Coordination assemblies based on a flexible tetrathiafulvalene derivative

A tetrathiafulvalene derivative bearing four peripheral 4-picolylthio units has been synthesized and employed for the formation of coordination assemblies with a series of divalent metal salts, highlighting the flexibility and adaptability of this ligand owing to the rotation allowed around the sulfur and carbon atoms of the thiomethyl spacer. [Display omitted] •The synthesis of a TTF derivative bearing 4-picolylthio groups has been optimized.•A [2 + 1] metallamacrocycle forms upon assembly of the TTF ligand with Zn(NCS)2.•1-D coordination polymers have been obtained with octahedral MX2 metal nodes.•The anion nature influences the packing of the coordination polymers in the crystal. A tetrathiafulvalene (TTF) derivative bearing four peripheral 4-picolylthio units has been synthesized and employed for the formation of coordination assemblies with a series of divalent metal salts, highlighting the flexibility and adaptability of this ligand owing to the rotation allowed around the sulfur and carbon atoms of the thiomethyl spacer. While a [2 + 1] metallamacrocycle has been obtained with the tetrahedral Zn(NCS)2 node, a series of 1D coordination networks has been characterized by X-ray diffraction with the octahedral Cd(NCS)2, CdBr2, MnCl2 and CoCl2 nodes. Within this series, the observed conformation of the TTF is the same with the 4-picolylthio groups either above or below the mean plane of the sulfur-rich core leading to analogous 1D arrangements. However, their packing differs depending on the nature of the anions. Indeed, 1D stacks of the TTF cores form with halide salts, whereas dimers are observed in the case of the thiocyanate system.