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

摘要

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, [Ag-2(terpy)(2)](CF3SO3)(2), have been, chosen. Their combination originates the polymeric derivatives [{AuR2}(2)Ag-2(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.