Syntheses, Structures And Magnetic Properties Of Octacyanometallate-based Transition Metal Complexes Linked By Different Organic-ligand

The research about the structure and magnetic property of octacyanometalate-based complexes is a new challenge and potential field in the future. In this paper, eleven novel complexes have been synthesized by the slow diffusion in the method of in-situ or secondary assembly using the octacyanometalate [HN(n-C4H9)3]3W(CN)8(M=W, Mo) as building blocks with transition metals and ligands. They are five complexes connected by bidentate chelated ligands with N-atom:[Mn(H2O)2(dpe)]6[Wv(CN)8]4·4(dpe)·14H2O(1),[Mn3(H2O)6(azpy)3][Wv(CN)8]2·3(azpy)·4H2O(2),[Mn(H2O)2(azpy)]2[MoⅣ(CN)8]·2(azpy)·2H2O(3),[Mn(H2O)3(azpy)]2[Mn(CH3CN)2(azpy)][Wv(CN)8]2·5(azpy)·2H2O(4),[Mn(tmphen)(CH3O)(DMF)]3[W(CN)8]2·3H2O (5), four complexes linked by bidentate chelated ligands with O-atom:[Ni2(bpdo)(H2O)4][Mo(CN)8]·nH2O(6), Ni9(CH3O-H)24[W(CN)8]6·2H2O bpdo(7), Mn(bpdo)(H2O)2Cl2(8), Mn(bpbo)3(ClO4)2(9), and two complexes synthesized by TCNE:Mn6(H2O)9[Wv(CN)8]4·2H2O(10),[Mn(DMF)3]2-[Mn(DMF)4][Wv(CN)8]2·2H2O (11). Firstly, the structures of those complexes have been determined by single-crystal X-ray diffraction. Secondly, the complexes were characterized by powder X-ray diffraction (PXRD), infared spectra (IR), and thermogravitry (TG).The magnetic properties of some complexes were studied by SQUID magnetometer.For the complexes1-5bridged by bidentate chelated ligands L with N-atom(L=dpe, azpy, tmphen), their crystal structures have a great difference for the reasons of solvents and preparation methods. The3D complexes1-3have been prepared by the method of secondary assembly, and their crystal systems and space groups are various. The1D complexes4and5are synthesized, employing the method of in-situ assembly, and4is a1D chain structure linked Mn2+and [M(CN)8]3-by azpy(azpy=4,4’-azopyridine), while5is formed by Mn2+and [M(CN)8]3+connected with cyanogroups. The complexes land3show ferromagnetic coupling interaction between Mn and M (M=W or Mo) atoms, while2and4show antiferromagnetic coupling interaction between Mn and W atoms.For the complexes6-9bridged by bidentate chelated ligands L with O-atom(L=bpdo), the3D complex6is obtained by [Mo(CN)8]3-as building blocks in the method of in-situ assembly, but in the process,[MoV(CN)8]3-is reduced to [MoⅣ(CN)8]4-in the final products,7is prepared by stirring, including [Mo(CN)8]3-units.8is a1D chain structure by the method of in-situ assembly, while2D layer complex9is synthesized by secondary assembly, and they both don’t contain the building blocks of [Mo(CN)8]3-The complexes10and11, which are prepared using the same starting materials of TCNE, Mn2+and [M(CN)8]3-, show different structures without TCNE ligands.Mn atoms connected with [Mo(CN)8]3-by cyanogroups extend into a3D networks10, whereas Mn atoms connected with [Mo(CN)8]3-lead to a2D layer compound11.