Design of Zn-, Cu-, and Fe-Coordination Complexes Confined in a Self-Assembled Nanocage

The encapsulation of coordination complexes in a tetragonal prismatic nanocage (1·(BArF)8) built from Zn-porphyrin and macrocyclic Pd-clip-based synthons is described. The functional duality of the guest ligand L1 allows for its encapsulation inside the cage 1·(BArF)8, along with the simultaneous coordination of ZnII, CuII, or FeIII metal ions. Remarkably, the coordination chemistry inside the host–guest adduct L1⊂1·(BArF)8 occurs in both solution solution and solid state. The resulting confined metallocomplexes have been characterized by means of UV-vis, ESI-HRMS, NMR, and EPR techniques. Furthermore, the emission of the Zn-porphyrin fluorophores of 1·(BArF)8 is strongly quenched by the encapsulation of paramagnetic complexes, representing a remarkable example of guest-dependent tuning of the host fluorescence.