Copper, cobalt, and zinc complexes of symmetrical and unsymmetrical macroheterocyclic ligands containing thiadiazole, pyridine, and 1,3-indandione fragments were prepared by reactions of these ligands with appropriate metal salts. The physicochemical properties of the complexes were studied.Interaction of transition metals with macroheterocyclic ligands is studied for a long time [133], and a large body of data have been accumulated on the nature of the metal3ligand chemical bonding [4,5].Metal complexes with macroheterocycles are used as pigments, dyes, and catalysts; some of them are ÄÄÄÄÄÄÄÄÄÄÄÄ biologically active and can be used for development of new drugs [6 38]. Also, these complexes can be considered as model objects for studying the chromophore systems of dyes, with the aim to elucidate the structure and mechanism of action of complex organic molecules. As such objects we chose the following complexes:N ] ; : M W5 N N S 9 9 M CH HC N NH HN O O O Cl 2 5 = N N 9 ML 1 ML 2 M = Cu 2+ , Co 2+ , Zn 2+ .
ÄÄÄÄÄÄÄÄÄÄÄÄThe macroheterocyclic ligands derived from 1,3-indandione, as well as the isoindole derivatives, do not contain an aromatic macrocyclic chromophore [3]. Therefore, their structure is not strictly planar, which is confirmed by molecular-mechanics (MM2) calculations. For L 1 : E b 2.38, E ba 231.90, E tors 81.6, E vdW 3 42.03, and E tot 273.92. For L 2 : E b 2.07, E ba 187.2, E tors 60.69, E vdW 336.56, and E tot 213.40.Here E b is the energy of bonds; E ba , energy of bond angles; E tors , energy of torsion angles; E vdW , energy of van der Waals forces; and E tot , total energy of formation of the compound (kcal mol !1 ).Macroheterocyclic compounds derived from 1,3-indandione were prepared in three steps. In the first step, by condensation of 1,3-indandione with 2,5-diamino-1,3,4-thiadiazole we prepared the corresponding arylenediamine. In the second step, we performed acylation of the arylenediamine, with substitution of the carbonyl oxygen atom with the benzoyloxy group [9]. Finally, in the third step, by the reaction of the o-benzoyloxy derivative with aromatic diamines in glacial acetic acid, we obtained macroheterocycle L 1 [10]. Construction of the 3D models of the macroheterocyclic compounds confirms the possibility of their existence [11].Coordination of macroheterocycles with the metal ion results in significant and regular changes in their