A perspective on solar energy conversion and water photosplitting by dithiolene complexes

Ζαρκαδούλας, Αθανάσιος; Koutsouri, Eugenia; Mitsopoulou, Christiana A.

doi:10.1016/j.ccr.2012.04.016

Cited by 84 publications

(76 citation statements)

References 82 publications

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“…A paper in 1991 reported that tris[1-(4-methoxyphenyl)-2-phenyl-1,2-ethylenodithiolene-S,S']tungsten(VI) catalyzed the reduction of protons by the radical cation of methyl viologen into hydrogen. 25,26 Here, for the first time, we characterize simple W-dithiolene complexes for their catalytic properties regarding electroreduction and photochemical reduction of protons into H 2 in organic solvents. On the basis of DFT calculations, the nature of the reactive species is elucidated and a reaction mechanism is proposed.…”

Section: Introductionmentioning

confidence: 99%

Bioinspired Tungsten Dithiolene Catalysts for Hydrogen Evolution: A Combined Electrochemical, Photochemical, and Computational Study

et al. 2015

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Bis(dithiolene)tungsten complexes, W(VI)O2 (L = dithiolene)2 and W(IV)O (L = dithiolene)2, which mimic the active site of formate dehydrogenases, have been characterized by cyclic voltammetry and controlled potential electrolysis in acetonitrile. They are shown to be able to catalyze the electroreduction of protons into hydrogen in acidic organic media, with good Faradaic yields (75-95%) and good activity (rate constants of 100 s(-1)), with relatively high overpotentials (700 mV). They also catalyze proton reduction into hydrogen upon visible light irradiation, in combination with [Ru(bipyridine)3](2+) as a photosensitizer and ascorbic acid as a sacrificial electron donor. On the basis of detailed DFT calculations, a reaction mechanism is proposed in which the starting W(VI)O2 (L = dithiolene)2 complex acts as a precatalyst and hydrogen is further formed from a key reduced W-hydroxo-hydride intermediate.

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Section: Introductionmentioning

confidence: 99%

Bioinspired Tungsten Dithiolene Catalysts for Hydrogen Evolution: A Combined Electrochemical, Photochemical, and Computational Study

et al. 2015

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“…16 Another key property of interest is that many dithiolene complexes undergo the reversible oxidation-reduction processes in solution. [5][6][7]17 As shown in Scheme 1 the oxidation of the dithiolate results in the removal of an electron from one of the sulfurs, which becomes delocalized due to the presence of the alkene functional group. 18 Thus, a key goal of the assessment was to determine which functional best describes the oxidation of C 2 H 2 S 2 −2 .…”

Section: Introductionmentioning

confidence: 99%

The one-electron oxidation of a dithiolate molecule: The importance of chemical intuition

Bushnell

Burns

Boyd

2014

The Journal of Chemical Physics

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A series of nine commonly used density functional methods were assessed to accurately predict the oxidation potential of the (C2H2S2(-2)/C2H2S2(•-)) redox couple. It was found that due to their greater tendency for charge delocalization the GGA functionals predict a structure where the radical electron is delocalized within the alkene backbone of C2H2S2(•-), whereas the hybrid functionals and the reference QCISD/cc-pVTZ predict that the radical electron remains localized on the sulfurs. However, chemical intuition suggests that the results obtained with the GGA functionals should be correct. Indeed, with the use of the geometries obtained at the HCTH/6-311++G(3df,3pd) level of theory both the QCISD and hybrid DFT methods yield a molecule with a delocalized electron. Notably, this new molecule lies at least 53 kJ mol(-1) lower in energy than the previously optimized one that had a localized radical. Using these new structures the calculated oxidation potential was found to be 2.71-2.97 V for the nine DFT functionals tested. The M06-L functional provided the best agreement with the QCISD/cc-pVTZ reference oxidation potential of 3.28 V.

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“…[2] Mueller-Westerhoff has shown that planar neutral bis(dithiolene) complexes of Ni, Pd, and Pt can be potentially used as nearinfrared dyes for Q-switching Nd:YAG lasers. [5] Dithiolene complexes can be used for energy conversion [6] and the development of photodetectors. Their intense near-infrared (NIR) absorption and high thermal as well photochemical stability make the optical properties of these derivatives suitable for NIR lasers and nonlinear optical materials.…”

Section: Introductionmentioning

confidence: 99%

Ni Dithiolenes – A Theoretical Study on Structure–Property Relationships

et al. 2013

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The linear and nonlinear optical (L&NLO) properties, the energy difference between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO-LUMO gap), the first excitation energy (E exc ), and four indices for the evaluation of the diradical character (DC) of a series of Ni dithiolene derivatives have been computed by employing density functional theory (DFT). The selected DFT functionals provide reliable results for several properties [e.g., excitation energies and (hyper)polarizabilities]. An Atoms in Molecules analysis has been performed and several related properties have been reported (e.g., the average de-[a] Institute

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A perspective on solar energy conversion and water photosplitting by dithiolene complexes

Cited by 84 publications

References 82 publications

Bioinspired Tungsten Dithiolene Catalysts for Hydrogen Evolution: A Combined Electrochemical, Photochemical, and Computational Study

Bioinspired Tungsten Dithiolene Catalysts for Hydrogen Evolution: A Combined Electrochemical, Photochemical, and Computational Study

The one-electron oxidation of a dithiolate molecule: The importance of chemical intuition

Ni Dithiolenes – A Theoretical Study on Structure–Property Relationships

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