A new family of optically pure tetrathiafulvalenium and tetraselenafulvalenium salts, D-3[M-III(S,S-EDDS)](2)center dot nH(2)O (where D = TTF, TSF; M = Co, Fe, Cr; EDDS = ethylenediaminedisuccinato), were synthesized electrochemically. These phases are semiconductors with conductivities between 6.9 x 10(-6) and. 1.3 x 10(-5) S.cm(-1) (E-a ca. 0.3 eV) for TTF and 2.8 x 10(-4) to 2.8 x 10(-5) S.cm(-1) (E-a ca. 0.1 eV) for TSF compounds. While some crystals suffer from twinning, other well resolved structures consist of TTF/TSF stacks which, under the influence of the chiral anion, exhibit a periodic undulation described by an elliptical helix. The crystallographic data, along with computational work, indicate charge localization in the semiconducting motifs.