Photoinduced electron transfer reactions of transition-metal complexes with amines. Mechanistic studies of alternate pathways to back electron transfer

DeLaive, Patricia J.; Foreman, Thomas K.; Giannotti, C.; Whitten, David G.

doi:10.1021/ja00537a037

Cited by 162 publications

(143 citation statements)

References 10 publications

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“…[24,25] In this case, photo-induced formation of P2 results from two processes, 1) the direct photoreduction of C2 by TEA as reported above and 2) the photoreductive catalytic cycle depicted in Figure 10 Figure 11. In the course of photolysis a large absorption band appears and increases in the red part of the spectrum in accordance with the formation of an Os À Os molecular wire.…”

Section: C3mentioning

confidence: 75%

Towards New Molecular Photocatalysts for CO₂ Reduction: Photo‐Induced Electron Transfer versus CO Dissociation within [Os(NN)(CO)₂Cl₂] Complexes

Chauvin

Lafolet

Chardon‐Noblat

et al. 2011

Chemistry A European J

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Optical excitation in the visible region of trans-(Cl)-[Os(bpy)(CO)(2)Cl(2)] (bpy=2,2'-bipyridine; C1) and trans-(Cl)-[Os(dmbpy)(CO)(2)Cl(2)] (dmbpy=4,4'-dimethyl 2,2'-bipyridine; C2) is known to induce the common CO dissociation reaction. However, the quantum yield of the reactions is less than 0.15, although C1 and C2 display pronounced photoluminescence in the visible region at room temperature with a lifetime of few tens of nanoseconds. Taking into account the characteristics of their emitting state, we have investigated the capability of C1 and C2 to act as a photosensitiser in redox reactions in different solvents (MeCN, PrCN and DMF). The efficient oxidation and reduction of both complexes under continuous irradiation in the presence of a sacrificial electron acceptor or donor is reported here. The photo-induced transformations and the nature of the resulting compounds were analysed by UV/Vis and IR spectroscopies and cyclic voltammetry. Photo-induced oxidation of C1 and C2 leads to the corresponding monocarbonyl oxidised species, whereas photo-induced reduction under argon leads mainly to the formation of the corresponding Os-bonded molecular wires P1 and P2 after exchange of two electrons associated with the loss of two chloro ligands. The chemical yield of the latter reaction (around 65%) becomes quantitative by adding [Ru(bpy)(3)](2+) as an external redox photosensitiser. This behaviour has been used to photocatalyse the two electron, two proton conversion of CO(2) to CO. Turnover numbers (TON) of 11.5 and 19.5 have been obtained respectively for C1 and C2 after 4.5 h of irradiation under CO(2) in DMF with triethanolamine as the electron donor. TON can be slightly increased by adding [Ru(bpy)(3)](2+) to the solution.

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Section: C3mentioning

confidence: 75%

Towards New Molecular Photocatalysts for CO₂ Reduction: Photo‐Induced Electron Transfer versus CO Dissociation within [Os(NN)(CO)₂Cl₂] Complexes

Chauvin

Lafolet

Chardon‐Noblat

et al. 2011

Chemistry A European J

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“…. [14,[32][33][34]. This dark reduction process explains the continued growth of [ReCl(CO) 3 (dppz-(CH 3 ) 2 )] − at time delays after the decay of the IL π-π* excited state.…”

Section: Introductionmentioning

confidence: 87%

Probing the use of long lived intra-ligand π–π* excited states for photocatalytic systems: A study of the photophysics and photochemistry of [ReCl(CO)3(dppz-(CH3)2)]

et al. 2017

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“…After oxidation, triethylamine decomposes and liberates protons. [24] ) The individual redox and protonation products were identified unambiguously on the basis of complementary studies using either spectroelectrochemistry or chemical reductants such as cobaltocene/ NaBH 4 and suitable acids. [23] Fujita, Tanaka, and coworkers focused on a molecular charge accumulation system which is bio-inspired in the sense that it contains a structural element that aims to mimic the enzymatic NAD + /NADH redox couple.…”

Section: A Few Specific Case Studies Of Photoinduced Charge Accumulationmentioning

confidence: 99%

Photoinduced Charge Accumulation in Molecular Systems

Bonn

Wenger²

2015

Chimia

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Fuel-forming reactions such as CO 2 reduction or water splitting require multiple redox equivalents. When aiming at light-driven production of energy-rich chemicals, nowadays often referred to as solar fuels, it therefore becomes important to master the photoinduced accumulation of electrons or holes on individual molecular components. Featured in this short review are some of the key molecular systems explored in this emerging field of research. This includes for example a trinuclear Ru(ii)-Rh(iii)-Ru(iii) complex or an Ir(iii)-sensitized polyoxotungstate hybrid, but also several systems in which electron or hole collection occurs at organic moieties such as perylenebis(dicarboximide), quinone-containing or oligotriarylamine-based units. In many cases the photodriven accumulation of charge requires the use of sacrificial electron donors, but there exist also a handful of studies in which redox equivalents can be accumulated without the use of such additives.

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Photoinduced electron transfer reactions of transition-metal complexes with amines. Mechanistic studies of alternate pathways to back electron transfer

Cited by 162 publications

References 10 publications

Towards New Molecular Photocatalysts for CO₂ Reduction: Photo‐Induced Electron Transfer versus CO Dissociation within [Os(NN)(CO)₂Cl₂] Complexes

Towards New Molecular Photocatalysts for CO₂ Reduction: Photo‐Induced Electron Transfer versus CO Dissociation within [Os(NN)(CO)₂Cl₂] Complexes

Probing the use of long lived intra-ligand π–π* excited states for photocatalytic systems: A study of the photophysics and photochemistry of [ReCl(CO)3(dppz-(CH3)2)]

Photoinduced Charge Accumulation in Molecular Systems

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Photoinduced electron transfer reactions of transition-metal complexes with amines. Mechanistic studies of alternate pathways to back electron transfer

Cited by 162 publications

References 10 publications

Towards New Molecular Photocatalysts for CO2 Reduction: Photo‐Induced Electron Transfer versus CO Dissociation within [Os(NN)(CO)2Cl2] Complexes

Towards New Molecular Photocatalysts for CO2 Reduction: Photo‐Induced Electron Transfer versus CO Dissociation within [Os(NN)(CO)2Cl2] Complexes

Probing the use of long lived intra-ligand π–π* excited states for photocatalytic systems: A study of the photophysics and photochemistry of [ReCl(CO)3(dppz-(CH3)2)]

Photoinduced Charge Accumulation in Molecular Systems

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Towards New Molecular Photocatalysts for CO₂ Reduction: Photo‐Induced Electron Transfer versus CO Dissociation within [Os(NN)(CO)₂Cl₂] Complexes

Towards New Molecular Photocatalysts for CO₂ Reduction: Photo‐Induced Electron Transfer versus CO Dissociation within [Os(NN)(CO)₂Cl₂] Complexes