1,4-Bis(2'-pyridylethynyl)benzene as a ligand in heteronuclear gold-thallium complexes. Influence of the ancillary ligands on their optical properties.

The reaction of 1,4-bis(2'-pyridylethynyl)benzene (L) with [{Au(C6X5)2}Tl]n affords new heterometallic Au(I)/Tl(I) complexes with different stoichiometries, structural arrangements and optical properties depending on the halogens present in the aryl group. The chlorinated derivative [{Au(C6Cl5)2}Tl(L)]n () displays polymeric chains built thanks to unsupported AuTl interactions and bridging bidentate ligands between adjacent chains, while in the fluorinated species [{Au(C6F5)2}2Tl2(L)2]n (), also containing N-donor bridging ligands and AuTl contacts, polymerization occurs via TlCaryl non-bonding interactions between neighbouring molecules. The optical properties of and have been studied experimentally and theoretically, concluding that the luminescence of in the solid state has its origin in the AuTl interactions, and that the TlCaryl interactions in favour a non-radiative deactivation pathway that avoids luminescence. The strength of the non-bonding interactions present in has also been theoretically studied at the HF and MP2 levels, revealing the metallophilic contact as the strongest one.