Studies On The Synthesis And Crystal Structure Of Complexes With 5-mercaptomethyl-2,4-dihydro-1,2,4-triazole-3-thione

In this thesis,the reactions of metal salts with 5-Mercaptomethyl-2,4-dihydro-1H-1,2,4triazole-3-thione(H3L)gave ten complexes which have not been reported.Number of specific compounds and molecular structures of short form as follows:(1)[Ni4(HL)4]·H2O·DMF(2)Ni4(HL)4(3)[Ni24(HL)24]·NO3·xG(4)[Zn24(HL)24(H2O)6]·NO3-xG(5)[Mn24(HL)24(H2O)6]·NO3·xG(6)[Cd24(HL)24(H2O)6]·ClO4-xG(7)[Cd(H2L)4Cl2]n·(C4H8O2)2(8)Cu(L1)2·1.5H2O(9)[Cu(L2)3Cl]n(HL2=3-carboxyl-1,2,4-triazole)(10)[Cu2(L3)2Br2]n(HL3=1,2,4-triazole)1.Complex(1)and complex(2)were separated from the reactions of H3L with NiSO4·6H2O,by the the method of solution method and solvothermal respectively.Complex(3)were separated from the reactions of H3L with NiSO4·6H2O and Cd(NO3)2·4H2O.Complex(1)and complex(2)were quadri-nuclear complex,the main body frame structures were similar with four-membered ring.By the coordination mode of ?3-?2:?1:?1,the coordination environment of central atoms was the same.Due to the effect of solvent molecules in the unit of complex(1),the main body frame was slight distortion compared to complex(2),thus the four-membered ring of central atoms translated rhombic-shaped structure into parallelogram sturcutre.Complex(3)is a wheel-shaped Ni24 cluster,hexagonal system.There is a nitrate ion located on the circular center,the cage was disposed about a crystallographic sixfold axis therefore there are only four nickel centers in the asymmetric unit.The geometrical configuration of nickel centers were distorted octahedral configurations,distorted tetragonal pyramid conformation,and two distorted tetrahedron configurations respectively.Ligands got to the coordination mode of ?4-?2:?1:?1;?1??3-?2:?1:?1 and ?5-?2:?1:?1:?1:?1.By the bridging model of ?2-S,six asymmetric unit connected to Ni24 wheel.The magnetic property of complex(4)and(5)revealed the presence of dominant antiferromagnetic interactions.2.Complex(4)was synthesized from the reactions of H3L with Zn(ClO4)2·6H2O,which is a wheel-shaped Zn24 cluster,triclinic system.There are twenty-four HL2-,twenty-four zinc ions,six coordinated water molecules in each cluster cell,and a nitrate ion located on the circular center,the cage was disposed about a crystallographic threefold axis therefore there are eight zinc centers in the asymmetric unit.Complex(5)was synthesized from the reactions of H3L with Mn(ClO4)2·6H2O,its structure is similarity with complex(5).During the process of synthesis of complexes(4)and(5),we all can get complexes(6),which is a wheel-shaped Cd24 cluster,monoclinic system.There are twenty-four HL2-,twenty-four cadmium ions,six coordinated water molecules in each,cluster cell,and a perchlorate ion located on the circular center,the cage was disposed about a crystallographic twofold axis,therefore there are twelve cadmium centers in the asymmetric unit.Complex(7)was synthesized from the reactions of H3L with CdCl2.Complex(7)is coordinated with bipolymer by coupling two ligands,cadmium ion was bridged with the beginning and end of the the bipolymer respectively,got a one dimensional chain structure.Two adjacent one dimensional chain formed a two-dimensional plane structure through ?…?.The fluorescence property of complex(4)and(7)revealed thefluorescence intensity of(4)and(7)are increased significantly compared with H3L.3.Under the condition of solvent thermal,we got complex(8)from the reactions of H3L with CuCl.The sulfhydryl groups of H3L form disulfide bond through coupling reaction.At the same time,N,N-dimethyl formamide decomposed and reacted with H3L.Then,the changed ligands reacted with CuCl,got a plane shape of mononuclear copper compound clusters.Furthermore,we added a small amount of diethylamine when H3L reacted with CuCl,a new compound named complex(9)was separated.The thione in the 5-substituent of triazole was removed,the mercaptomethyl in the 3-substituent of triazole was oxidized to carboxyl.H3L turned into 3-carboxyl-1,2,4-triazole,by the nitrogen atoms and carboxyl oxygen,complex(10)present a three-dimensional metal organic framework structure.The reactions of H3L with CuBr2 and EDTA gave complex(10).In complex(10),3-substituent and 5-substituent were removed,H3L turned into 1,2,4-triazole and coordinate with copper ion,the geometrical configuration of copper centers were distorted tetragonal pyramid configurations.By reason of the action of three nitrogen thiazole rings,the adjacent one dimensional chain extending in all directions to form the three-dimensional network structure,and each of the one dimensional chain are parallel to others.