Synthesis, x-ray structure, and spectroscopic and electrochemical properties of novel heteronuclear ruthenium-osmium complexes with an asymmetric triazolate bridge

Hage, Ronald; Haasnoot, Jaap G.; Nieuwenhuis, Heleen A.; Reedijk, J.; Ridder, D. J. A. De; Vos, Johannes G.

doi:10.1021/ja00181a029

Cited by 114 publications

(65 citation statements)

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“…Alternatively, it can highlight chemically irreversible redox processes and provide valuable information from the resultant spectra about the constitution of the product. 25 …”

Section: Experimental Methods For the Investigation Of The Electronicmentioning

confidence: 99%

Elucidating Excited State Electronic Structure and Intercomponent Interactions in Multicomponent and Supramolecular Systems

et al. 2005

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Rational design of supramolecular systems for application in photonic devices requires a clear understanding of both the mechanism of energy and electron transfer processes and how these processes can be manipulated. Central to achieving these goals is a detailed picture of their electronic structure and of the interaction between the constituent components. We review several approaches that have been taken towards gaining such understanding, with particular focus on the physical techniques employed. In the discussion, case studies are introduced to illustrate the key issues under consideration. IntroductionMolecular devices, based on supramolecular (multicomponent) assemblies employing covalent and non-covalent bonds between components, are of increasing interest in the development of molecular electronics and photonic devices. One of the primary goals behind the construction of supramolecular systems is to control the direction and rate of electron and energy transfer processes, both energetically and spatially. Although the energetic characteristics of these systems can be manipulated relatively easily, spatial control, in terms of both direction and rate, of energy and electron transfer can be achieved only when the orbital nature of both ground and excited electronic states is understood. Multinuclear transition metal complexes, such as those based on d 6 polypyridyl complexes (i.e., Re(I), Ru(II), Os(II) Rh(III), Ir(III)) have received considerable attention, both in fundamental studies and for application in molecular photonics. 2 The attraction of these metal compounds arises from the well-defined electrochemical and photophysical properties of their polypyridyl complexes and the extensive synthetic chemistry available, which enables systematic tuning of these properties for particular applications. 3 An additional advantage of employing 2nd and 3rd row transition metal complexes in studying intercomponent interactions lies in the stability of these complexes in different redox states. In consequence, the present tutorial review focuses primarily on metal-centred systems. However, it must be emphasised that the techniques discussed and approaches taken in these studies are not exclusive to metal based systems but can be applied equally well to organic systems. Han Vos, where he used density functional theory to study the electronic structures and Raman spectra of ruthenium complexes. After completing his PhD in 2004, he was appointed as a postdoctoral researcher in the group of P r o f . C i a r a n R e g a n i n University College Dublin. His current research interests involve the application of computational techniques to systems of biological interest.

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“…Alternatively, it can highlight chemically irreversible redox processes and provide valuable information from the resultant spectra about the constitution of the product. 25 …”

Section: Experimental Methods For the Investigation Of The Electronicmentioning

confidence: 99%

Elucidating Excited State Electronic Structure and Intercomponent Interactions in Multicomponent and Supramolecular Systems

et al. 2005

Self Cite

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“…[19][20][21][22][23] Whereas Browne and co-workers [24] concluded that the stereoisomeric identity of the ∆Λ, Λ∆, ∆∆ and ΛΛ forms of [{Ru(bpy) 2 } 2 (µ-bpt -)] 3+ had no influence on the photophysical properties of the complexes either at 77 K or room temperature, the influence of stereochemical effects on the IVCT properties of the systems were not addressed. Previous studies have, however, reported the redox and spectroscopic characteristics, [9,11,12,[25][26][27] resonance Raman spectra [28] and photophysical behavior [9,29] of stereoisomeric mixtures of the homo-and hetero-dinuclear complexes of ruthenium, osmium, rhodium and iridium incorporating bpt -and its protonated analog, Hbpt. It must be noted that due to the inequivalence of the metal coordination sites, the ∆Λ/Λ∆ form comprises a pair of geometric isomers.…”

Section: } 2 (µ-Bl)]mentioning

confidence: 99%

“…Because the unsymmetrical component in bpt -may be exploited to facilitate vectorial electron-and energy-transfer processes in polynuclear complexes, which form the basis of novel molecular-scale devices, [9,11,12,24,25,[27][28][29][30][31][32][33][34][35][36][37][38][39][40] stereochemical effects may also offer a novel means of "fine-tuning" the metal-metal interactions.…”

Section: } 2 (µ-Bl)]mentioning

confidence: 99%

“…Of the three examples of dinuclear species containing unsymmetrical bridging ligands, [12,49] two have contained the bpt -bridging ligand. In both cases, the crystals were obtained in the ∆Λ/Λ∆ form during an attempt to separate the diastereoisomers of the complexes through fractional crystallization.…”

Section: Structural Considerations: X-ray Crystallographymentioning

confidence: 99%

“…[11] As a consequence, a "redox asymmetry" (denoted by ∆E 0 ) exists between the inequivalent coordination sites. [12,13] The classical theory developed by Hush [14,15] provides a conceptual framework for the contribution of redox asymmetry effects to the electron-transfer barrier through the analysis of the intervalence charge-transfer (IVCT) transitions generated in the mixed-valence forms of dinuclear complexes. In accordance with Equation (1), the energy (ν max ) of an IVCT band, which is typically observed in the near-infrared (NIR) region of the absorption spectrum of the mixed-valence complex, is given in terms of the redox asymmetry and the Franck-Condon reorganizational energy contributions.…”

Section: Introductionmentioning

confidence: 99%

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The Effective Electron‐Transfer Distance in Dinuclear Ruthenium Complexes Containing the Unsymmetrical Bridging Ligand 3,5‐Bis(2‐pyridyl)‐1,2,4‐triazolate

et al. 2006

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Photochemically Induced Isomerisation of Ruthenium Polypyridyl Complexes

Fanni¹,

Weldon²,

Hammarström³

et al. 2001

Eur. J. Inorg. Chem.

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The synthesis and characterisation of a series of ruthenium polypyridyl complexes containing pyridyltriazole ligands in different coordination modes are described. The electrochemical and electronic properties of the compounds with respect to the coordination mode of the pyridyltriazole ligand are reported. Upon photolysis of the complex containing the 1‐methyl‐3‐(pyridin‐2‐yl)‐1,2,4‐triazole ligand, irreversible ligand isomerisation is observed.

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Synthesis, x-ray structure, and spectroscopic and electrochemical properties of novel heteronuclear ruthenium-osmium complexes with an asymmetric triazolate bridge

Cited by 114 publications

References 1 publication

Elucidating Excited State Electronic Structure and Intercomponent Interactions in Multicomponent and Supramolecular Systems

Elucidating Excited State Electronic Structure and Intercomponent Interactions in Multicomponent and Supramolecular Systems

The Effective Electron‐Transfer Distance in Dinuclear Ruthenium Complexes Containing the Unsymmetrical Bridging Ligand 3,5‐Bis(2‐pyridyl)‐1,2,4‐triazolate

Photochemically Induced Isomerisation of Ruthenium Polypyridyl Complexes

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