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], bearing perhalophenyl derivatives, and dinuclear acid silver terpyridine species, Ag(terpy), have been chosen. Their combination originates the polymeric derivatives [{AuR}Ag(terpy)] (R = CF, CClF) or [{Au(CCl)}Ag(terpy)]. 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 = CF and CClF species, whereas the more classical + - + - disposition was found for the bulkiest CCl 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.