HIGHLY EXTENDED, PLANAR AND SULFUR-RICH TETRATHIAFULVALENE DERIVATIVES - TOWARDS AN INCREASED DIMENSIONALITY OF ORGANIC METALS

Highly extended pi-donors 1-3 have been obtained through twofold or fo urfold Wittig olefinations of polyformyl tetrathiafulvalenes with P-yl ids bearing the 1,3-dithiol-2-ylidene moiety. Their powerful pi-donor properties as well as their ability to generate cation-radical salts o f mixed valency have been evaluated by both classical and thin layer c yclic voltammetry. Such extended pi-donors prove to be planar in the n eutral state, with very short intramolecular S ... S distances, as dem onstrated by the X-ray diffraction study of the model compound 16b. Su ch extended sulfur-rich tetrathiafulvalene derivatives are prone to ge nerate highly dimensional materials as demonstrated in the case of the 3a. ClO4 cation-radical salt which presents a unique type of two-dime nsional network in the solid-state.