The near- and mid-infrared spectrum of the Creutz-Taube ion in aqueous solution: an application of FTIR spectroelectrochemical techniques

Best, Stephen P.; Clark, Robin J. H.; McQueen, Roderick C. S.; Joss, S.

doi:10.1021/ja00184a023

Cited by 57 publications

(40 citation statements)

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“…To this model, two Ru-NH 3 spectator modes are added using a model equivalent to that developed by Talaga & Zink (2001). Regions of the available parameter space are found which support the simultaneous interpretation of the band maximum and width of the IT transition of the Creutz-Taube ion (Creutz & Taube 1969, 1973 along with the observed properties of the spectator modes (Creutz & Taube 1973;Beattie et al 1976;Fürholz et al 1984;Best et al 1989).…”

Section: Introductionmentioning

confidence: 54%

“…The synthesis of the Creutz-Taube ion was very important historically, as it provided the first example of an inorganic mixed-valence ion in which the charge appeared to be delocalized over both the metal atoms. Assignments of a delocalized nature were based both on qualitative features, such as the appearance of a near-symmetric X-ray structure (Beattie et al 1977;Hush et al 1980), the appearance of only one spectator Ru-NH 3 infrared stretching mode (Creutz & Taube 1973;Beattie et al 1976;Fürholz et al 1984;Best et al 1989), the absence of the observation of expected characteristic tunnelling vibrational modes (Krausz et al 1981), and on the quantitative analysis of the electronic absorption band intensity and width (Hush 1980) and its chemical variation (Hush 1982). Such features are clearly expected for delocalized complexes based on Born-Oppenheimer theory.…”

Section: Introductionmentioning

confidence: 99%

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Towards a comprehensive model for the electronic and vibrational structure of the Creutz–Taube ion

Reimers

Wallace

Hush

2007

Phil. Trans. R. Soc. A.

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Since the synthesis of the Creutz-Taube ion, the nature of its charge localization has been of immense scientific interest, this molecule providing a model system for the understanding of the operation of biological photosynthetic and electron-transfer processes. However, recent work has shown that its nature remains an open question. Many systems of this type, including photosynthetic reaction centres, are of current research interest, and thereby the Creutz-Taube ion provides an important chemical paradigm: the key point of interest is the details of how such molecules behave. We lay the groundwork for the construction of a comprehensive model for its chemical and spectroscopic properties. Advances are described in some of the required areas including: simulation of electronic absorption spectra; quantitative depiction of the large interaction of the ion's electronic description with solvent motions; and the physics of Ru-NH 3 spectator-mode vibrations. We show that details of the solvent electron-phonon coupling are critical in the interpretation of the spectator-mode vibrations, as these strongly mix with solvent motions when 0.75!2J/l!1. In this regime, a double-well potential exists which does not support localized zero-point vibration, and many observed properties of the Creutz-Taube ion are shown to be consistent with the hypothesis that the ion has this character.

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Section: Introductionmentioning

confidence: 54%

Section: Introductionmentioning

confidence: 99%

Towards a comprehensive model for the electronic and vibrational structure of the Creutz–Taube ion

Reimers

Wallace

Hush

2007

Phil. Trans. R. Soc. A.

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“…It is ironic that the correct description of the ground state of the Creutz-Taube ion remains controversial so many years later. It has been thought for some time that the correctness of a completely delocalized description on the vibrational time scale was validated by the smooth variation of intramolecular infrared frequencies as the charge on the ion increases from C4 to C5 and C6 (Beattie et al 1976;Best et al 1989) and by the demonstration that the excited intervalence state had zero dipole moment (Oh et al 1991). However, quite recently, Demadis et al (2001) presented compelling evidence that many mixed-valence ions may be regarded as occupying the class 2-3 borderline and suggested that the Creutz-Taube ion may also be so described (Concepcion et al 2008).…”

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confidence: 99%

Mixed valence: origins and developments

Day

Hush

Clark

2007

Phil. Trans. R. Soc. A.

144

109

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Mixed-valence compounds were recognized by chemists more than a century ago for their unusual colours and stoichiometries, but it was just 40 years ago that two seminal articles brought together the then available evidence. These articles laid the foundations for understanding the physical properties of such compounds and how the latter correlate with molecular and crystal structures. This introduction to a discussion meeting briefly surveys the history of mixed valence and sets in context contributions to the discussion describing current work in the field.

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“…The spectroscopic techniques used in association with electrochemical systems (''spectroelectrochemistry'') include UV-Vis absorption spectroscopy, infrared absorption spectroscopy, Raman spectroscopy and electron spin resonance spectroscopy. [5][6][7][8][9][10][11][12][13][14][15] The experiments can be carried out in situ: applying the electrode potential and simultaneously monitoring the spectroscopic changes. The vibrational features observed for pristine and doped conjugated polymers are different and are used as signatures for the electronic and the molecular structural changes due to doping.…”

Section: Introductionmentioning

confidence: 99%

In situ FTIR spectroelectrochemical characterization of n- and p-dopable phenyl-substituted polythiophenes

Yohannes

Lattante

Neugebauer

et al. 2009

Phys. Chem. Chem. Phys.

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In situ attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroelectrochemistry during oxidation (p-doping) and reduction (n-doping) of three phenyl-substituted polythiophenes, namely POPT, PEOPT and POMeOPT is presented. All the three phenyl substituted polythiophenes show both n- and p-doping. The infrared active vibration (IRAV) patterns obtained during electrochemical oxidation (p-doping) and reduction (n-doping) are compared. HOMO and LUMO energy levels are estimated from cyclic voltammetric experiments and from IRAV patterns during oxidation and reduction. A comparison shows that the standard graphical procedure to determine the onset of oxidation and reduction peaks in the cyclic voltammogram can be improved using in situ spectroscopy.

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The near- and mid-infrared spectrum of the Creutz-Taube ion in aqueous solution: an application of FTIR spectroelectrochemical techniques

Cited by 57 publications

References 0 publications

Towards a comprehensive model for the electronic and vibrational structure of the Creutz–Taube ion

Towards a comprehensive model for the electronic and vibrational structure of the Creutz–Taube ion

Mixed valence: origins and developments

In situ FTIR spectroelectrochemical characterization of n- and p-dopable phenyl-substituted polythiophenes

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