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The reactions of solutions of TlPF6 and OPPh3 in tetrahydrofuran or acetone with NBu4[AuR2] (R=C6Cl5, C6F5) gave the new complexes [Au(C6Cl5)2]2[Tl(OPPh3)][Tl(OPPh3)(L)] (L=THF (1), acetone (2)) and the previously reported [Tl(OPPh3)2][Au(C6F5)2] (3). The crystal structures of complexes 1 and 2 display extended unsupported chains with short intermolecular interactions between alternating gold(I) and thallium(I) centres. Moreover, the Tl^I centres show two different types of geometrical environments, such as pseudotetrahedral and distorted trigonal-bipyramidal, due to the presence of solvent molecules that act as ligands in the solid-state structure. Quasirelativistic and nonrelativistic ab initio calculations were performed to study the nature of the intermetallic Au^I–Tl^I interactions and are consistent with the presence of a high ionic contribution (80 %) and dispersion-type (van der Waals) interaction with a charge-transfer contribution (20 %) when relativistic effects are taken into account. All complexes are luminescent in the solid state at room temperature and at 77 K. Complexes 1 and 2 show site-selective excitation, probably due to the different environments around the Tl^I centres. The DFT and time-dependent (TD)-DFT calculations are in agreement with the experimental excitation spectra for all complexes and confirm the site-selective excitation behaviour as a function of the Tl^I geometrical environment.

The reactions of solutions of TlPF6and OPPh3in tetrahydrofuran or acetone with NBu4[AuR2] (R=C6Cl5, C6F5) gave the new complexes [Au(C6Cl5)2]2[Tl(OPPh3)][Tl(OPPh3)(L)] (L=THF (1), acetone (2)) and the previously reported [Tl(OPPh3)2][Au(C6F5)2] (3). The crystal structures of complexes 1and 2display extended unsupported chains with short intermolecular interactions between alternating gold(I) and thallium(I) centres. Moreover, the TlIcentres show two different types of geometrical environments, such as pseudotetrahedral and distorted trigonal‐bipyramidal, due to the presence of solvent molecules that act as ligands in the solid‐state structure. Quasirelativistic and nonrelativistic ab initio calculations were performed to study the nature of the intermetallic AuI–TlIinteractions and are consistent with the presence of a high ionic contribution (80 %) and dispersion‐type (van der Waals) interaction with a charge‐transfer contribution (20 %) when relativistic effects are taken into account. All complexes are luminescent in the solid state at room temperature and at 77 K. Complexes 1and 2show site‐selective excitation, probably due to the different environments around the TlIcentres. The DFT and time‐dependent (TD)‐DFT calculations are in agreement with the experimental excitation spectra for all complexes and confirm the site‐selective excitation behaviour as a function of the TlIgeometrical environment.