The Synthesis And Properties Of Coordination Complexes Based On The Derivatives Of Thiol Pyrimidine Ligand

Thiol pyrimidine and its derivatives were a class of heterocyclic organic ligandscontaining N, S atoms, which was widely studied no matter in the coordination or activities.Thiol pyrimidine heterocyclic compounds can coordinate with a variety of metal ions to formmany complexes result from the diversity of its own structure. This class of compounds withnovel structure and unique function can form π…π stacking, hydrogen bonding and otherforces easily. In this paper, we choose2-mercaptopyrimidine (pymtH) and4-methy-2-mercaptopyrimidine (HMMPY) as organic ligands coordinate with differenttransition metal ions to form a total of ten novel comlpexes under three series by thehydrothermal/solvothermal synthesis method and characterized by single-crystal X-raydiffraction, Infrared Radiation spectra (IR), elemental analysis and thermogravimetric analysis(TGA), etc. Moreover, the fluorescent and magnetic properties have been detailed discussionand investigated. The main contents are as follows:1. Four complexes based on pymtH ligand have been succussfully synthesized underhydrothermal/solvethermal conditions, namely,[Pb(pymt)2]n(1),[Cd(pymt)2]n(2),[Cu11(pymt)4I7]n(3),[Co(pymt)2]n(4). In complex1, the two adjacent PbIIions bridged by Satoms can form a one-dimensional helical chain structure, but interestingly, we found the spindirection of such a one-dimensional helical chain is opposite, including left-handness andright-handness. In complex2, the pymt-ligand ion connected with the adjacent CdIIion form1D zig-zig chains and the adjacent1D chains connected through the bidentate ligands ionpymt-forming a2D layered structure eventually. In complex3, there are a total of six kinds ofcoordination modes about CuIion, such as linear of-N2-and-NS-, triangle of-N2I-and-NSI-, distorted tetrahedral of-S2I2-,-NSI2-and-I4-. The coordination mode of pymt-is μ5-1,kN:2,3,4kS:5,kN’. Because of the rich coordination geometry of CuI, the complex3canform a two-dimensional layered structure eventually. In complex4, the range of angle is84.40–139.95°, deviate from the perfect diamond (109.05°), so the topological structure canbe regarded as diamond-like framework.2. Two complexes based on HMMPY ligand have been succussfully synthesized underhydrothermal/solvethermal conditions at the same temperature with different solvent, namely,{[Ni(MMPY)2(N2H4)]·H2O}n(5),[Cd(MMPY)2]n(6),[Pb(MMPY)2]n(7). In complex5, twoadjacent metal ions NiIIare bridged by N2H4·H2O molecules to form a zero dimensionalstructure complexe which have antiferromagnetic. The complex6are synthesized by twokinds of coordination mode ligand ion MMPY-and CdII, and it shows honeycomb2D layeredstructure with strong fluorescence. In complex7, the adjacent PbIIis bridged by MMPY-toform a1D zig-zig chain, the adjacent zig-zig chains is connected by molecular interaction(π…π=3.3575) to form a2D layered structure.3. Ligands are often occurs in situ reaction under the hydrothermal/solvothermalconditions. The main in situ reactions of thiol are coupling reaction, sulfonation reaction andtransfer reaction between organic and inorganic sulfur. The thiol is oxidized to SO42-based onthe in situ reaction of thiol pyrimidine. We obtained three sulfate skeleton complexes byadjusting the pH value of the solution, namely,[(CoSO4)3K2O2(OH)2](8),[Mn2(SO4)3]·(H3O)2(9),[Mn3(SO4)2(OH-)2(H2O)2](10). In complex8, the CoIIthree nuclearstructure unit is bridged by OH-to form a Co3(OH)2cationic chain, such a cationic chain isconnected by SO42-to form a2D layered structure, and finally form a3D supramolecularstructure through the bridge of K+layer. In complex9, there is strong hydrogen bondinginteraction (dO2w···O2＝2.9508(29)). The formation of hydrogen bond make the lattice watermolecules can be stably fixed in the cage. In complex10, layered structure are connected bysulfate to form a three-dimensional framework.