Tetraalkyl- and dialkyl-substituted BEDT-TTF derivatives and their cation-radical salts : synthesis, structure, and properties.
Tetraalkyl and dialkyl derivatives, where alkyl=ethyl and propyl, of the organic electron donor molecule bis(ethylenedithio)tetrathiafulvalene, BEDT-TTF or ET, have been synthesized via the Diels-Alder approach. Several cation-radical salts of these new donors have been prepared and structurally characterized, and found to contain donor molecules in nominally higher oxidation states (+1, +1.5 and +2) than the typically observed oxidation state of +0.5 in BEDT-TTF salts. The higher solubility of the tetraalkyl and dialkyl derivatives in solvents used for crystal growth is proposed as the principal reason for this finding. Surprisingly, X-ray crystallographic studies reveal that the alkyl groups in the neutral tetraethyl-ET as well as the oxidized tetraethyl-ET and diethyl-ET molecules in their cation-radical salts adopt axial configurations, rather than the expected equatorial configurations. Electrical properties of the cation-radical salts have been found to be either insulating or semiconducting, consistent with the higher oxidation states of the donor molecules in the salts and the crystal structures.
- Research Organization:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Organization:
- ER
- DOE Contract Number:
- DE-AC02-06CH11357
- OSTI ID:
- 942426
- Report Number(s):
- ANL/CHM/JA-31319; JMACEP; TRN: US200915%%549
- Journal Information:
- J. Mater. Chem., Vol. 9, Issue 1999; ISSN 0959-9428
- Country of Publication:
- United States
- Language:
- ENGLISH
Similar Records
Coexistence of magnetic and delocalized electrons in hybrid molecular materials: The series of organic-inorganic radical salts (BEDT-TTF){sub 8}[XW{sub 12}O{sub 40}](solv){sub n} (X = 2(H{sup +}), B{sup III}, Si{sup IV}, Cu{sup II}, Fe{sup III}; solv=H{sub 2}O, CH{sub 3}CN)
Synthesis, crystal structure and physical properties of (BEDT-TTF)[Ni(tdas){sub 2}]: the first monomeric [Ni(tdas){sub 2}]{super -} monoanion, (BEDT-TTF = bis (ethylenedithio)tetrathiafulvalene; tdas = 1,2,5-thiadiazole-3,4-dithiolate).