Phosphorescent Host-Guest Complexes on the Basis of Polyhedral Oligomeric Silsesquioxane-Functionalized...

Phosphorescent host-guest systems have attracted considerable attention because of their intriguing properties and diverse applications. In this study, a polyhedral oligomeric silsesquioxane-functionalized gold(III) tweezer receptor has been designed and synthesized. It is capable of sandwiching platinum(II) terpyridine compounds into its cavity with a high noncovalent binding affinity (association constants: ∼10⁵ M^-1 in chloroform). The resulting heterometallic host-guest complexes exhibit enhanced phosphorescent emission compared with those of the individual species in chloroform, thanks to the prevention of vibration and rotation upon noncovalent complexation. They can further assemble into nanospheres in chloroform/diethyl ether (1:9, v/v) owing to phase segregation between the metallotweezer/guest motif and the peripheral polyhedral oligomeric silsesquioxane unit. When terpyridine platinum(II) chloride serves as the complementary guest, the resulting noncovalent system displays an intraligand emission at the individual host-guest complexed state yet excimeric emission at the supramolecular assembled state, yielding the phosphorescent solvatochromic behaviors. Overall, the polyhedral oligomeric silsesquioxane-functionalized metallotweezer combines guest encapsulation and supramolecular assembly capabilities, which provides new avenues for color-tunable phosphorescent materials.