Preparations, x-ray crystal structures, EH band calculations, and physical properties of [(TTF)6(H)(XM12O40)(Et4N)] (M = tungsten, molybdenum; X = phosphorus, silicon): evidence of electron transfer between organic donors and polyoxometalates

Ouahab, L.; Bencharif, Mustapha; Mhanni, A.; Pelloquin, D.; Halet, J.‐F.; Peña, O.; Padiou, J.; Grandjean, D.; Garrigou‐Lagrange, C.

doi:10.1021/cm00021a032

Cited by 86 publications

(54 citation statements)

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“…The solid electrodeposited onto an ITO electrode (at 0.2 V for 30 min), was, while still adhered to the surface, thoroughly rinsed with MeCN solvent to remove soluble excess starting materials and supporting electrolyte. [29][30][31] Assuming that the polyoxometalate anion is in its fully oxidized form as [P 2 W 18 O 62 ] 6À (consistent with the electrochemical conditions used in the electrodeposition as well as the voltammogram in DMSO and the EPR data discussed below), an oxidation level of +1 per TTF unit is implied. Elemental analysis reported C, 9.25; H, 0.97; N, 0.20; S 12.04%, corresponds to an approximate stoichiometry of (TTF) 5 11.97%).…”

Section: Compositional Analysis and Structural Assignmentsmentioning

confidence: 75%

Controlled potential electrodeposition of a microcrystalline thin film of the charge transfer material tetrathiafulvalene–polyoxometalate of approximate composition (TTF)5.3(Bu4N)0.7[P2W18O62]·3H2O

Zhao

Bond

et al. 2011

J. Mater. Chem.

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Electrocrystallisation provides a systematic approach to the preparation of tetrathiafulvalene (TTF)-polyoxometalate materials in the form of films having significant conductivity. In this study, a highly uniform microcrystalline thin film derived from TTF + and the Dawson-Wells anion [a-P 2 W 18 O 62 ] 6À has been deposited onto glassy carbon, gold and indium tin oxide surfaces by controlled potential oxidative electrolysis of TTF in the presence of K 6 [P 2 W 18 O 62 ] in acetonitrile (0.1 M [Bu 4 N][PF 6 ]). Elemental analytical data are consistent with the formation of this conducting charge transfer salt having the approximate composition (TTF) 5.3 (Bu 4 N) 0.7 [P 2 W 18 O 62 ]$3H 2 O. Spectroscopic data support this conclusion. Mechanistic aspects of the electrocrystallisation process have been monitored by cyclic voltammetry, electrochemical quartz crystal microbalance and chronoamperometric methods. A less crystalline form of this material with a slightly different composition also can be produced by bulk electrolysis of TTF to TTF + followed by addition of K 6 [P 2 W 18 O 62 ]. The conductivity of the film at room temperature is in the semiconducting range. The EPR spectra, together with the field strength and temperature dependence of the magnetic susceptibility, suggest that regions of film behave as a quasi one-dimensional system, with antiferromagnetic and spin-flop behaviour at low temperatures. The Raman spectra are consistent with an average TTF charge state of +1, while voltammetry confirms the presence of [P 2 W 18 O 62 ] 6À . The morphology and crystallinity of the electrocrystallised and chemically prepared materials were investigated by scanning electron microscopy and X-ray diffraction, respectively.

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Section: Compositional Analysis and Structural Assignmentsmentioning

confidence: 75%

Controlled potential electrodeposition of a microcrystalline thin film of the charge transfer material tetrathiafulvalene–polyoxometalate of approximate composition (TTF)5.3(Bu4N)0.7[P2W18O62]·3H2O

Zhao

Bond

et al. 2011

J. Mater. Chem.

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“…The one-electron-reduced [PMo 12 O 40 ] 4¹ has one S = 1/2 spin on the cluster. 26 The temperature-dependent molar magnetic susceptibilities (T» mol ) of salts 13 were evaluated to confirm the electronic states of [PMo 12 O 40 ] 4¹ and their intercluster interactions in the crystals. The T» mol plots of salts 13 showed paramagnetic behavior in the temperature range from 2 to 300 K, following the CurieWeiss law ( Figure S7).…”

Section: Resultsmentioning

confidence: 99%

Molecular Motions and Hydrogen-Bonding Networks in (o-Aminoanilinium)–(Crown Ethers)–[PMo12O40]4− Crystals

Endo

Akutagawa²,

Kubo

et al. 2012

Bulletin of the Chemical Society of Japan

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Single crystals formed from hydrogen-bonding supramolecular cations of o-aminoanilinium (HOPD +)crown ethers, (HOPD +)([12]crown-4), (HOPD +)([15]crown-5), and (HOPD +)([18]crown-6), and one-electron-reduced [PMo 12 O 40 ] 4¹ Keggin-type clusters were synthesized. The crystal structures and dielectric responses of the three new compounds (HOPD +) 4 ([12]crown-4) 4 [PMo 12 O 40 ] 4¹ ¢4CH 3 CN (1), (HOPD +) 4 ([15]crown-5) 4 [PMo 12 O 40 ] 4¹ (2), and (HOPD +) 4 ([18]crown-6) 4 [PMo 12 O 40 ] 4¹ ¢8CH 3 CN (3) were examined. The CH 3 CN molecules in salts 1 and 3 were included in zero-dimensional pores and one-dimensional channels, respectively; higher thermal stability was observed in the former lattice because of its extended hydrogen-bonding network. Large frequencyand temperature-dependent dielectric responses were confirmed in salts 2 and 3, whereas the dielectric response of salt 1 was quite small. The fixed orientation of HOPD + because of the hydrogen-bonding network was consistent with the dielectric property of salt 1. In contrast, large magnitudes of dielectric responses in the temperature range above 280 K were observed for salt 3. Thermal motions of CH 3 CN molecules in the channel were the origin of such dielectric responses. In salt 2, the thermally activated coupled motion of the orthogonally arranged HOPD + pair along the CNH 3 +-axis with the potential energy barrier of ca. 80 kJ mol ¹1 resulted in large dielectric responses.

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“…Crystal structures of many Keggin anions have been reported, such as [PMo 12 O 40 ] 3- [14] and [SiMo 12 O 40 ] 4- [15]. Interestingly, [SiM 12 O 40 ] 4-(M = Mo, W) is usually present in combination with organic ammonium cations [15][16][17][18][19][20][21][22][23][24][25][26][27] O (0.138 g, 0.5 mmol) were dissolved in 50 mL of water. Diehylenetriamine (H 2 N-C 2 H 4 -NH-C 2 H 4 -NH 2 ) (1 mL, 1mmol) was added slowly to the mixture under stirring and the pH was adjusted to 1.9 by adding hydrochloric acid (HCl).…”

Section: Introductionmentioning

confidence: 99%

Hydrothermal synthesis and crystal structure of an inorganic-organic hybrid heteropolymolybdate (C4H16N3)2[NiMo12O40]Cl2 · 9H2O

Ftini

Haddad

2014

Crystallogr. Rep.

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A novel inorganic-organic hybrid polyoxomolybdate (C 4 H 16 N 3 ) 2 [NiMo 12 O 40 ]Cl 2 ⋅ 9H 2 O has been synthesized under hydrothermal conditions and structurally caracterised by elemental analysis, TG, IR and single crystal X ray diffraction. The crystals are orthorhombic, a = 10.138(3) Å, b = 19.508(2) Å, c = 26.790(4) Å, Z = 4, sp. gr. Pcnb. Keggin polyoxomolybdate anion [NiMo 12 O 40 ] 4-, protonated diethylen etriamine molecules, chloride anions and water molecules are linked via a large number of hydrogen bonds.

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Preparations, x-ray crystal structures, EH band calculations, and physical properties of [(TTF)6(H)(XM12O40)(Et4N)] (M = tungsten, molybdenum; X = phosphorus, silicon): evidence of electron transfer between organic donors and polyoxometalates

Cited by 86 publications

References 1 publication

Controlled potential electrodeposition of a microcrystalline thin film of the charge transfer material tetrathiafulvalene–polyoxometalate of approximate composition (TTF)5.3(Bu4N)0.7[P2W18O62]·3H2O

Controlled potential electrodeposition of a microcrystalline thin film of the charge transfer material tetrathiafulvalene–polyoxometalate of approximate composition (TTF)5.3(Bu4N)0.7[P2W18O62]·3H2O

Molecular Motions and Hydrogen-Bonding Networks in (o-Aminoanilinium)–(Crown Ethers)–[PMo12O40]4− Crystals

Hydrothermal synthesis and crystal structure of an inorganic-organic hybrid heteropolymolybdate (C4H16N3)2[NiMo12O40]Cl2 · 9H2O

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