A peptide approach to covalently linked [Ru(bipy)3]2+–ferrocene and [Ru(bipy)3]2+–tyrosine conjugates

Geißer, Bernd; Alsfasser, Ralf

doi:10.1016/s0020-1693(02)01339-7

Cited by 15 publications

(9 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A myriad of architectures and model systems for ET have utilized [Ru(bpy) 3 ] 2+ due to its rich photophysics. , Intermolecular donor–acceptor (D···A) systems employing ruthenium bipyridine complexes and ferrocene (Fc) derivatives have been developed for a wide variety of applications including anion sensing, − electrochemiluminescnce (ECL), − photoactivated chemotherapy agents, peptide-inspired D–A building blocks, , and charge/energy transfer model systems. − Owing to the significant number of photophysical and charge transfer studies involving either [Ru(bpy) 3 ] 2+ or Fc as well as prior work focusing on distinct [Ru(bpy) 3 ] 2+ Fc assemblies, developing a full mechanistic understanding of the interactions between these two moieties remains critical.…”

Section: Introductionmentioning

confidence: 99%

Role of Electrostatics in Influencing the Pathway by Which the Excited State of [Ru(bpy)₃]²⁺ Is Deactivated by Ferrocene Derivatives

et al. 2019

View full text Add to dashboard Cite

Excited states of tris(2,2′-bipyridine)ruthenium(II), [Ru(bpy) 3 ] 2+ , can be deactivated by a wide range of ferrocene derivatives. The pathway by which deactivation takes place, either energy transfer (EnT) or electron transfer (ET), depends on several factors inherent to each specific donor−acceptor (D•••A) system. In this work, we provide mechanistic insight into bimolecular quenching between [Ru(bpy) 3 ] 2+ * and several ferrocene (Fc) derivatives in a variety of solvents. By introducing various functional groups onto the cyclopentadienyl ring of ferrocene, the chemical properties of the organometallic complexes were altered by tuning the oxidation potentials and charge of the iron complexes, and the manner in which the [Ru(bpy) 3 ] 2+ excited state is quenched by each ferrocene complex in solvents of various dielectric constants, including anhydrous acetonitrile (ACN), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and water (pH 10), was assessed. Through the use of transient absorption (TA) spectroscopy, the mechanism of [Ru(bpy) 3 ] 2+ * quenching by each of five ferrocene derivatives (i.e., either EnT or ET) in the aforementioned solvents was evaluated. On the basis of these studies, electrostatic factors relating to the charge on the ferrocene moiety were found to influence the quenching pathway(s) for the [Ru(bpy) 3 ] 2+ •••Fc systems under interrogation. When the ferrocene moiety is positively charged, the [Ru(bpy) 3 ] 2+ excited state is quenched by EnT to Fc, while when the ferrocene moiety is neutral or negatively charged, the [Ru(bpy) 3 ] 2+ excited state is quenched via reductive ET.

show abstract

Section: Introductionmentioning

confidence: 99%

Role of Electrostatics in Influencing the Pathway by Which the Excited State of [Ru(bpy)₃]²⁺ Is Deactivated by Ferrocene Derivatives

et al. 2019

View full text Add to dashboard Cite

show abstract

“…Incorporating metal complexes in a biological assembly is thus of the greatest interest since it produces redox-active biomaterials which may act as sensing and/or switching devices. − In this rapidly growing research area, amino acids or peptide−ferrocene conjugates have recently been the subject of intense investigations. , As a matter of fact, due to its unique structural and well behaved redox properties combined with an extensive chemical reactivity, the ferrocenyl group is undoubtly the most convenient building block for the construction of redox-responsive bioconjugates 15 and generally speaking to build selective receptors that can effectively convert a molecular recognition event into a physically measurable quantity, e.g., an electrochemical signal . Another crucial step toward electrochemical devices is the immobilization of redox chemosensors onto electrodes, which requires the introduction of suited functionality allowing electrode surface derivatization.…”

mentioning

confidence: 99%

Redox-Active Biomolecular Architectures and Self-Assembled Monolayers Based on a Cyclodecapeptide Regioselectively Addressable Functional Template

et al. 2006

View full text Add to dashboard Cite

A nanometer scale redox active biomolecular architecture has been successfully synthesized through an efficient chemoselective oxime based coupling between ferrocenyl groups and a regioselectively addressable cyclodecapeptide. This molecular tool exhibits electronic, structural, and chemical properties driven by the biomimetic recognition activity of the polypeptide skeleton associated to the well-defined electrochemical activity of metallocenyl probes. Biomolecular materials obtained by confinement of the redox cyclopeptide in self-assembled monolayers on gold surfaces shows efficient through-bond electron transfer from the ferrocenes to the electrode surface via the peptidic backbone, as well as markedly improved sensing properties toward anionic species in organic electrolyte, as compared to those observed in homogeneous solution.

show abstract

“…cyanides, [47] DNA, [48] polypeptides, [49] aliphatic chains, [50] pphenylenevinylene oligomers, [51] polyenes, [52] polyalkynes, [53] polyphenylenes, [54] polyphenylalkynes, [55] or polythiophene units [56] ) have been employed for the construction of dinuclear systems possessing interesting redox and photophysical properties.…”

Section: Metal-mediated Formation Of Dinuclear Cyclometalated Ru II Amentioning

confidence: 99%

Organic Transformations on σ‐Aryl Organometallic Complexes

et al. 2007

View full text Add to dashboard Cite

This work reviews recent developments in the field of organic transformations on sigma-aryl organometallic complexes. The general notion that M--C sigma bonds are kinetically labile, highly reactive, and incompatible with typical reaction conditions met in organic synthesis has limited the use of these synthetic strategies thus far. However, organic transformations on metal-bound sigma-aryl fragments are being used more and more by chemists in both industry and academia. In this Review, emphasis is put on the synthetic methods applied in this field up to now. The simplicity and generally good yields of these methods are very attractive for the construction of functionalized organometallic building blocks that are potentially useful as photochemical molecular devices, biosensors and -conjugates, or molecular switches. Thus, this Review has been tailored for a broader audience with the aim of encouraging the application of these strategies.

show abstract

A peptide approach to covalently linked [Ru(bipy)3]2+–ferrocene and [Ru(bipy)3]2+–tyrosine conjugates

Cited by 15 publications

References 31 publications

Role of Electrostatics in Influencing the Pathway by Which the Excited State of [Ru(bpy)₃]²⁺ Is Deactivated by Ferrocene Derivatives

Role of Electrostatics in Influencing the Pathway by Which the Excited State of [Ru(bpy)₃]²⁺ Is Deactivated by Ferrocene Derivatives

Redox-Active Biomolecular Architectures and Self-Assembled Monolayers Based on a Cyclodecapeptide Regioselectively Addressable Functional Template

Organic Transformations on σ‐Aryl Organometallic Complexes

Contact Info

Product

Resources

About

A peptide approach to covalently linked [Ru(bipy)3]2+–ferrocene and [Ru(bipy)3]2+–tyrosine conjugates

Cited by 15 publications

References 31 publications

Role of Electrostatics in Influencing the Pathway by Which the Excited State of [Ru(bpy)3]2+ Is Deactivated by Ferrocene Derivatives

Role of Electrostatics in Influencing the Pathway by Which the Excited State of [Ru(bpy)3]2+ Is Deactivated by Ferrocene Derivatives

Redox-Active Biomolecular Architectures and Self-Assembled Monolayers Based on a Cyclodecapeptide Regioselectively Addressable Functional Template

Organic Transformations on σ‐Aryl Organometallic Complexes

Contact Info

Product

Resources

About

Role of Electrostatics in Influencing the Pathway by Which the Excited State of [Ru(bpy)₃]²⁺ Is Deactivated by Ferrocene Derivatives

Role of Electrostatics in Influencing the Pathway by Which the Excited State of [Ru(bpy)₃]²⁺ Is Deactivated by Ferrocene Derivatives