The syntheses of BEDT-TTF (ET) derivatives with potential metal ion binding pyridyl, bipyridyl and terpyridyl groups are achieved either by stepwise construction of the organosulfur core or via reactions of hydroxymethyl-ET for which a cheap and efficient four step route is reported. The tosylate of hydroxymethyl-ET, reported for the first time, undergoes nucleophilic substitutions with pyridyl, bipyridyland terpyridyl-thiolates to give new donors. The X-ray crystal structures of two

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... ET derivatives show considerable deviation of the organosulfur donor system from planarity by bending about the short molecular axis of the ET group. The radical cation salts of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) 1, have been extensively studied because of their wide variety of electrical properties, 1 including the occurrence of superconductivity in salts such as ET 2 [Cu(SCN) 2 ] and ET 2 (ICl 2 ). 2 Substituted derivatives of ET are more difficult to prepare, however a number of mono-, di-and tetrasubstituted materials are now reported, 3 and some of their radical cation salts have been studied. 4 Materials with novel combinations of electrical and magnetic properties are a current theme of research in which a transition metal ion provides a magnetic centre. 5 The latter may feature in the anion, as in Day's paramagnetic superconductor (ET) 4 [Fe(oxalate) 3 ].H 2 O.C 6 H 5 CN, 6 the Kobayashis' radical cation salts of BETS 2 with FeX 4 -(X = Cl, Br) whose electrical