Tailor-Made Luminescent Polymers through Unusual Metallophilic Interaction Arrays Au···Au···Ag···Ag

A novel and efficient strategy for the synthesis of luminescent polymers bearing metallophilic interactions with unprecedented charge sequences has been designed. For this end suitable basic gold units such as [AuR 2 ] −, bearing perhalophenyl derivatives, and dinuclear acid silver terpyridine species, [Ag 2 (terpy) 2 ](CF 3 SO 3 ) 2, have been chosen. Their combination originates the polymeric derivatives [{AuR 2 } 2 Ag 2 (terpy) 2 ] n (R = C 6 F 5, C 6 Cl 2 F 3 ) or [{Au(C 6 Cl 5 ) 2 }Ag(terpy)] n . The change of the perhalophenyl group in the gold complex modulates the strength in the metallophilic contacts and, consequently, the polymer arrays and luminescent properties. The X-ray diffraction studies of these derivatives revealed that there are polymers with unusual + + – – + + – – charge sequences for the R = C 6 F 5 and C 6 Cl 2 F 3 species, whereas the more classical + – + – disposition was found for the bulkiest C 6 Cl 5 derivative. Their luminescent properties also vary depending on the formation of these polymer arrays, and time-dependent density functional theory calculations were performed to determine the origin of the luminescence.