two Pt(IV) complexes, denoted cis,cis,trans-[PtCl2(NH3)2(O2CCH2CH2COOH)2] (1)...
In this work, we present the preparation of a complex [(tpy)(bpy)Ru(μ-CN)Ru(py)4(OH2)](PF6)3 (tpy = 2,2',6',2''-terpyridine; bpy 2,2'-bipyridine; py pyridine) that combines ruthenium chromophore linked to another ion bears labile position trans bridge. Substitution in is very attractive, as it allows us place quencher maximizing separation between them. This allowed prepare family cyanide-bridged polypyridines general formula [Ru(tpy)(bpy)(μ-CN)Ru(py)4(L)]2/3+ (L Cl-, NCS-,...