Capture of the Complex [Ni(dto)2]2– (dto2– = Dithiooxalato Ligand) in a Mo12 Ring: Synthesis, Characterizations, and Application toward the Reduction of Protons

Hijazi, Akram; Kemmegne‐Mbouguen, Justin Claude; Floquet, Sébastien; Marrot, Jérôme; Mayer, Cédric R.; Artero, Vincent; Cadot, Emmanuel

doi:10.1021/ic201239y

Cited by 31 publications

(24 citation statements)

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“…37 In the absence of TFA, no noticeable peak in CV was observed, in agreement with previous studies performed on oxothiomolybdenum rings in similar medium. 17 [24][25][26]40 Note that an additional, yet small, signal also appeared near −1.75V vs. Ag/AgCl for TFA concentrations greater than 255 μM. This wave corresponds to the non-catalytic reduction of protons at a bare glassy carbon electrode (see Fig.…”

Section: Electrocatalytic Propertiesmentioning

confidence: 88%

“…In this field, we recently evidenced that [Mo 2 O 2 S 2 ]-based cyclic PolyOxoThioMetalates (POTMs) are able to function as efficient electrocatalysts, both in organic and aqueous media. [17][18][19] This class of compounds is based on the self-condensation of [M 2 O 2 S 2 ] 2+ oxothiocations (M = Mo V , W V ) around anionic templates, either mono-or polyphosphates, metalates or poly-carboxylates, the [M 2 O 2 S 2 ] 2+ building units being self-connected through double hydroxo bridges. 20,21 The parameters which govern electrocatalytic properties of this class of molecular materials are not well understood but the chemical potentialities, based upon the diversity of the host-guest combinations, should offer some relevant optimization perspectives.…”

Section: Introductionmentioning

confidence: 99%

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Syntheses, characterizations and properties of [Mo2O2S2]-based oxothiomolybdenum wheels incorporating bisphosphonate ligands

et al. 2012

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We report the syntheses and characterizations of the first polyoxothiometalate complexes isolated from the reaction of the oxothiocationic [Mo(V)(2)O(2)S(2)](2+) precursor and bisphosphonate ligands H(2)O(3)PCR(OH)PO(3)H(2) (R = C(4)H(5)N(2), zoledronic acid; R = C(3)H(6)NH(2), alendronic acid). [(Mo(2)O(2)S(2)(H(2)O))(4)(O(3)PC(O)(C(4)H(6)N(2))PO(3))(4)](8-) (Mo(8)S(8)(Zol)(4)) and [(Mo(2)O(2)S(2)(H(2)O))(4)(O(3)PC(O)(C(3)H(6)NH(3))PO(3))(4)](8-) (Mo(8)S(8)(Ale)(4)) contain four Mo(V) dimers connected via bisphosphonate ligands. These compounds offer a unique opportunity to compare the structures and properties of cyclic compounds obtained with [Mo(2)O(2)S(2)](2+) and with [Mo(2)O(4)](2+). The oxothio compounds appear less stable in solution than the oxo analogue, confirming the higher lability and versatility of [Mo(2)O(2)S(2)]-based compounds compared to [Mo(2)O(4)]-based POMs. Multinuclear and multidimensional solid-state NMR studies were carried out to complement X-ray diffraction analysis. Information on short-range interactions, dynamic behaviors, and local disorder within the crystalline materials are therefore reported. Furthermore, the electrocatalytic properties of Mo(8)S(8)(Ale)(4) and of the analogous [(Mo(2)O(4)(H(2)O))(4)(O(3)PC(O)(C(3)H(6)NH(3))PO(3))(4)](8-) (Mo(8)O(8)(Ale)(4)) immobilized onto the surface of a glassy carbon electrode were studied, thus evidencing the ability of [Mo(2)O(2)S(2)]-based cycles to promote the reduction of protons into hydrogen, whereas the oxo analogue appeared inactive.

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Section: Electrocatalytic Propertiesmentioning

confidence: 88%

Section: Introductionmentioning

confidence: 99%

Syntheses, characterizations and properties of [Mo2O2S2]-based oxothiomolybdenum wheels incorporating bisphosphonate ligands

et al. 2012

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“…(1) (2) Since they can store several electrons with modest difference in potentials between successive reduction steps, 31,32 polyoxometallates (POMs) are attractive candidates to further illustrate charge photoaccumulation. While electrocatalytic reduction of protons by POMs has been thoroughly investigated, [33][34][35] their activity in water photoreduction has been far less developed and only under UV-light excitation, [36][37][38] with two recent notable exceptions.…”

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confidence: 99%

Charge photo-accumulation and photocatalytic hydrogen evolution under visible light at an iridium(iii)-photosensitized polyoxotungstate

Matt

Fize

Moussa

et al. 2013

Energy Environ. Sci.

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115

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Steady-state irradiation under visible light of a covalent Ir(III)-photosensitized polyoxotungstate is reported. In the presence of a sacrificial electron donor, the photolysis leads to the very efficient photoreduction of the polyoxometalate. Successive formation of the one-electron and two-electron reduced species, which are unambiguously identified by comparison with spectroelectrochemical measurements, is observed with a significantly faster rate reaction for the formation of the oneelectron reduced species. The kinetics of the photoreduction, which are correlated to the reduction potentials of the polyoxometalate (POM), can be finely tuned by the presence of an acid. Indeed light-driven formation of the two-electron reduced POM is considerably facilitated in the presence of acetic acid. The system is also able to perform photocatalytic hydrogen production under visible light without significant loss of performance over more than 1 week of continuous photolysis and displays higher photocatalytic efficiency than the related multi-component system, outlining the decisive effect of the covalent bonding between the POM and the photosensitizer. This functional and modular system constitutes a promising step for the development of charge photoaccumulation devices and subsequent photoelectrocatalysts for artificial photosynthesis.Photoconversion of light into chemical fuels is emerging as a major scientific challenge. [1][2][3][4] In the past decades, molecular approaches have mostly focused on one hand on the design of photosensitive systems displaying long-lived photo-induced charge separation states to permit further electron transfers 5-10 and, on the other hand, on catalysts able to use these photogenerated charges for achieving either oxygen [11][12][13][14][15][16][17][18] or hydrogen evolution. [19][20][21][22][23][24] As these two reactions are multi-electronic processes while photosensitizers deliver electrons and holes sequentially, the charges need to be directed to a charge accumulation site. 25 However, only a few molecular photoactive systems with a designed charge accumulation site have been described so far. [26][27][28][29][30] Another requirement is crucial for efficient charge accumulation in such systems: when partially filled, the reservoir should not interfere with the photoactive moiety. Indeed, in classical donor-acceptor (D-A) systems, the electron acceptor, once reduced, potentially becomes an electron donor and often displays lightabsorbing properties. Thus it may act, in a subsequent light-driven process, as a deleterious 47,48 In the previously mentioned study, transient absorptions measurements only allowed for the characterization of the first photo-induced electron transfer. Charge photo-accumulation studies can be achieved in the presence of an additional electron donor in the solution that can irreversibly quench the charge separation state, regenerate the initial state of the photosensitizer and make a second photo-induced process possible. We herein provide unprecedente...

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“…This class of compounds exhibits unique electron structure and efficient electrocatalytic properties [3][4][5]. Molybdenum disulfide (MoS 2 ) and its derivatives have been widely used as catalysts for hydrodesulfurization (HDS) of petroleum [6,7].…”

Section: Introductionmentioning

confidence: 99%

Characterization and catalytic performance of {Mo2O2S2}-based oxothiomolybdenum cyclic clusters supported on mesoporous SBA-15

Xin

Wei

Chen

et al. 2015

Catalysis Communications

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Capture of the Complex [Ni(dto)₂]^2– (dto^2– = Dithiooxalato Ligand) in a Mo₁₂ Ring: Synthesis, Characterizations, and Application toward the Reduction of Protons

Cited by 31 publications

References 68 publications

Syntheses, characterizations and properties of [Mo2O2S2]-based oxothiomolybdenum wheels incorporating bisphosphonate ligands

Syntheses, characterizations and properties of [Mo2O2S2]-based oxothiomolybdenum wheels incorporating bisphosphonate ligands

Charge photo-accumulation and photocatalytic hydrogen evolution under visible light at an iridium(iii)-photosensitized polyoxotungstate

Characterization and catalytic performance of {Mo2O2S2}-based oxothiomolybdenum cyclic clusters supported on mesoporous SBA-15

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