Electrochemical properties of the [SiW 10 O 36 (M 2 O 2 E 2 )] 6− polyoxometalate series (M = Mo( v ) or W( v ); E = S or O)

International audienceElectronic Supplementary Information (ESI) available: FT-IR spectra of the compounds used in this study (Figure S1); Additional electrochemical data (Figure S2-S6), additional UV-Vis-NIR spectroelectrochemistry experiments (Figure S7-S12); effect of addition of an excess of Br2 on the electronic spectra of {SiW10-Mo2O2S2} in DMF (Figure S13); 29 Si NMR spectra of {SiW10-Mo2O2S2} in DMF/CH3CN mixtures before and after addition of one equivalent of Br2 (Figure S14). See This paper deals with the electrochemical studies performed in DMF on three iso-structural and iso-electronic compounds of general formula γ−[SiW10O36(M2O2E2)] 6-, which differ either by the nature of the metallic centers (M = Mo(V) or W(V)) or by the nature of the bridges between Mo(V) atoms (E = O 2-or S 2-). Interestingly, cyclic voltammetry experiments performed in dry DMF reveal electrochemical processes both in oxidation and in reduction modes. The nature of these processes are studied and elucidated by various electrochemical techniques such as coulometry, rotating disk electrodes, spectro-electrochemistry (IR and UV-Vis), NMR and DFT calculations

Reactivity of tetrathiometalates with alkynes. Synthesis and characterisation of dithiolene complexes of Mo, W, and V by ESMS and XRD

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A new organic-inorganic hybrid material based on a preformed chalcogenide building block and lanthanide

International audienceChalcogenide cluster [Mo3S4(HNTA)3]2− was used as precursor to generate new organic-inorganic hybrid material. La2Cl[Mo3S4(NTA)3]⋅17H2O (1) was obtained by hydrothermal synthesis starting from [Mo3S4 (NTA)3]5− and La3+ cation. Compound (1) was fully characterised by XRD, FTIR, TGA and elemental analysis. (1) crystallises in the P-1 space group with a=11.2219(3)Å, b=13.2435(3)Å, c=17.6351(5)Å, α=82,365(1)°, β=72,787(1)°, γ=68,608 (1)°, V=2330.11(11)Å3 and Z=2. Single-crystal X-ray diffraction analyses evidenced that the resulting 3D network consists of [Mo3S4(NTA)3]5− units connected through La3+ cations

Synthesis and characterizations of [Mo3S4(NDABu)(HNDABu)2]3- and [Mo3S4(HNDAPr)3]2- anions as new building blocks for organic-inorganic hybrid solids

International audienceThe polymetallic cation [Mo3S4(H2O)9]4+ was used as an inorganic precursor to generate new hybrid organic-inorganic chalcogenide clusters. Three organic compounds with flexible and hanging arms were synthesized and investigated as ligands for coordination complexes with the rigid and electroactive inorganic {Mo3S4} unit. Interestingly, the {Mo3S4} core formed hybrid structures with the flexible H3NDABu [N- (3-carboxypropyl)iminodiacetic acid] and H3NDAPr [N-(2- carboxyethyl)iminodiacetic acid] ligands, which were characterized by X-ray crystallography. Surprisingly, no crystals were isolated, when the more rigid H3NDABn [N-(4-methoxycarbonylbenzyl)iminodiacetic acid] ligand was used. The two coordination complexes [Mo3S4(NDABu)(HNDABu)2]3- and [Mo3S4(HNDAPr)3]2- were characterized by X-ray diffraction (XRD), IR spectroscopy, thermal gravimetric analysis (TGA), 1H NMR spectroscopy, elemental analysis, and electrochemistry. The organic ligands H3NDABu, H3NDAPr, and H3NDABn were characterized by XRD, IR, HR mass, and 13C and 1H NMR spectroscopy. [Mo3S4(NDABu)(HNDABu)2]3- and [Mo3S4(HNDAPr)3]2- constitute promising preformed building blocks to generate new organic-inorganic hybrid molecular or extended material

Novel Mo(V)-Dithiolene Compounds: Characterization of Nonsymmetric Dithiolene Complexes by Electrospray Ionization Mass Spectrometry

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Mass spectral and theoretical characterisation of non-symmetric Mo(V) dithiolene complexes

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Electrochromic behavior of drop-casted thin films combining a semi-conducting polymer mixed with a Keggin-type polyoxometalate

WOS:000430774300039A drop-casted thin film consisting of a Keggin-type polyoxometalate cluster K3PMo12O40 mixed with the semi-conducting poly(N-vinylcarbazole) (PVK) was deposited on top of ITO substrates. The resulting hybrid organic/inorganic film was characterized by electrochemistry, FT-IR spectroscopy, microscopies and spectroelectrochemistry. Interestingly, an electrochromic behavior could be evidenced from the resulting composite. (C) 2018 Elsevier B.V. All rights reserved

Robust ionic liquid@MOF composite as a versatile superprotonic conductor

International audienceA highly performing proton conducting composite was prepared through the impregnation of EMIMCl ionic liquid in the mesoporous MIL-101(Cr)–SO3H MOF. The resulting EMIMCl@MIL-101(Cr)–SO3H composite displays high thermal and chemical stability, alongside retention of a high amount of EMIMCl even at temperatures as high as 500 K, as well as under moisture conditions. Remarkably, this composite exhibits outstanding proton conductivity not only at the anhydrous state (σ473 K = 1.5 × 10−3 S cm−S) but also under humidity (σ(343 K/60%–80%RH) ≥ 0.10 S cm−1) conditions. This makes EMIMCl@MIL-101(Cr)–SO3H a unique candidate to act as a solid state proton conductor for PEMFC applications under versatile conditions