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 ](CF3 SO3 )2 , have been chosen. Their combination originates the polymeric derivatives [{AuR2 }2 Ag2 (terpy)2 ]n (R = C6 F5 , C6 Cl2 F3 ) or [{Au(C6 Cl5 )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 = C6 F5 and C6 Cl2 F3 species, whereas the more classical + - + - disposition was found for the bulkiest C6 Cl5 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.