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 center dot(BArF)(8)) built from Zn-porphyrin and macrocyclic Pd-dip-based synthons is described. The functional duality of the guest ligand L-1 allows for its encapsulation inside the cage 1 center dot(BArF)(8), along with the simultaneous coordination of Zn-II, Cu-II, or Fe-III metal ions. Remark-ably, the coordination chemistry inside the host-guest adduct L-1 subset of 1 center dot(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 center dot(BArF)(8) is strongly quenched by the encapsulation of paramagnetic complexes, representing a remarkable example of guest-dependent tuning of the host fluorescence.