Calix[4]thiacrowns as Ditopic Hosts for Homo- and Heterobinuclear Accommodation: First Report of a Chopsticks-Type π-Coordination

Calix[4]thiacrowns with hetero-L1 and a homodonor set (L2) were synthesized and characterized by X-ray analysis. From the reaction of L2 with
AgPF6, disilver complex [Ag2(L2)](PF6)2 (1) was isolated. By comparing 1,3-alternate conformations of L2 and 1, we found a considerable
decrease of dihedral angles of two opposite aromatic rings upon complexation. This finding can be explained in terms of the “chopsticks
process”, which illustrates how Ag+−arene π-coordination occurs. Heterobinuclear complexation of L1 in solution was also observed.