Synthesis and crystal structure of new tetrathiafulvalene derivatives incorporated into thiacrown ether macrocycles

Condensation of 2-thioxo-1,3-dithiole-4,5-dithiolate dianion 2 with 1,5-dibromo-3-thiapentane gave largely the 2:2 macrocycle 4 which could be converted into the novel tetrathiafulvalene-cage macrocycle 5 on treatment with triethyl phosphite. Treatment of the dithiolate dianion 2 with 1,9-dibromo-3,7-dithianonane gave the 1 :1 macrocycle 6 which could be converted into the planar tetrathiafulvalene derivative 7. The cyclic voltammogram of 7 showed a marked response on the addition of silver perchlorate, but no response when alkali metal perchlorates were added. Crystal structures of macrocycles 3 and 5 are also reported.