| This thesis reports three Schiff base ligands: 3,5-dibromosalicylaldehyde salicylhydrazone(H2Ll) , N,N'-o-phenylenebis-(3,5-dibromosalicylideneimine)(H2L2) and 3,5-dibromosalicylidene anthranilic acid(H2L3), as well as seventeen coordination compounds of their Zn( II), Cu( II), Ni( II), Cd( II )and Mn( II) complexes. All of the compounds above have been characterized by elemental analysis, UV-vis, IR, molar conductivity and X-ray single crystal diffraction. The ligands were identified by 1H-NMR and MS additionally. The full-optimized molecular geometries of the complexes were calculated at HF/STO-3G, HF/6-31G, B3LYP/6-31G and B3LYP/ STO-3G levels with Gaussian 03W program.The crystal structures of Zn(Ll)(py)2(complex5) , Zn(Ll)(py)3(complex6) , Ni(C13H6N2OBr2)2(complex17, [Zn(L2)(py)] · DMF(complex7) and Ni(L2)(2-Me-py) (complex8)(py=pyridine , 2-Me-py=2-methylpyridine , DMF=N,N-dimethylforma -mide)were determined by X-ray diffraction. These complexes are all neutral, the crystal data are as follows:The crystal structure of Zn(Ll)(py)3(complex6) belongs to monoclinic crystal system P21/n space group, with a=0.99978(6)nm, b=1.95111(13)nm, c=1.49602(10)nm, β=97.1260(10)° , V=2.8957(3)nm3 , Z=4 , Mr=714.71 , Dc=1.639g/cm3 , μ(Mo-Ka)=3.647mm-1 F (000)=1424, R=0.0610, wR=0.1414. The center zinc(II) is bonded to two oxygen atoms and one nitrogen atom from a tridentate ligand(H2Ll) and three nitrogen atoms from three solvent pyridine molecules to form a six-coordinate distorted octahedron.The crystal structure of Zn(Ll)(py)2(complex5) belongs to triclinic crystal systemP1 space group, with a=0.89000(11)nm, b=1.22172(14)nm, c=1.31342(16)nm, β=103.519°, V=1.2329(3)nm3, Z=2,Mr=636.62, Dc=1.715g/cm3,μ(Mo-Ka)= 4.270mm-1, F(000)= 630, R= 0.0526, wR=0.1246. The center Zn(II) is bonded to two oxygen atoms and one nitrogen atom from a tridentate ligand(H2Ll) and two nitrogen atoms from two solvent pyridine molecules to form a five-coordinate distorted trigonal bipyramid.The crystal structure of Zn(L2)(py)-DMF(complex7) belongs to monoclinic crystal system P2}/c space group, with a=0.82289(9)nm, Z?=1.52809(17)nm, c=2.3793(3) nm, ￡=95.946(2)°, F=2.9757(6)nm3, Z=4, Mr=847.51, ￡c=1.892g/cm3, ^(Mo-Ki) =6.233mm"1, F(000)=1648, #=0.0684, w/?=0.1616. The center Zn(II) is bonded to two oxygen atoms and two nitrogen atoms from a quadridentate ligand (H2L2) an d one nitrogen atom from one solvent pyridine molecule to form a five-coordinate square pyramid.The crystal structure of [Ni(L2)(2-Me-py)J (complex8) belongs to monoclinic crystal system P2;/e space group , with a=0.82156(6)nm , fc=2.36234(17)nm , c=2.9604(2)nm,j3=93.9760(10)°,F=5.7318(7)nm3,Z=4,Mr=862.82,Z)c=1.930g/cm3, ^(Mo-Kj)= 6.288mm1, F (000)= 3228, R= 0.0616, wR= 0.1445. The center Ni(II) is bonded to two oxygen atoms and two nitrogen atoms from a quadridentate ligand(H2L2) and one nitrogen atom from one solvent 2-methylpyridine molecule to form a five-coordinate square pyramid.The crystal structure of Ni(Ci3H6N2OBr2)2 (complexl7) belongs to tetragonal crystal system I4(l)/a space group, with a=1.24177(14)nm, 6=1.24177(14)nm, c=3.3389(6)nm, fi = 90°, F=5.1456(12)nm3, Z=8, Mr=790.75, Dc = 2.040g/cm3, MMo-Ka)= 6.995mm1, F (000)=3040, R= 0.0650, wR= 0.1546. The center Ni(II) is bonded to two oxygen atoms and two nitrogen atoms from two ligands to form a distorted tetrahedron.H2LI, H2L2 and their zinc complexes revealed obvious fluorescence activities. The electrochemical activities of nickel complexes were studied in the solvent of pyridine and DMF, respectively. Epoxidation of styrene catalyzed by some manganese complexes of the three ligands as model compounds of oxygenase has been studied. |
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