In order to elucidate the influence of both ligand’s structure and central ion on the strength and character of exchange interaction between paramagnetic centers, the series of type I novel binuclear metallochelates with unsymmetrical exchange fragment including heterocycles has been synthesized.figureThe conditions determining the sign of exchange interaction have been established by the directed varying the substituent’s (R) nature in the ligand molecules as well as heterocyclic moieties. Namely, the complexes in which the 2J values are in the range from -300 to +200 cm-1 have been obtained for both copper (II) and vanadyl (II) ions, the nature of magnetic orbital in which is quite different. The quantum-chemical calculations for heterocyclic as well as the unsymmetrical exchange fragments have been carried out. The theoretical data obtained have been compared with the experimental values of exchange parameters that allowed to carry out their theoretical interpretation. The obtained complexes can be used as the precursors for the directed synthesis of novel magneto active materials – molecular magnets, possessing nanoscale structure.