Application of deuteriation to determine the location of the emitting state in mixed-ligand Ru<sup>II</sup>polypyridyl complexes

Keyes, Tia E.; Weldon, Frances; Müller, Emil; Péchy, Péter; Grätzel, Michaël; Vos, Johannes G.

doi:10.1039/dt9950002705

Cited by 29 publications

(29 citation statements)

References 17 publications

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“…Raman spectra of these complexes were obtained as their neat perchlorate powders and interestingly the Raman scattering intensities due to the per-deuterio ligand in the mixed ligand complex were found to be significantly higher than for the per-protio ligand. This is not an unusual occurrence and has also been found the Humbs et al to [40][41][42].…”

Section: Deuteriation and Luminescence Lifetimesmentioning

confidence: 69%

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The effect of deuteriation on the emission lifetime of inorganic compounds

Browne

Vos

2001

Coordination Chemistry Reviews

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Abstract.The application of deuteriation of both ligands and solvents on the photophysical properties of transition metal complexes in solution and glassy matrices is reviewed. The reduction in amplitude and frequency of vibrational modes due to deuterium's increased mass, relative to hydrogen, has a significant effect on non-radiative deactivation processes, which can occur through both intra-and inter-molecular vibrational coupling. The effect of deuteriation on excited state lifetimes has allowed for its application in probing the nature of excited state decay processes. The effects of isotopic exchange on vibrational spectroscopies such as resonance Raman and low temperature high-resolution emission spectroscopies are also addressed briefly.

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Section: Deuteriation and Luminescence Lifetimesmentioning

confidence: 69%

“…pyridyls, pyrazyls, triazoles etc) [40,41]. This latter method, which produces yields in excess of 80 % [40-42] without the need for derivatisation, has the advantage over the method of Fischer et al in that the catalyst is commercially available and requires no pretreatment.…”

Section: Hydrogen Isotope Exchange Reactions Involving O-h N-h and mentioning

confidence: 99%

The effect of deuteriation on the emission lifetime of inorganic compounds

Browne

Vos

2001

Coordination Chemistry Reviews

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“…6 Deuteration was carried out using the methods described by Keyes et al 12 Calf thymus DNA (Aldrich Sigma) was purified by solvent extraction with equilibrated phenol and chloroform. 13 …”

Section: Methodsmentioning

confidence: 99%

Transient resonance Raman investigation of excited states of [Ru(phen)2dppz]2+ and deuterated analogues in aqueous and non-aqueous environments

Coates

Callaghan

McGarvey

et al. 2000

J. Raman Spectrosc.

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Transient resonance Raman (TR 2 ) spectroscopy was used to investigate the complex [Ru(phen) 2 dppz] 2Y (phen = 1; 10-phenanthroline; dppz = dipyridophenazine) following nanosecond pulsed laser excitation in three types of media: aqueous solution, DNA and acetonitrile. Studies were carried out at several excitation wavelengths spanning the absorption range of the metal-ligand charge-transfer (MLCT) excited state populated by the pulsed laser. In addition to the complex with the natural abundance dppz ligand, studies were also conducted with the complex containing the dppz ligand isotopically substituted at the phenanthroline hydrogens (i.e. d 6 -dppz). The intensity variations observed for some of the prominent bands of the dppz −ž radical anion in the TR 2 spectra as a function of excitation wavelength show that several distinct transitions contribute to the excited-state absorption. While many of the bands observed can most readily be attributed to vibrations which involve the entire dppz ligand skeleton, the behaviour of a few features upon isotopic substitution suggests the involvement also of more confined vibrational modes. The results of the transient resonance Raman studies are discussed in the context of recent proposals concerning the nature of the MLCT excited states possibly involved in the well-known use of the [Ru(phen) 2 dppz] 2Y complex as a 'light-switch reporter' for DNA.

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“…Indeed it has been shown for triazine based complexes that deuteriation of the bipy ligands will have no effect when the excited state is located on a non-bipy ligand. 25…”

Section: Isotope Effects On Emission Lifetimesmentioning

confidence: 99%

Resonance Raman and lifetime studies on regioselectively deuteriated ruthenium(ii) polypyridyl complexes

Browne

Henry

Passaniti

et al. 2007

Photochem Photobiol Sci

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Two series of ruthenium(II) polypyridyl complexes [Ru(bipy)(2)(phpytr)](+) and [Ru(bipy)(2)(phpztr)](+) (where Hphpytr = 2-(5-phenyl-1H-[1,2,4]triazol-3-yl)-pyridine and Hphpztr = 2-(5-phenyl-1H-[1,2,4]triazol-3-yl)-pyrazine) are examined by electrochemistry, UV/Vis, emission, resonance Raman, transient resonance Raman and transient absorption spectroscopy, in order to obtain a more comprehensive understanding of their excited state electronic properties. The interpretation of the results obtained is facilitated by the availability of several isotopologues of each of the complexes examined. For the pyridine-1,2,4-triazolato based complex the lowest emissive excited state is exclusively bipy based, however, for the pyrazine based complexes excited state localisation on particular ligands shows considerable solvent and pH dependency.

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Application of deuteriation to determine the location of the emitting state in mixed-ligand Ru^IIpolypyridyl complexes

Cited by 29 publications

References 17 publications

The effect of deuteriation on the emission lifetime of inorganic compounds

The effect of deuteriation on the emission lifetime of inorganic compounds

Transient resonance Raman investigation of excited states of [Ru(phen)2dppz]2+ and deuterated analogues in aqueous and non-aqueous environments

Resonance Raman and lifetime studies on regioselectively deuteriated ruthenium(ii) polypyridyl complexes

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Application of deuteriation to determine the location of the emitting state in mixed-ligand RuIIpolypyridyl complexes

Cited by 29 publications

References 17 publications

The effect of deuteriation on the emission lifetime of inorganic compounds

The effect of deuteriation on the emission lifetime of inorganic compounds

Transient resonance Raman investigation of excited states of [Ru(phen)2dppz]2+ and deuterated analogues in aqueous and non-aqueous environments

Resonance Raman and lifetime studies on regioselectively deuteriated ruthenium(ii) polypyridyl complexes

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Application of deuteriation to determine the location of the emitting state in mixed-ligand Ru^IIpolypyridyl complexes