Σύμπλοκα του Cu(II) και Mn(II) με φαινοξυαλκανοϊκά οξέα και μεταλλοκορονοειδείς ενώσεις του Ni(II)

Abstract

Complexes of Mn(II) and Cu(II) with phenoxyalkanoic herbicides as ligands as wellas metallacrowns of Ni(II) hosting herbicides were prepared and characterized. The herbicidesligands L 2,4-DP, MCPA, 2,4,5-T, 2,4-D and 2,3-D have the characteristic existence of thecarboxylato group. All complexes were characterized spectroscopically (IR, UV-Vis, EPR),analytically and magnetically.Mn(II) complexes have the general type [Mn(L)2(H2O)2]n. In these complexes, thecarboxylate group of the ligands is coordinated in a bidentate bridging mode. The crystalstructure of the 2-dimensioned complex [Mn(MCPA)2(H2O)2]n was determined with X-Ray.This complex shows weak antiferromagnetic behavior.Cu(II) complexes have the general types Cu(L)2(MeOH)2 or Cu2(L)4(MeOH)2,Cu(L)2(L')(H2O), [Cu(L)(L')2]Cl and Cu2(L)4(bipyam)2, where L': a heterocyclic N-donorligand (bipy, phen, bipyam). In complex Cu2(2,3-D)4(MeOH)2, the carboxylate group of theligand 2,3-D is coordinated in a bidentate bridging mode, in complexes of the general typeCu(L)2(L')(H2O) and [Cu(L)(L')2]Cl the carboxylate group is in a monodentate mode, while indinuclear complexes of the type Cu2(L)4(bipyam)2 both monodentate mode and bidentatebridging mode for the carboxylate group were found. In all complexes Cu+2 ion is five coordinatedand could be described as having highly distorted square pyramidal to trigonalbipyramidal geometry. The neutral mononuclear complexes of the type Cu(L)2(L’)(H2O)exhibit magnetochemical properties which are characteristic of a di- or multi-nuclear structureand are due to intra- and inter-molecular hydrogen bonds. Antimicrobial studies of thecomplexes showed that the best inhibition is provided by the cationic mononuclear complexesof the type [Cu(L)(L')2]Cl.Ni(II) metallacrowns hosting herbicides are of the general type NiII2(L)2(CH3OH)3(H2O)[12-MCNi(II)N(shi)2(pko)2-4][12-MCNi(II)N(shi)3(pko)-4], where H3shi=salicyl-hydroxamic acidand Hpko=di-(2-pyridyl)-ketonoxim, and are consisted of two metallacrown rings with +1 and-1 charges. Both metallacrown rings have an encapsulated Ni(II) ion and are held togetherthrough Ni-O bonds. Magnetic measurements for complex NiII2(MCPA)2[12-MCNi(II)N(shi)2(pko)2-4][12-MCNi(II)N(shi)3(pko)-4](CH3OH)3(H2O) showed weak antiferromagneticbehavior.