Thallium(I) acetylacetonate as building blocks of luminescent supramolecular architectures

dThe heteropolynuclear complexes [AuTIR2](n) (R = C6F5, C6Cl5) react with [Tl(acac)] in 1:1 or 1:2 molar ratio, leading to products of stoichiometry [AuTl2(acac)(C6Cl5)(2)] (2) and [AuTl3(acac)(2)(C6F5)(2)] (3). The new complexes obtained display Tl-2(acac)(2) units acting as bridges between linear chains of [AuTl(C6Cl5)(2)](n) in 2 or between [AuTl(C6F5)(2) units in 3. In both structures, in addition to the (AuTl)-Tl-... interactions, Tl(I)Tl-...(l) contacts also appear, which are considered to be in part responsible for the luminescent behavior. The comparison of these properties in solution to that of the starting complex [Tl(acac)] allows us to propose the presence of Tl(I)T-...(I) interactions also in solution. TD-DFT calculations show that Tl-2(acac)(2) units would be responsible for the luminescent behavior of Tl(acac) and complexes 2 and 3 in acetonitrile solution.