CROWN-ANNELATED TETRATHIAFULVALENES - SYNTHESIS OF NEW FUNCTIONALIZEDDERIVATIVES AND SPECTROSCOPIC AND ELECTROCHEMICAL STUDIES OF METAL COMPLEXATION

Synthetic routes to the first unsymmetrical annelated tetrathiafulvale ne-S2O4 crowns are reported; the methodology is versatile, affording t he parent system 8, functionalised derivatives 6, 7 and 9-12, and amph iphilic derivatives 6 and 13. UV-VIS spectroscopic studies of metal bi nding (Na+, Ag+ and Ba2+) to the crown-TTF systems 8 and 13, and the b is(crown)-TTF 14 have been performed in solution, and stability consta nts have been calculated, The data establish that for the crown compou nds 8 and 13 1: 1 complexes are formed, whereas for the bis(crown) com pound 14 both 1:1 [14(Na+)] and 1:2 [14(Na+)(2)] complexes are formed, Solution electrochemical studies reveal that metal complexation to-th e crown unit leads to a small anodic shift in the first oxidation pote ntial of the TTF system, Langmuir-Blodgett films of amphiphilic compou nd 13 have been assembled on solid substrates by Y-type deposition.