Since first bis-thiamacrocycle L1 was reported by Loeb group1, no bis-thiamacrocycle system has been reported till now. In this work, we report the synthesis of new serious of the bis-thiamacrocycles and their complexes with supramolecular structures. L1-L3 were synthesized by 1,3-bis-cyclization between tetrabromide and corresponding dithiol in the presence of Cs2CO3 under high dilution condition. In preparing L2, 1,2-bis-cyclization product L2a as an isomer was also isolated as a minor product by recrystallization. From the reaction of thiaphilic metal salts with L1-L3, several complexes were obtained and structurally characterized. For example, a dilead(II) complex 1, with a formula [Pb2(L2)(CH3CN)2(H2O)2(ClO4)2](ClO4)2, and a zigzag?type 1-D coordination polymer 2 with a formula [Ag(L2)]n(PF6)n were isolated. In 2, the silver(I) which links the L2 via exocyclic Ag-S bonds is four-coordinated with a distorted tetrahedral geometry.
1. S. J. Loeb, G. K. H. Shimizu, Inorg. Chem. 1993, 32, 1001-1006.