Effects of Solvent Additives on the Crystal Architecture of Supramolecular Conductors Based on Diiodo(ethylenedithio)tetraselenafulvalene and Indium Tetrahalide Anions

Six new organic conductors were prepared on the basis of the iodine-bonded π donor diiodo(ethylenedithio)tetraselenafulvalene and indium tetrahalide anions. The utilization of solvent additives made it possible to modify the quality, structure, morphology, and composition of the crystals. Among the additives, the addition of a few drops of water for the electrochemical crystallization induced the in situ transformation of the tetrahedral [InCl4]– anion to the octahedral [InCl4(H2O)2]– anion. Other small solvent molecules, such as methanol or ethanol, worked as well for the crystallization. All new salts include strong and directional iodine-based halogen bonds, that is, the iodine bond, and the novel supramolecular structures are successfully tailored by characteristic intermolecular interaction. It is also worth noting that the tetrahedral geometry of the counteranion plays a key role in the construction of the solid-crossing double-layer structure of the donor molecules, which is observed in the newly prepared InCl4 and [InCl4(H2O)2] salts.