TY - JOUR
T1 - Structural diversity and physical properties of paramagnetic molecular conductors based on bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and the tris(chloranilato)ferrate(III) complex
AU - Atzori, Matteo
AU - Pop, Flavia
AU - Auban-Senzier, Pascale
AU - Gómez-García, Carlos J.
AU - Canadell, Enric
AU - Artizzu, Flavia
AU - Serpe, Angela
AU - Deplano, Paola
AU - Avarvari, Narcis
AU - Mercuri, Maria Laura
PY - 2014/7/7
Y1 - 2014/7/7
N2 - Electrocrystallization of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) in the presence of the tris(chloranilato)ferrate(III) [Fe(Cl2An) 3]3- paramagnetic chiral anion in different stoichiometric ratios and solvent mixtures afforded three different hybrid systems formulated as [BEDT-TTF]3[Fe(Cl2An)3]·3CH 2Cl2·H2O (1), δ-[BEDT-TTF] 5[Fe(Cl2An)3]·4H2O (2), and α‴-[BEDT-TTF]18[Fe(Cl2An)3] 3·3CH2Cl2·6H2O (3). Compound 1 presents an unusual structure without the typical alternating organic and inorganic layers, whereas compounds 2 and 3 show a segregated organic-inorganic crystal structure where layers formed by Λ and Δ enantiomers of the paramagnetic complex, together with dicationic BEDT-TTF dimers, alternate with layers where the donor molecules are arranged in the δ (2) and α‴ (3) packing motifs. Compound 1 behaves as a semiconductor with a much lower conductivity due to the not-layered structure and strong dimerization between the fully oxidized donors, whereas 2 and 3 show semiconducting behaviors with high room-temperature conductivities of ca. 2 S cm-1 and 8 S cm-1, respectively. The magnetic properties are dominated by the paramagnetic S = 5/2 [Fe(Cl2An) 3]3- anions whose high-spin character is confirmed by electron paramagnetic resonance and magnetic susceptibility measurements. The correlation between crystal structure and conductivity behavior was studied by means of tight-binding band structure calculations, which support the observed conducting properties.
AB - Electrocrystallization of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) in the presence of the tris(chloranilato)ferrate(III) [Fe(Cl2An) 3]3- paramagnetic chiral anion in different stoichiometric ratios and solvent mixtures afforded three different hybrid systems formulated as [BEDT-TTF]3[Fe(Cl2An)3]·3CH 2Cl2·H2O (1), δ-[BEDT-TTF] 5[Fe(Cl2An)3]·4H2O (2), and α‴-[BEDT-TTF]18[Fe(Cl2An)3] 3·3CH2Cl2·6H2O (3). Compound 1 presents an unusual structure without the typical alternating organic and inorganic layers, whereas compounds 2 and 3 show a segregated organic-inorganic crystal structure where layers formed by Λ and Δ enantiomers of the paramagnetic complex, together with dicationic BEDT-TTF dimers, alternate with layers where the donor molecules are arranged in the δ (2) and α‴ (3) packing motifs. Compound 1 behaves as a semiconductor with a much lower conductivity due to the not-layered structure and strong dimerization between the fully oxidized donors, whereas 2 and 3 show semiconducting behaviors with high room-temperature conductivities of ca. 2 S cm-1 and 8 S cm-1, respectively. The magnetic properties are dominated by the paramagnetic S = 5/2 [Fe(Cl2An) 3]3- anions whose high-spin character is confirmed by electron paramagnetic resonance and magnetic susceptibility measurements. The correlation between crystal structure and conductivity behavior was studied by means of tight-binding band structure calculations, which support the observed conducting properties.
UR - http://www.scopus.com/inward/record.url?scp=84903983817&partnerID=8YFLogxK
U2 - 10.1021/ic501001r
DO - 10.1021/ic501001r
M3 - Article
SN - 0020-1669
VL - 53
SP - 7028
EP - 7039
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 13
ER -