Formation of a Fluorous/Organic Biphasic Supramolecular Octopus Assembly for Enhanced Porphyrin Phosphorescence in Air

The trinuclear triangle‐shaped system [tris{3,5‐bis(heptafluoropropyl)‐1,2,4‐triazolatosilver(I)}] (1) and the multi‐armed square‐shaped metalloporphyrin PtOEP or the free porphyrin base H2OEP serve as excellent octopus hosts (OEP=2,3,7,8,12,13,17,18‐octaethyl‐21H,23H‐porphine). Coupling of the fluorous/organic molecular octopi 1 and H2OEP or PtOEP by strong quadrupole–quadrupole and metal–π interactions affords the supramolecular assemblies [1⋅PtOEP] or [1⋅H2OEP] (2 a), which feature nanoscopic cavities surrounding the upper triangular and lower square cores. The fluorous/organic biphasic configuration of [1⋅PtOEP] leads to an increase in the phosphorescence of PtOEP under ambient conditions. Guest molecules can be included in the biphasic double‐octopus assembly in three different site‐selective modes. Glowing supramolecular octopi: A fluorous/organic biphasic supramolecular octopus pair with two nanoscopic cavities was constructed by coupling of a fluorous Ag3 macrocycle with a metalloporphyrin through strong quadrupole–quadrupole interactions. The unique configuration of this system enhances the phosphorescence of the metalloporphyrin under ambient conditions.