Harnessing ICl reduction processes for synthesis of different BEDT-TTF-based molecular conductors.
Both calculations and experimental data, showing the possibility of formation of I3-, I2Cl-, and ICl2- anions through ICl reduction processes, are described in detail. The above processes were used successfully for the preparation of different molecular conductors based on trihalide anions and bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF). The reaction between ICl and BEDT-TTF occurring in a strong polar reaction media (epsilon > or = 34.8 D) results in the formation of novel molecular conductors containing different sets of the I3-, I2Cl-, and ICl2- anions: beta-(BEDT-TTF)2[(I3)0.4(I2Cl)0.6], beta'BEDT-TTF)2[(I2Cl)0.2(ICl2)0.8], and beta' '-('-(BEDT-TTF)2[(I3)0.075(I2Cl)0.150(ICl2). These molecular conductors reveal semiconducting (beta'-phase) as well as metallic (beta- and beta' '-phases) transport properties. It is also shown that in the reaction media with polarity less than 18.4 D only the I3- anion is incorporated in the BEDT-TTF-based molecular crystals. This fact is an unexpected outcome of our study.
Laukhina
Elena
E
Institut de Ciència de Materials de Barcelona (CSIC) Campus UAB E-08193 Bellaterra, Spain. laukhina@icmab.es
Tkacheva
Vladislava
V
Chuev
Igor
I
Wojciechowski
Roman
R
Ulanski
Jacek
J
Vidal-Gancedo
Jose
J
Veciana
Jaume
J
Laukhin
Vladimir
V
Rovira
Concepció
C