Issue 2, 2006

Supramolecular organic conductors based on diiodo-TTFs and spherical halide ion X (X = Cl, Br)

Abstract

Novel organic conductors based on four diiodotetrathiafulvalene derivatives, DIET (2-(4,5-diiodo-[1,3]dithiol-2-ylidene)-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiine), DIETSe (2-(4,5-diiodo-[1,3]diselenol-2-ylidene)-5,6-dihydro-[1,3]diselenolo[4,5-b][1,4]dithiine), DIEDO (2-(4,5-diiodo-[1,3]dithiol-2-ylidene)-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dioxine) and DIEDO-STF (2-(4,5-diiodo-[1,3]diselenol-2-ylidene)-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dioxine) have been prepared using spherical halide ion X (X = Cl, Br) as the counter anion. Crystal structure analyses have revealed that all halide salts contain supramolecular structures tailored by the strong I⋯X iodine bond and their molecular arrangement depends on the combination of the group 16 elements included in the donor molecule. The temperature dependence of the electrical resistivity of (DIET)2X(H2O)2 is metallic down to 4.2 K, and they have ideally two-dimensional Fermi surfaces within the donor layer. (DIETSe)2X(CH2Cl2) salts show small temperature dependence of the resistivity down to low temperatures and their “double column” structure is dominated by the Y-shaped architecture composed of the halide ion and the crystalline solvent. On the other hand, (DIEDO)2X and (DIEDO-STF)2X are semiconducting from room temperature. They have another type of “double column” structure, i.e. the adjacent donor molecules along the side-by-side direction are solid-crossing and two types of column are included in the donor layer. The packing motifs of the halide salts based on the oxygen-substituted donor molecules are the same but their electronic states are sensitive to changes in the chalcogen atoms on the inner TTF skeleton.

Graphical abstract: Supramolecular organic conductors based on diiodo-TTFs and spherical halide ion X− (X = Cl, Br)

Supplementary files

Article information

Article type
Paper
Submitted
24 Aug 2005
Accepted
27 Sep 2005
First published
27 Oct 2005

J. Mater. Chem., 2006,16, 162-173

Supramolecular organic conductors based on diiodo-TTFs and spherical halide ion X (X = Cl, Br)

T. Imakubo, T. Shirahata, K. Hervé and L. Ouahab, J. Mater. Chem., 2006, 16, 162 DOI: 10.1039/B512036E

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