Synthesis and cryptate complexes of azathia macropolycyclic ligands based on 12-membered N2S2 and 15-membered N2S3 macrocyclic subunits
Abstract
The cyclindrical macrotricyclic ligands 4,16-dioxa-10,22,27,32-tetrathia-1,7,13,19-tetra-aza-tricyclo[17.5.5.57,13]tetratriacontane (L2) and 4,19-dioxa-10,13,25,28,33,38-hexathia 1,7,16,22-tetra-aza-tricyclo[20.8.5.57,16]tetracontane (L7) have been synthesised by high-dilution condensation of macrocyclic ligands containing 12-membered N2S2 and 15-membered N2S3 subunits, following different reaction sequences. The macrocycles 4,10-dimethyl-1,7-dithia-4,10-diazacyclododecane and 7,13-dimethyl-1,4,10-trithia-7,13-diazacyclopentadecane and the macrotricycles L2 and L7 form respectively mono- and di-nuclear complexes with CuII, NiII, and AgI. The reduced CuI and NiI complexes are strongly stabilized whilst the dinuclear complexes function as dielectronic receptors, exchanging two electrons in a single wave.