Investigations On Synthesis, Characterizations,Flame Resistances And Antibacterial Activities Of Ammonium O,O’-Diaryldithiophosphates And Their Complexes

O,O’-diaryldithiophosphates:(p-C6H4O2)PS2H,(2,4,6-Br3C6H2O)2PS2H,(p-BrC6H4O)2PS2NH2Et2,(p-ClC6H4O)2PS2NH2Et2,(PhCH2CH2O)2PS2NH2-Et2,(p-MeC6H4O)2PS2NHEt3,(PhO)2PS2NH2Et2,(p-ButC6H4O)2PS2NH2Et2,(o-C6H4O2)PS2NH2Et2,13transition metaI complexes and5rare earth metal complexes were synthesized in this paper. The complexes were fully characterized by elemental analysis、IR spectra、UV-vis spectra、fluorescence spectroscopy、thermal-gravimetric analysis、1H NMR spectra、 Mass Spectrometry,as well as for7representatives by X-ray crystallography.The thirteen transition metal complexes containg Cd,Cu,Hg or Pb,which are summarized as follows:[(PhCH2CH2O)2PS2]2Cd}n(1),{[(PhCH2CH2O)2PS2]2Cd·(2,2’-bipy)}(2),{[(PhCH2CH2O)2P S2]2Cd·phen}(3),{[(p-C6H4O2)2P2S4Cd]·(4,4’-bipy)}n(4),{[(o-C6H4O2)PS2]2Cd}·(4,4’-bipy)(5),[NH2Et2]+{[(p-ButC6H4O)2PS2]3Cd]}-·EtOH(6)；Cu cluster{CuCl[(PhO)2PS2]3.Phen2}(7)；{[(PhCH2CH2O)2PS2]2Hg}n(8),{[(μ-PhCH2CH2O)2PS2]2Hg·phen}2(9)；[(PhCH2CH2O)2PS2]2Pb(10),{Pb2[(PhCH2CH2O)2PS2]4·(4,4-bipy)}(11),[(PhCH2CH2O)2PS2]2Pb·Phen}(12),{Pb2[S2P(OC6H4Me-p)2]2[μ-S2P(OC6H4Me-p)2]2}(13).The rare earth metal complexes including Sc,Y or Er, which are summarized as follows {[(p-MeC6H4O)2PS2]3Sc}.(4,4-bipy)(14),{[(p-BrC6H4O)2PS2]3Sc}.(4.4-bipy)(15),{[(PhO)2PS2]3Y}.(4,4-bipy)(16),{[(2,4,6-Br3C6H2O)2PS2]3Er}.(2,2-bipy)(17)and{[(PhCH2CH2O)2P S2]3Er}.(2,2-bipy)(18).The flame resistances of(p-BrC6H4O)2PS2NH2Et2and (p-ClC6H4O)2PS2NH2Et2in polypropylene(PP)have been studied.The result showed that when the added amount of the compound(p-BrC6H4O)2PS2NH2Et2in PP was30wt％,the LOI was26.5％,and the vertical flammability rating reached V-2level.The LOI of was25.0％when the added amount of the compound(p-ClC6H4O)2PS2NH2Et2was30wt％.The result also showed that the flame resistance of (p-BrC6H4O)2PS2NH2Et2in PP is better than that of in PP, which may be associated with the complex containing bromine.The complexes1and8are both coordination polymers. Each asymmetric unit consists of two metal atoms and two bidentate ligand (C6H5CH2CH2O)2PS2-. The continuous extension of the ligand (C6H5CH2CH2O)2PS2-formed polymer.In the complex2, the Cd atom is coordinated by four S atoms from two bidenate ligands (C6H5CH2CH2O)2PS2-and two N atoms from one molecule2,2’-bipyridine. Due to the existence of the weak bond Cd-S4, the Cd atom presents a distorted octahedral coordination. One-dimensional zigzag chain structure is formed by π...π stack interactions between2,2’-bipy and benzene, and π...π stack interactions from molecules2,2’-bipy.Complex6contains cation [Et2NH2]+、aion{[(p-Bu’C6H4O)2PS2]3Cd}-and a molecule CH2CH2OH. Cd atom lies in the distortion hexacoordination octahedral environment, and the ligand (p-ButC6H4O)2PS2-is asymmetric chelating bidentate ligand. There are a large number of short contacts and hydrogen bonding in the molecule, which form a three-dimension supramolecular structure.The complex7contains cation Cu(phen)2Cl+and anion (C6H5O)2PS2-. Cu atom lies in a five-coordinated square pyramidal envioronment, which is coordinated by four N atoms and a Cl atom. In the molecule, two phen planes are almost vertical, non-classical hydrogen bonds C-H...S and π...π stacking interactions of the complexes make the complex7form a two-dimensional network structure.The complexes9and13are both binuclear complex. The ligand (PhCH2CH2O)2PS2-in the complex9is bridged tridentate ligand, and Hg atom lies in a seven-coordinated polyhedron HgS5N2environment. One-dimensional chain structure is formed by π...π stack interactions. The ligand (p-MeC6H6H4O)2PS2-in the complex13exits bridged tridentate and chelating bidentate coordination modes. In the complex13, the aromatic plane of bridge ligand C81-C131and Pb1atom form a weak π coordination, which make Pb atom lie in the distorted absence pentagonal bipyramidal Pb(S5ArE) structure, at the same time, the complex13exits a eight-membered ring of chair conformation.Finally, the antibacterial activities of the ligands and synthesized complexes on staphylococcus aureus, bacillus subtilis and E. coli have been studied by the filter paper method. The result shows that O, O’-diaryldithiophosphates and their complexes having a good bactericidal activity against the three strains.