Synthesis of Electron-Rich Thiamacrocycles

The stepwise syntheses of large [4+4] electron-rich thiamacrocycles, which aim at fullerene complexation, were performed using two types of building blocks, viz. 1,4-bis(bromomethyl)benzene or its dibutoxylated analogue and 4,5-bis(2-cyanoethyl-sulfanyl)-1,3-dithiole-2-thione. Alternatively, a multicomponent mixture of thiamacrocycles, ranging in size from [2+2] to [6+6] units, was generated by the direct reaction of bis(tetraethylammonium) bis(thioxo-1,3-dithiole-4,5-dithiol)zincate with 1,4-bis(bromomethyl)-2,5-dibutoxybenzene, and the individual macrocycles were successfully separated.