The reaction of the Ni(II) complex of 5,14-dihydro-6,8,15,17-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetrade cine with succinyl dichloride leads to di- and monosubstituted derivatives bearing β,γ-unsaturated-γ-lactonic rings at the meso positions of the macrocycle. An aminolytic cleavage of these lactonic substituents gives rise to open-chain pendant groups containing the corresponding amide functions. A range of new complexes have been synthesized in this way with use of primary and secondary aliphatic and heterocyclic amines. The new products have been characterized by elemental analyses, 1 H, 1 3 C NMR, IR and ESI-MS spectral data. Single crystal X-ray studies revealed that the saddle-shaped molecules of [5,14-dihydro-7,16-bis(2-oxo-3H-furan-5-yl)-6,8,15,17-tetramethyldibenzo[b,i ][1,4,8,11]tetraazacyclotetradecinato(2-)-κ 4 N]nickel(II) act as receptors with molecules of toluene forming 1:1 supramolecular complexes.