A novel macrocyclic 1,7-dioxa-[2.1.11-(2,6)-pyridinophane ligand has been synthesized and crystallographically characterized. Two derived metal complexes, dichloropalladium(II) and chlorocopper(I), were prepared. In the palladium(II) complex LPdCl2, both in the solid state, according to its crystallographic characterization, and in CH2Cl2 solutions at -40 degrees C, according to H-1 NMR spectroscopy, the ligand adapts a C-1-symmetric kappa(2)-N,N-coordination mode in which the metal atom binds to two nonequivalent pyridine fragments of the macrocycle. The complex is fluxional at 20 degrees C. In the crystalline copper(I) complex LCuCl, the macrocyclic ligand is also kappa(2)-N,N-coordinated to the metal, but it utilizes two equivalent pyridine fragments for the binding. The copper(I) complex is fluxional in CH2Cl2 solutions in the temperature range between 20 and -70 degrees C and is proposed to be involved in a fast intermolecular macrocyclic ligand exchange which is slowed down below -40 degrees C. DFT calculations predict a lower thermodynamic stability of the dioxapyridinophane-derived complexes LPdCl2 and LCuCl, as compared to their [2.1.1]-(2,6)-pyridinophane analogs containing bridging CH2 groups instead of the oxygen atoms. The electron poor dioxapyridinophane chlorocopper(I) complex, in combination with NaBAr4F (BAr4F = tetrakis[3,5-bis(trifluoromethyl)-phenyllborate) in dichloromethane solutions, can serve as an efficient catalyst for aziridination of various olefins with PhINTs at 0-22 degrees C.