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注册: 2016-09-19
专业: 环境工程

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ABSTRACT: Electrocrystallization of enantiopure (S,S,S,S)-
and (R,R,R,R)-tetramethyl-bis(ethylenedithio)-tetrathiafulva?lene (TM-BEDT-TTF) donors, as well as the racemic mixture,
in the presence of potassium cations and the tris(chloranilato)-
ferrate(III) [Fe(Cl2An)3]
3? paramagnetic anion afforded a
complete series of chiral magnetic molecular conductors
formulated as β - [ ( S,S,S,S )-TM-BEDT?TTF]3PPh4[KI
FeIII(Cl2An)3]·3H2O (1), β-[(R,R,R,R)-TM?BEDT-TTF]3PPh4[KI
FeIII(Cl2An)3]·3H2O (2), and β-[(rac)-
TM-BEDT-TTF]3PPh4[KI
FeIII(Cl2An)3]·3H2O (3). Com?pounds 1?3 are isostructural and crystallize in triclinic space
groups (P1 for 1 and 2, P?1 for 3) showing a segregated
organic?inorganic crystal structure, where anionic honeycomb layers obtained by self-assembling of the Λ and Δ enantiomers of
the paramagnetic complex with potassium cations alternate with organic layers where the chiral donors are arranged in the β
packing motif. Compounds 1?3 show a molecular packing strongly influenced by the topology of the inorganic layers and
behave as molecular semiconductors with room-temperature conductivity values of ca. 3 × 10?4 S cm?1
. The magnetic properties
are dominated by the paramagnetic S = 5/2 [Fe(Cl2An)3]
3? anions whose high-spin character is confirmed by magnetic
susceptibility measurements. The correlation between crystal structure and conducting behavior has been studied by means of
tight-binding band structure calculations which support the observed conducting properties.

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