Studies On The Synthesis,Structure And Properties Of Complexes BearingPlanar Aromatic Ketones And Oximes

Metal complexes have attracted much attention for their unique properties and potential applications inmagnetic,optical and biological fields.In this paper,the planar aromatic ketones and oximes bearing five and seven-membered conjugated rings were designed as ligands.Their reactions with transition metal salts and rare earth metal saltsgave thirteen novel complexes,the structures of which were studied.Their magnetic properties were investigated,which revealed single molecular magnetic behaviors for three complexes and single chain magnet for one complex.Following is the main contents1.The reactions of the ligand of tropolone with Dy(NO3)3·6H2O,Co(OAc)2·4H2O,Ni(OAc)2·4H2O and Cu(OAc)2-H2O in sealed vacuated galss tubes gave three Dy(Ⅲ)copmlexes[Dy(L1)3(H2BTC)(H2O)]·H2O(1),[Dy(L1)3(phen)]·H2O(2),and[Dy2(L1)4(oc)(H2O)4]·7H2O(3),and three transition metal complexes[CoⅡ2(L1)4(DMF)2](4),[CuⅡ2(L1)2(MepH)2(OAc)2](5)and[NiⅡ2(L1)4(4,4’-Bipy)2]n(6).Complex(1)is a Dy(Ⅲ)mononuclear complex with the ancillary ligands of trimesic acid involved in corrdination.Complex(2)is also a mononuclear complex,which is different from complex(1)in ancillary ligands.Complex(3)has a binuclear Dy(Ⅲ)structure with the oxalate ligand linking the two Dy(Ⅲ)ions through chelating-briding coordination modes.Complexes(4)presents a dinuclear structure formed from the linkage of the two Co(Ⅱ)ions bythe tropolone ligands.Complex(5)is one mononuclear Cu(Ⅱ)complex with the ancillary ligands of mepH and acetate involved Ⅲ coordination.Complex(6)features dinuclear units which are linked by 4,4’-bipyridine molecules to form a one-dimensional chain.Two of the rare earth complexes in this research work presentssingle-molecule magnet behavior.Antiferromagnetic interactions are dominant in the transition metal complexes.2The reactions of acenaphthenequinone monooxime or acenaphthenequinone dioxime ligands with Co(OAc)2·4H2O,Ni(OAc)2·4H2O,Er(NO)3·6H2O or Mn(OAc)2·4H2O in sealed vacuated galss tubes gave four novel complexes[Co7(OH)4L28(OAc)2(H2O)6](7),[Ni7L24(OAc)6(H2O)2(CH30)4(Im)2](8),[Mn6(μ3-O)2(L3)6(CH3OH)2(CH3COO)2(DMF)2]n(9)and[Mn3(μ3-O)(L3)3(CH3OH)4(CH3COO)]n(10).Complex(7)is a heptanuclear Co(Ⅱ)7 complex with imidazole and acetateparticipating in coordination as the ancillary ligands.Complex(8)has a heptanuclear Ni7 structure with the participatation of methanol and watermolecules in coordination.Complex(9)features a hexanuclear unit formed from the linkage of two planar triangular trinuclear units by anti-anti bridging acetate anions.The adjacent hexanuclear units interact with each other through mutual weak coordination bonds,forminga one-dimensional coordination polymer.The one-dimensional structure of complex(10)is constructed from the connection of planar triangular trinuclear units by anti-anti bridging acetate anions.The magnetic measurements revealed a single-chain magnet for complex(10)and the presence of dominant antiferromagnetic interactions between the metal ions in the other complexes.3Acenaphthene quinone dioxime was used as the main ligand to react with Gd(NO3)3·6H2O,Tb(NO3)3-6H2O,Dy(NO3)3·6H2Oin sealed vacuated galss tubes in the presence of Mn(OAc)2·4H2O,producing three newisomorphous3d-4f heterometallic complexes[Mn2Gd(L3)6(DMF)2](11),[Mn2Tb(L3)6(DMF)2](12)and[Mn2Dy(L3)6(DMF)2](13).There are two Mn(Ⅲ)ions,one Ln(Ⅲ)ion,six acenaphthenequinone dioxime ligands,and two lattice DMF solvent molecules per formular unit.The magnetic investigation indicate the presence of single-molecular magnet behavior for the Dy(Ⅲ)compound.