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 [AuR2]−, bearing perhalophenyl derivatives, and dinuclear acid silver terpyridine species, [Ag2(terpy)2]­(CF3SO3)2, have been chosen. Their combination originates the polymeric derivatives [{AuR2}2Ag2(terpy)2] n (R = C6F5, C6Cl2F3) or [{Au­(C6Cl5)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 = C6F5 and C6Cl2F3 species, whereas the more classical + – + – disposition was found for the bulkiest C6Cl5 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.