Controlled emission of platinum(II) terpyridyl complexes with poly-l-glutamic acid

Poly-l-glutamic acid, P(Glu), bearing multiple negatively charged side chains served as a polymeric spatially aligned scaffold for the aggregation of positively charged platinum(II) complexes [Pt(trpy)CCR](OTf) (trpy = 2,2′,6′,2″-terpyridine; R = Ph (PtH), PhC₁₂H ₂₅-p (PtC₁₂)) through electrostatic interaction, resulting in tunable emission properties. PtC₁₂ was found to exhibit gradual increase in the emission intensity based on the triplet metal-metal-to-ligand charge transfer (³MMLCT) in a tris/HCl buffer (pH 7.6)/MeOH (v/v = 1/14) solution with concomitant decrease in the emission intensity based on the triplet metal-to-ligand charge transfer (³MLCT)/the triplet ligand-to-ligand charge transfer (³LLCT) as the amount of P(Glu) was increased. Such synergistic effect was not observed in the case of PtH, wherein the emission intensity based on ³MLCT/³LLCT was increased by the increase in the amount of P(Glu), indicating that alkyl long chain of PtC₁₂ is considered to play an important role in the aggregation of the platinum(II) terpyridyl moieties to show Pt(II)-Pt(II) and π-π interactions.