Crystal design of cation-radical salts based on the supramolecular self-organizing arrangement of mellitate anions

Abstract
Mellitate anions form hydrogen-bonding infinite networks in the salts with pyridinium cations. The network pattern depends on the number of deprotonation ( n) from the mellitic acid; for n = 3, triangular hydrogen-bond units form a two-dimensional sheet, while for n = 2, dual hydrogen-bond units induce one-dimensional belts or two-dimensional grids. These self-organizing properties have been utilized for the crystal design of the TTF-type radical cation salts. Crystallization with TMTTF gave two kinds of crystals. One of the radical cation salt crystals consists of a channel network of the anions and one-dimensional columns of TMTTF in the channels. In the other TMTTF salt, the anions with n = 1 form a two-dimensional sheet with methanol molecules. The TMTTF radicals are packed between the sheets with their molecular planes parallel to the anion planes. Key words. Hydrogen-bond - mellitate anion - crystal design - radical cation salt - infinite network.