Synthesis and Physical Properties of two Organic Donor Derivatives of 12-Molybdophosphate Anion [PMO12O40] n-: New Examples of Mixed-Valence Organic Donor-Inorganic Acceptor Compounds

1992 ◽  
Vol 247 ◽  
Author(s):  
D. Attanasio ◽  
C. Bellitto ◽  
M. Bonamico ◽  
G. Righini ◽  
G. Staulo
Keyword(s):  
Electrical Conductivity ◽  
Physical Properties ◽  
Radical Cation ◽  
Organic Semiconductors ◽  
Mixed Valence ◽  
Two Dimensional ◽  
Keggin Anion ◽  
Radical Cation Salts ◽  
Mixed Valence Compounds ◽  
Derivatives Of

ABSTRACTTetrathiafulvalene and bis(ethylenedithio)tetrathiaful-valene radical-cation salts of the a-Keggin anion [PMo12O40] have been synthesized and characterized. They both are mixed-valence compounds and contain the paramagnetic anion [PMO12O40] 4-. The former contains irregular TTF ϱ+ chains isolated by the inorganic anions. From the IR spectrum a ϱ=+0.5 is suggested. The latter is two-dimensional, where BEDT-TTF molecules are ionised, ϱ=+0.5, and arranged in irregular chains. They show electrical conductivity typical of organic semiconductors.

Radical Cation Salts of an Unsymmetrical BEDT-TTF Derivative: Molecular Structure and Physical Properties of (DIMET*)2CIO4 X THF

1985 ◽  
Vol 40 (12) ◽  
pp. 1703-1710 ◽  
Author(s):  
R. Heid ◽  
H. Endres ◽  
H. J. Keller
Keyword(s):  
Molecular Structure ◽  
Electrical Conductivity ◽  
Physical Properties ◽  
Crystal And Molecular Structure ◽  
Average Charge ◽  
Two Dimensional ◽  
X Ray ◽  
Radical Cation Salts ◽  
Solvent Molecules ◽  
Ray Methods

Abstract 4.5-Dimethyl-4'.5'-ethylenedithiolotetrathiafulvalene (DIMET) was obtained by reacting 4.5- ethylenedithiolo-1.3-dithioliumtetrafluoroborate with 4.5-dimethyl- 1.3-dithiolium-tetrafluoroborate in the presence of diisopropylethylamine or triethylamine. Electrocrystallization of this donor in different solvents like dichloromethane or tetrahydrofurane (THF) and with varying supporting electrolytes, like tetrabutylammonium hexafluorophosphate, triiodide, nitrate, perrhenate or perchlorate, results in a large number of well crystallizing compounds. The crystal and molecular structure of one of the isolated solids was elucidated by X-ray methods. (C10)H10S6)2CIO4 x C4H8O, Mr = 816.66, is triclinic, P1̄ , a = 6.731(5), b - 7.632(3), c = 33.32(3) Å , α = 96.53(5), β = 92.99(6), γ = 103.13(5)°, V - 1650.7 Å3, Z = 2, dc = 1.64 gem-3, final Rw = 0.077 for 1844 observed independent reflections. Sheets of cations with an average charge of 1/2+ are separated by sheets of anions and THF solvent molecules. Intermolecular S···S contacts result in two-dimensional physical properties. Electrical conductivity and thermopower measurements indicate two broad phase transitions at around 200 K and 80 K

Synthesis, Crystal Structure and Spectroscopic Studies of New Charge Transfer Compounds Obtained by Reaction of TTF and the Polyoxoanion [Mo6O19]2−

1989 ◽  
Vol 173 ◽  
Author(s):  
C. Bellitto ◽  
D. Attanasio ◽  
M. Bonamico ◽  
V. Fares ◽  
P. Imperatori ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Electrical Conductivity ◽  
Charge Transfer ◽  
Room Temperature ◽  
Mixed Valence ◽  
Spectroscopic Studies ◽  
Chemical Formula ◽  
Xps Spectra ◽  
Radical Cation Salts ◽  
A Chain

ABSTRACTTwo different tetrathiafulvalene radical cation salts of the [M06O19]2−polyoxoanion have been isolated and characterized. Compound 1 corresponds to the chemical formula (TTF)3[Mo6019]. The crystal structure shows a ID stack of the donor TTF molecule, and each stack fits into channels formed by the anions. Within the stack a chain of trimers is identified, the inter-trimeric distance being 3.51 Å. The I.R., electronic and XPS spectra suggest the compound to be a mixed-valence salt. The electrical conductivity at room temperature is σ = 10−4Ω−1cm−1Compound 2 corresponds to the chemical+formula (TTF)2[M06019] . The compound consists of isolated (TTF+•)2dimers, interspersed with the polyoxoanions. In agreement with this crystal structure the compound is a diamagnetic insulator.

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