Radical cation salts of CLEDO‐TTF with octahedral anions

Abstract

AbstractA new π‐donor, 4‐chloro‐4′,5′‐ethylenedioxytetrathiafulvalene (CLEDO‐TTF) was synthesized from 4‐methoxycarbonyl‐4′,5′‐ethylenedioxytetrathiafulvalene in the yield of 85%. In the crystal of neutral molecule, the head‐to‐head type uniform stacking column, in which the donor molecules are related by a unit cell translation, was formed. The electrocrystallization of CLEDO‐TTF with PF6 afforded two kinds of 1:1 salts of purple rods and green plates as miner species. In both 1:1 salts, the head‐to‐tail dimers with ring‐over‐ring overlapping mode were formed. Geometrically, the dimers were included in slipped stacking column in the purple rod salt, while the two‐dimensional network was formed in the green plate salt. The significant steric effect of chlorine atom along the molecular long axis was confirmed by the intermolecular arrangement in the green plate salt, in which the chlorine atom is faced to the hydrogen atom of the neighbouring donor along the long axis. The normal mode analyses were carried out for the neutral and monocationic CLEDO‐TTF, which agreed well with the observed Raman spectra. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)