An evaluation of the excited state absorption spectrum of Ru(bpy)32+ in aqueous and acetonitrile solutions

Yoshimura, Akio; Hoffman, Morton Z.; Sun, Haiyi

doi:10.1016/1010-6030(93)80005-t

Cited by 100 publications

(86 citation statements)

References 27 publications

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“…2 the time profiles of the absorption at 380 nm and 510 nm in the presence of TEA are presented. At 380 nm the MLCT state has an absorption maximum (24) whereas at 510 nm Ru(bpy) 3 + absorbs. It can be seen that the growth at 510 nm is much slower than the decay of the MLCT.…”

Section: Resultsmentioning

confidence: 99%

Photoreduction of Ru(bpy)32+ by Amines in Aqueous Solution. Kinetics Characterization of a Long-Lived Nonemitting Excited State†

Rivarola

Bertolotti

Previtali

2006

Photochem Photobiol

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The photochemistry of Ru(bpy)(3)+2 in the presence of amines was investigated in water by laser flash photolysis. N,N'-Dimethylaniline and p-phenylenediamine quench the luminescent metal to ligand charge transfer (MLCT) excited state of the complex by an electron transfer reaction that produces the semireduced form Ru(bpy)3+ in relatively high yields. On the other hand, triethylamine (TEA) and aniline do not quench the MLCT. Nevertheless, when laser flash irradiation at 532 nm is carried out in the presence of these amines, the formation of Ru(bpy)3+ is clearly detected by its transient absorption at 510 nm. These results are interpreted by an electron transfer reaction with the participation of a nonemitting excited state of the complex, formed independently of the MLCT from the Franck-Condon or the relaxed singlet excited state. The rate constants for the quenching of this state by TEA and aniline and the quantum yields for Ru(bpy)(3)+ were determined. The new state is formed in a very fast process and has a lifetime of ca 4 micros in water.

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Section: Resultsmentioning

confidence: 99%

Photoreduction of Ru(bpy)32+ by Amines in Aqueous Solution. Kinetics Characterization of a Long-Lived Nonemitting Excited State†

Rivarola

Bertolotti

Previtali

2006

Photochem Photobiol

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“…2. Three main spectral features are observed: a moderate absorption near 380 nm associated with →* transitions of a dpplocalized radical anion [30], a prominent bleach of the GS→MLCT band at 501 nm, and a weak broad absorption extending red of 600 nm that is assigned to various →* transitions and ligand-to-metal transitions involving the formally oxidized Ru [33,34]. Transient spectra collected in aqueous solution were similar, with small differences in peak positions.…”

Section: Spectral Evolution Of Rubrhmentioning

confidence: 87%

Ultrafast kinetics of supramolecules with a Ru(II)- or Os(II)-polypyridyl light absorber, cis-Rh(III)Cl2-polypyridyl electron collector, and 2,3-bis(2-pyridyl)pyrazine bridge

Zigler

Morseth

White

et al. 2017

Inorganica Chimica Acta

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The femtosecond transient absorption spectra (fsTA) and excited state kinetics for a series of six structurally related mixed-metal polypyridyl supramolecules are reported. Each complex consists of one or two light absorbers (LA) with Ru(II) or Os(II) centers attached to a Rh(III)centered electron collector (EC) by an aromatic bridging ligand (BL). The resulting bimetallic and trimetallic complexes have LA-BL-EC and LA-BL-EC-BL-LA architectures, respectively. Excitation at 470 nm light populates metal-to-bridging ligand charge transfer states (MLCT), showing a transient absorption band near 380 nm due to →* transitions of a bridging ligandlocalized radical anion and a transient bleach around 525 nm resulting from formal oxidation of the LA metal in the excited state. Loss of the ligand localized radical signal during the first 10 ps reflects conversion of the excited state population from an MLCT state into metal-to-metal (i.e. M(d)-to-Rh(d*)) charge transfer states (MMCT). Each complex shares a similar ultrafast component, indicating that the kinetics governing MLCT→MMCT population transfer do not depend on the nature of the LA. Return to the ground state, however, is strongly LA dependent and controlled by the free-energy difference between the MMCT state and ground state, as well as an associated large reorganization energy.

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“…were developed by several groups [57][58][59][60][61][62][63][64][65]. Such a strategy is interesting since it prevents diffusional issues by linking the excited state was lastly reported to be Δε = −10000 M -1 cm -1 at 452 nm [41], resulting in a huge signal bleach observed in the blue side of visible region after flashing the compound with a laser.…”

Section: Methodsmentioning

confidence: 99%

Transient absorption spectroscopy studies of proton-coupled electron transfers

Bonin

Routier²

2013

Artificial Photosynthesis

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On the course to sustainable energy, artificial photosynthesis is one of the greatest scientific challenges of our time. From a chemist point of view, the understanding of proton-coupled electron transfers which take place during the process is a fundamental issue. To decipher them, transient absorption spectroscopy, applied to model systems, is a method of choice. General methods and most recent results obtained by this technique are the object of the present review.

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An evaluation of the excited state absorption spectrum of Ru(bpy)32+ in aqueous and acetonitrile solutions

Cited by 100 publications

References 27 publications

Photoreduction of Ru(bpy)32+ by Amines in Aqueous Solution. Kinetics Characterization of a Long-Lived Nonemitting Excited State†

Photoreduction of Ru(bpy)32+ by Amines in Aqueous Solution. Kinetics Characterization of a Long-Lived Nonemitting Excited State†

Ultrafast kinetics of supramolecules with a Ru(II)- or Os(II)-polypyridyl light absorber, cis-Rh(III)Cl2-polypyridyl electron collector, and 2,3-bis(2-pyridyl)pyrazine bridge

Transient absorption spectroscopy studies of proton-coupled electron transfers

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