On the nature of tris(2,2'-bipyridine)ruthenium(1+) ion in aqueous solution

Mulazzani, Quinto G.; Emmi, Salvatore S.; Fuochi, P. G.; Hoffman, Morton Z.; Venturi, M.

doi:10.1021/ja00471a059

Cited by 82 publications

(52 citation statements)

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“…[19] It is well known that the emission of the excited state of [Ru(bpy) 3 ] 2+ ([Ru(bpy) 3 ] 2+ *) at l = 600 nm is efficiently quenched in the presence of NaHA by photoinduced electron transfer from HA À to [Ru(bpy) 3 ] 2+ * ( Figure S3 in the Supporting Information). [21] The absorption arising from ascorbate radical anion (AC À ), which is produced by deprotonation of ascorbate radical (HAC), [22] is overlapped at l = 360 nm. Nanosecond laser excitation at l = 455 nm of a deaerated buffer solution containing [Ru-(bpy) 3 ] 2+ , H 2 A, and NaHA results in formation of [Ru(bpy) 3 ] + ( Figure 2).…”

Section: Shunichi Fukuzumi* Takeshi Kobayashi and Tomoyoshi Suenobumentioning

confidence: 99%

Photocatalytic Production of Hydrogen by Disproportionation of One‐Electron‐Reduced Rhodium and Iridium–Ruthenium Complexes in Water

2010

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Section: Shunichi Fukuzumi* Takeshi Kobayashi and Tomoyoshi Suenobumentioning

confidence: 99%

Photocatalytic Production of Hydrogen by Disproportionation of One‐Electron‐Reduced Rhodium and Iridium–Ruthenium Complexes in Water

2010

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“…2+ . The reduction of [Ru(bpy) 2 (pbn)] 2+ by e aq -/CO 2 •-leads to the formation of the reduced species [Ru(bpy) 2 (pbn •-)] + that exhibits a distinctive UV-vis spectrum that is different from that of [Ru(bpy) 3 ] + , 30 indicating that it is predominantly the pbn ligand that is reduced. The rate constant of the reaction between e aq -and [Ru(bpy) 2 (pbn)] 2+ (3.0 × 10 10 M -1 s -1 ; pH ) 10) is diffusion-controlled and is comparable to those reported for reactions of ruthenium polypyridine complexes with e aq -(3.1 × 10 10 to 8.2 × 10 10 M -1 s -1 ).…”

Section: Discussionmentioning

confidence: 99%

Mechanism of Hydride Donor Generation Using a Ru(II) Complex Containing an NAD⁺ Model Ligand: Pulse and Steady-State Radiolysis Studies

et al. 2008

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The mechanistic pathways of formation of the NADH-like [Ru(bpy) 2(pbnHH)] (2+) species from [Ru(bpy)2(pbn)](2+) were studied in an aqueous medium. Formation of the one-electron-reduced species as a result of reduction by a solvated electron (k=3.0 x 10(10) M(-1) s(-1)) or CO2(*-) (k=4.6 x 10(9) M(-1) s(-1)) or reductive quenching of an MLCT excited state by 1,4-diazabicyclo[2.2.2]octane (k=1.1 x 10(9) M(-1) s(-1)) is followed by protonation of the reduced species (p K a = 11). Dimerization (k7a=2.2 x 10(8) M(-1) s(-1)) of the singly reduced protonated species, [Ru(bpy) 2(pbnH(*))](2+), followed by disproportionation of the dimer as well as the cross reaction between the singly reduced protonated and nonprotonated species (k8= 1.2 x 10(8) M(-1) s(-1)) results in the formation of the final [Ru(bpy)2(pbnHH)](2+) product together with an equal amount of the starting complex, [Ru(bpy)2(pbn)](2+). At 0.2 degrees C, a dimeric intermediate, most likely a pi-stacking dimer, was observed that decomposes thermally to form an equimolar mixture of [Ru(bpy)2(pbnHH)](2+) and [Ru(bpy)2(pbn)](2+) (pH<9). The absence of a significant kinetic isotope effect in the disproportionation reaction of [Ru(bpy)2(pbnH(*))](2+) and its conjugate base (pH>9) indicates that disproportionation occurs by a stepwise pathway of electron transfer followed by proton transfer.

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“…Ru(bpy)"t is stable in deaerated acetonitrile solution where it can be generated electrochemically in the controlled-potential reduction of Ru(bpy)? + (69) but it is unstable in aqueous medium, apparently undergoing slow (k^ ^ 0.2 s --1 -) interaction with water (70). The instabilities of Ru(bpy)j and Ru(bpy)3 in aqueous solution restrict their use as charge carriers in aqueous photogalvanic cells; investigations of their roles in non-aqueous cells should be carried out in the future.…”

Section: +mentioning

confidence: 99%

Photochemical Determinants of the Efficiency of Photogalvanic Conversion of Solar Energy

Hoffman

Lichtin

1979

Solar Energy

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A photogalvanic cell is a battery in which the cell solution absorbs light directly to generate species which, upon back reaction through an external circuit with the aid of suitable electrodes, produces electric power; photoactivation of the electrodes is 'not involved. The charge-carrying species have storage capacity if they are long-lived and can be prevented from engaging in degradativc back reactions in bulk solution. The efficiency of a photogalvanic cell for the conversion of photon energy into electrical energy is determined by photochemical and electrochemical factors. Among the latter are the choice of electrode materials and the kinetics of electron transfer at the heterogeneous surfaces. In this paper we examine '"the photochemical determinants of the efficiency of photogalvanic eel] operation: the absorption spectral characteristics of the cell solution, the efficiency of formation of separated charge carriers, and the lifetimes of the carriers toward back electron transfer. Modulation of bulk solution dynamics can be achieved by variation of the solution medium. The photochemical determinants are discussed with particular reference to the use of thionine or Ru(bpy)2+ as the light absorbing species.

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On the nature of tris(2,2'-bipyridine)ruthenium(1+) ion in aqueous solution

Cited by 82 publications

References 12 publications

Photocatalytic Production of Hydrogen by Disproportionation of One‐Electron‐Reduced Rhodium and Iridium–Ruthenium Complexes in Water

Photocatalytic Production of Hydrogen by Disproportionation of One‐Electron‐Reduced Rhodium and Iridium–Ruthenium Complexes in Water

Mechanism of Hydride Donor Generation Using a Ru(II) Complex Containing an NAD⁺ Model Ligand: Pulse and Steady-State Radiolysis Studies

Photochemical Determinants of the Efficiency of Photogalvanic Conversion of Solar Energy

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On the nature of tris(2,2'-bipyridine)ruthenium(1+) ion in aqueous solution

Cited by 82 publications

References 12 publications

Photocatalytic Production of Hydrogen by Disproportionation of One‐Electron‐Reduced Rhodium and Iridium–Ruthenium Complexes in Water

Photocatalytic Production of Hydrogen by Disproportionation of One‐Electron‐Reduced Rhodium and Iridium–Ruthenium Complexes in Water

Mechanism of Hydride Donor Generation Using a Ru(II) Complex Containing an NAD+ Model Ligand: Pulse and Steady-State Radiolysis Studies

Photochemical Determinants of the Efficiency of Photogalvanic Conversion of Solar Energy

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Mechanism of Hydride Donor Generation Using a Ru(II) Complex Containing an NAD⁺ Model Ligand: Pulse and Steady-State Radiolysis Studies