Metal Complexes Based On Oxime And Hydroxyl Oxime Acid Including Aromatic Rings: Syntheses, Structures And Properties

Owing to the multiple of oxime and hydroxamic acid ligands, these old and evergreenligands can easily coordinate with metal cations to form complexes, most of which areM-N-O metallacrowns. The investigation proved that these complexes display specialchemical properties, biological activities and magnetic properties, and some complexescontaining MnIII, CoII, NiII, DyIIIand3d-4f heterometal exhibit single-molecule magneticbehavior. Herein,23complexes, including14metallacrowns, were characterized byelemental analysis, FT-IR spectra and X-ray single crystal diffraction. These complexeswere synthesized from the reactions of oxime and hydroxamic acid including aromaticrings with different metal salts. The main sections of the thesis are as follows:1. The reactions of salicylaldoxime (saoH2),2-hydroxy-1-napthaldoxime (napth-saoH2)and3-methyloxysalicylaldoxime (H2vanox) with different metal salts produced13complexes:[Mn6O2(sao)6(OAc)2(C2H5OH)2(H2O)2]·2H2O (1),[Mn6O2(sao)6(OAc)2(CH3OH)2(H2O)2]·4H2O (2),[Mn6O2(napth-sao)6(PhCOO)2(Py)2(CH3OH)2]·2CH3CN (3),[Mn6O2(napth-sao)6(PhCOO)2(C2H5OH)4(CH3OH)2](4),[Mn6O2(napth-sao)6(OAc)2(HOAc)2(C2H5OH)2]·2H2O (5),[Fe6O(OH)(vanox)6(MeO)3(H2O)3]·6CH3OH·6H2O (6),[Co2IICo2III(Hvanox)2(vanox)2(N3)4(C2H5OH)2]·2C2H5OH (7),[Tb3(Hvanox)4(vanox)2(OAc)(MeOH)]·MeOH (8),[Gd2(Hvanox)4(CH3COO)2(H2O)2]·2H2O (9),[Pr2(Hvanox)4(PhCOO)2(CH3OH)2](10),[Nd2(Hvanox)4(PhCOO)2(CH3OH)2](11),[Sm2(Hvanox)4(PhCOO)2(CH3OH)2](12),[Eu2(Hvanox)4(PhCOO)2(CH3OH)2](13). In these complexes,salicylaldoxime and2-hydroxy-1-napthaldoxime ligands coordinate to metal cations withthe tridentate, fully deprotonated models, and3-methyloxysalicylaldoxime ligandcoordinate to metal cations with the tetradentate, mono-deprotonated/fully deprotonatedfashions. Complexes1-5are hexanuclear manganese complexes, which contain two[MnIII3(μ3-O)]7+9-MC-3metallacrown structure units, and the two metallacrown units arebridged by two Mn-O coordination bonds to form off-set structures. In complexes1-5,MnIIIcations show two kinds of coordination environments: distorted octahedral withhexa-coordinated and distorted tetragonal pyramid with penta-coordinated. Complex6is a hexanuclear ferrum complex including two9-MC-3metallacrown subunits:[FeIII3(μ3-O)(Me-sao)3]+and [FeIII3(μ3-OH)(Me-sao)3]2+. The Fe cations in eachmetallacrown subunits are linked by three methanol O atoms and three water O atoms toform a onset structure. All FeIIIcations are present in distorted octahedral coordinationenvironments. Complex7is a mixed-valence tetranuclear cobalt complex, involving twoCoIIIcations and two CoIIcations. All four Co cations display distorted octahedralcoordination environments. Complexes8-13are lanthanide complexes. Complex8is a Tb3cluster, both of which are octa-coordinated and one is nona-coordinated. Complexes9-13are homobinuclear lanthanide complexes with all Ln cations adopting distorted tricappedtrigonal prismatic coordination environments with nona-coordinated. Studies of themagnetic properties indicate the presence of dominant antiferromagnetic in complexes1-5,9,11and ferromagnetic in complex7, and complexes1,2,4and5also exhibitsingle-molecular magnets (SMM) behavior.2. Four complexes were obtained from the reactions of2-hydroxyccetophenoneoxime(Me-saoH2) with different metal salts:[CoIII2CoII(Me-saoH)4(PhCOO)2(Py)2](CH3O)2(14),[Mn6O2(Me-sao)6(PhCOO)2(CH3OH)6]·2CH3OH (15),[Mn6O2(Me-sao)6(PhCOO)2(DMF)2]·DMF·H2O (16),[Mn7O2(Me-sao)6(OAc)4(CH3O)(Py)(H2O)2]·CH3OH·H2O (17).In these complexes,2-hydroxyccetophenoneoxime ligand coordinate to metal cations withthe tridentate, mono-deprotonated/fully deprotonated fashions. Complex14is a linearmix-valence Co3cluster containing one CoIIcation and two CoIIIcations, and all Cocations adopting distorted octahedral coordination environments. Complexes15and16arehexanuclear manganese complexes, two off-set [MnIII3(μ3-O)]7+9-MC-3metallacrownrings are bridged by Mn-O coordination bonds. In complex15, all MnIIIcations are locatedin hexa-coordinated distorted octahedral coordination environments. While in complex16,two MnIIIcations adopt distorted octahedral coordination environments with sixcoordination, and four MnIIIcations show distorted tetragonal pyramid coordinationenvironments with penta-coordinated. Complex17is a heptanuclear manganese complexwith all MnIIIcations adopting hexa-coordinated distorted octahedral coordinationenvironments, which contains two [MnIII3(μ3-O)]7+9-MC-3metallacrown rings. The seventh MnIIIcation links two9-MC-3metallacrown rings through three acetic acid anionsto form a sandwich-type structure. Studies of the magnetic properties indicate the presenceof dominant antiferromagnetic in complex15and ferromagnetic in complex17, andcomplexes15and17also exhibit single-molecular magnets (SMM) behavior.3. The reactions of3-hydroxy-2-naphthylhydroxamic acid (H3Nha) with different metalsalts afforded five complexes:(t-Bu4N)2[Cu5(Nha)4py](18),(t-Bu4N)2[Cu5(Nha)4py](19),(t-Bu4N)4[Cu10(Nha)8]·6H2O (20),(t-Bu4N)4[Cu10(Nha)8]·4CH3OH·4DMF (21), Sr9(Nha)6(DMF)8(H2O)14·2CH3OH·2H2O (22). In these complexes,3-hydroxy-2-naphthyl-hydroxamic acid coordinates to metal cations with the tetradentate, fully deprotonatedmodel. Complex18is a pentanuclear copper complex containing a12-MC-4metallacrownstructure, which is very similar to complex19. One Cu cation is located in the core of the12-MC-4metallacrown structure. Complexes20and21are decanuclear copper complexesinvolving two12-MC-4metallacrown structure units, and two metallacrown units arebridged by Cu-O coordination bonds to form off-set structures. In complexes18-21, Cucations show two kinds of coordination geometry: planar square and tetragonal pyramid.Complex22is a18-MC-6metallacrown, in which a Sr cation is bondaged in the corner ofthe metallarown ring by six hydroxylamine O atoms, and the other two Sr cations are intwo sides of the metallarown ring. Studies of the magnetic properties indicate the presenceof dominant antiferromagnetic in complexes19,20,21. In addition, by using a standardMTT assay, the antitumor test shows that complexes18-21each possesses no in vitroantitumor activity.