Encapsulated, Sandwiched, or Sticking Out: Closed-Shell Interactions of d10 Metal Centers with Thallium(I)

The assembly of a new class of metallocryptands A and “metallosandwiches” B, as well as studies on the bonding of Tl+ with d10-configured Group 10 and 11 complexes in solution and in the solid state have established relatively strong “metallophilic” interactions between d10 metal centers and thallium(I). These materials have interesting luminescence properties which differ markedly from those of the individual components. The stability of the d10–s2 aggregates contrasts with the weak attraction between s2-metal centers proposed in the solid state for many thallium(I) compounds and which is frequently superceded by competing intra- and intermolecular interactions. Bz=benzyl.