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Driving Multi-electron Reactions with Photons: Dinuclear Ruthenium Complexes Capable of Stepwise and Concerted Multi-electron Reduction

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Abstract

Using biological precedents, it is expected that concerted, multi-electron reduction processes will play a significant role in the development of efficient artificial photosynthetic systems. We have found that the dinuclear ruthenium complexes [(phen)2Ru(tatpp)Ru(phen)2]4+ (P) and [(phen)2Ru(tatpq) Ru(phen)2]4+ (Q) undergo photodriven 2- and 4-electron reductions, respectively, in the presence of a sacrificial reductant. Importantly, these processes are completely reversible upon exposure to air, and consequently, these complexes have the potential to be used catalytically in multi-electron transfer reactions. A localized molecular orbital description of the ligands and complexes is used to explain both the function and spectroscopy of these complexes. In both complexes, the reducing equivalents are stored in the π* orbitals of the bridging ligands and depending on the solution pH, various protonation states of the reduced species of P and Q are obtained. Under basic conditions, the photochemical pathway favors sequential single-electron reductions, while neutral or slightly acidic conditions give rise to proton-coupled multi-electron transfer. In fact, at sufficiently acidic pH, only a coupled two-electron, 2-proton process is seen. Few molecular photocatalysts are capable of proton-coupled multi-electron transfer, which is believed to be a fundamental component of light-activated energy storage in nature.

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Abbreviations

BL:

Bridging Ligand

CS:

Charge-separated

CV:

Cyclic Voltammetry

dppz:

dipyrido [3,2-a:2′,3′-c]phenazine)

HER:

H2 Evolution Reaction

HOMO:

Highest Occupied Molecular Orbital

LC:

Ligand Centered

LUMO:

Lowest Unoccupied Molecular Orbital

MeCN:

Acetonitrile

MET:

Multi-electron Transfer

MLCT:

Metal to Ligand Charge Transfer

MV2+ :

Methylviologen

MO:

Molecular Orbital

OEC:

Oxygen Evolving Complex

P :

[(phen)2Ru-tatpp-Ru(phen)2]4+

PCET:

Proton-coupled Electron Transfer

PCMET:

Proton-coupled Multi-electron Transfer

Q :

[(phen)2Ru-tatpq-Ru(phen)2]4+

SCE:

Saturated Calomel Electrode

SEC:

Spectroelectrochemistry

SR:

Sacrificial Reductant

tatpp:

9,11,20,22-tetraazatetrapyrido[3,2-a:2′,3′-c:3′′,2′′-l:2′′′,3′′′-n]pentacene

tatpq:

9,11,20,22-tetraazatetrapyrido[3,2-a:2′,3′-c:3′′,2′′-l:2′′′,3′′′-n]pentacene-10,21-quinone

TEA:

Triethylamine

TEOA:

triethanolamine

tpphz:

tetrapyrido[3,2-a:2′,3′-c:3′′,2′′-h:2′′′,3′′′-j]phenazine)

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, TX, 76019-0065, USA

    Kelly L. Wouters, Norma R. de Tacconi, Rama Konduri & Frederick M. MacDonnell

  2. INIFTA, Universidad Nacional de La Plata CC, 16, Suc. 4, La Plata, B1906ZAA, Argentina

    Reynaldo O. Lezna

Authors
  1. Kelly L. Wouters
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  2. Norma R. de Tacconi
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  3. Rama Konduri
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  4. Reynaldo O. Lezna
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  5. Frederick M. MacDonnell
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Correspondence to Frederick M. MacDonnell.

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Wouters, K.L., de Tacconi, N.R., Konduri, R. et al. Driving Multi-electron Reactions with Photons: Dinuclear Ruthenium Complexes Capable of Stepwise and Concerted Multi-electron Reduction. Photosynth Res 87, 41–55 (2006). https://doi.org/10.1007/s11120-005-6398-8

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