Study On Syntheses,Crystal Structures And Luminescent Properties Of Salamo-type 3D-4f Hetero-bimetallic Complexes

Salen-type metal complexes have been widely used in the fields of biology,catalysis and magnetic materials,especially Salen-type 3d-4f complexes,which have become the focus of coordination chemistry as potential materials in recent years.Salamo-type ligands,which are derived from Salen-type ligands,can form more flexible metal complexes due to their more stable chelating function.In order to further study the synthesis,crystal structures and photophysical properties of Salamo-type 3d-4f heterometallic complexes,a hexadentate Salamo-type ligand and six 3d-4f heteronuclear bimetallic complexes [Zn(L)(OAc)Sm(NO3)2](1),[Zn(L)(OAc)Eu(NO3)2](2),[Zn(L)(OAc)Tb(NO3)2](3),[Zn(L)(OAc)Dy(NO3)2](4),[Cu(L)Nd(NO3)2(C2H5OH)](5)and [Zn(L)(OAc)Ce(NO3)2(CH3OH)](6)are designed and successfully synthesized.[Zn(L)(OAc)Sm(NO3)2]: Empirical formula,C22H25SmN4O14 Zn,Formula weight,785.18,Monoclinic,P21/n,Unit call dimensions: a = 13.1508(10)?,b = 13.2882(9)?,c = 16.3883(9)?,β = 104.519(7)°,Z = 4,V = 2772.4(3)?3,R1 = 0.0724,w R2 = 0.0931;[Zn(L)(OAc)Eu(NO3)2]: Empirical formula,C22H25EuN4O14 Zn,Formula weight,786.82,Monoclinic,P21/n,Unit call dimensions: a = 13.1508(7)?,b = 13.2769(5)?,c = 16.3725(9)?,β = 104.442(6)°,Z = 4,V = 2768.3(2)?3,R1 = 0.0490,wR2 = 0.0639;[Zn(L)(OAc)Tb(NO3)2]: Empirical formula,C22H25TbN4O14 Zn,Formula weight,793.75,Monoclinic,P21/n,Unit call dimensions: a = 13.1130(6)?,b = 13.2655(5)?,c = 16.3649(7)?,β = 104.340(5)°,Z = 4,V = 2758.0(2)?3,R1 = 0.0386,wR2 = 0.0610;[Zn(L)(OAc)Dy(NO3)2]: Empirical formula,C22H25DyN4O14 Zn,Formula weight,797.33,Monoclinic,P21/n,Unit call dimensions: a = 13.0950(5)?,b = 13.2699(4)?,c = 16.3621(6)?,β = 104.270(4)°,Z = 4,V = 2755.52(17)?3,R1 = 0.0337,wR2 = 0.0563;[Cu(L)Nd(NO3)2(C2H5OH)]: Empirical formula,C22H28CuN5NdO16,Formula weight,826.27,Monoclinic,P21/n,Unit call dimensions: a = 9.4291(3)?,15.2896(4)?,c = 21.3512(4)?,β = 92.353(2)°,Z = 4,V = 3075.55(14)?3,R1 = 0.0352,w R2 = 0.0587;[Zn(L)(OAc)Ce(NO3)2(CH3OH)]: Empirical formula,C23H29CeN4O15 Zn,Formula weight,806.99,triclinic,P1,Unit call dimensions: a = 9.0577(8)?,b = 12.0332(13)?,c = 15.4757(13)?,α = 99.496(8)°,β = 102.562(7)°,γ =111.854(9)°,Z = 2,V = 1470.7(3)?3,R1 = 0.0345,wR2 = 0.0649;The ligand H2 L and all complexes are characterized by 1H NMR,elemental analysis and IR spectra and structurally characterized by X–ray single crystal diffraction.Additional,the fluorescence properties and magnetic properties of ZnIILnIII(Ln = Sm,Eu,Tb and Dy)complexes are analyzed and the mechanism of the luminescence is discussed.