Synthesis,Characterization And Magnetic Properties Of Clusters Bridged By Phenolic Hydroxyl Groups

Polyphenol amine compounds contain N,O atoms which have strong coordination ability,this kind of ligands have spatial confinement and coordination sites.The metal complexes have the potential performance of catalytic chemistry,biological chemical,magnetic material,molecular recognition etc.In this paper,by using polyphenol amine compounds H4L,H2L1 and H2L2 as the ligands,16 complexes with rare-earth metal ions and transition metal ions are synthesized.They are characterized by IR,XRD and TG and their crystal structures are determined by single crystal X-Ray diffraction structural analysis.In the first chapter,the introduction outline the characteristics and applications of the polyphenol amine compounds,the research progress on polyphenol amine complexes,as well as the research basis,purpose,meaning in this paper.In the second chapter,six complexes based on ligand[2-[1,3-bis(2-hydroxy benzyl)-2(2-hydroxyphenyl)-5-(2-pyridyl)-4-alkyl imidazole]phenol(H4L)with transition metal ions have been isolated and the structures of these compounds are researched completely.1.[Cu4(H2L)2(NO3)2](NO3)2(1)2.[Cu4(HL)2(DMF)2](ClO4)2(NC3H6)2(2)3.[Ni4(L)2](CH3OH)2(3)4.[Co4(L)2](CH3O)2(4)5.[Ni4(L)2(DMF)2](NC2H6)2(5)6.[Co4(L)2]·[Co4(L)2(DMF)2](DMF)2(6)H2L2-performs as a heptadentate mode to chelate two Cu2+ ion to form a[Cu2(H2L)]fragment,while two[Cu2(H2L)]fragments are bridged to each other via two Cu-0phenolate bond,resulting in a linear tetranuclear complex(1).Moreover,when HL3-ligand performs as a hexadentate mode to chelate two Cu2+ion,a[Cu2(HL)]fragment is formed,while two[Cu2(HL)]fragments are bridged to each other via Cu-Ophenolate bond,resulting in a linear tetranuclear complex(2),nitrate of complex(1)performs as a monodentate mode to coordinated to terminal Cu2+,DMF of complex(2)coordinated to terminal Cu2+.Four Cu atoms are five-coordinated with tortile quadrangular pyramid.The complexes of(3)and(4)are homeomorphism in which L4-ligand performs as a heptadentate mode to chelate two M2+ ion(M=Ni,3;Co,4)to form a[M2L]fragment,while two[M2L]fragments are bridged to each other via four M-0phenolate,resulting in a M4O6 tetranuclear based on "cutaway cubane" structure.Four metal atoms are two six-coordinated with Octahedron and two five-coordinated with tortile trigonal bipyramid.The coordination mode of complex(5)is similar to complex(3),and the difference of complex(5)is that two DMF coordinated to terminal Ni(?),resulting in four Ni atoms are six-coordinated with Octahedron.Complex(6)is a co-crystal complex,which consist[Co4(L)2]and[Co4(L)2(DMF)2].[Co4(L)2]is the same with complex(4),the structure of[Co4(L)2(DMF)2]are all the same to the complex(5).In the third chapter,three complexes based on ligand bis(2-hydroxybenzyl)amine(H2L1)with transition metal ions have been isolated and the structures and properties of these compounds are researched completely.7.[Cu2(L)2(7)8.[Cu8(L)4(OH)4(H2O)4](ClO4)(8)9.[Ni3(HL)2(AC)4(DMF)2](9)Li2-ligand performs as a tridentate mode to chelate a Cu2+ion to form a[Cu(L)]fragment,while two[Cu(L)]fragments are bridged to each other via Cu-Ophenolate bond,resulting in a binuclear complex(7).Two Cu atoms are four-coordinated with parallelogram.Moreover,four such fragments are alternatively bridged by four additional Cu2+ via Cu-Ophenolate bond,resulting in a cyclic octanuclear complex(8),?3-OH are connected by two bridging Cu2+and one chelating Cu2+,and water coordinated to chelating Cu2+.Eight Cu atoms were four four-coordinated with plane quadrilateral and four five-coordinated with tortile quadrangular pyramid.HL1-ligand performs as a tridentate mode to chelate one Ni2+ ion to form a[Ni(HL)]fragment,while two[Ni(HL)]fragments are alternatively bridged by a additional Ni2+ via Ni-Ophenolate bond and acetate,resulting in a catenarian trinuclear complex(9),and DMF coordinated to chelating Ni2+.Three Ni atoms are six-coordinated with Octahedron.Magnetic indicates that complex(8)exhibits anti-ferromagnetic properties in the temperature range of 300-2.0K,while complex(9)is ferromagnetic and anti-ferromagnetic synergistic effect.In the fourth chapter,seven complexes based on ligand bis(2-hydroxy-3-methoxy)benzyl amine(H2L2)with rare-earth metal ions and transition metal ions have been isolated and the structures of these compounds are researched completely.10.[Ni4(L)2(NO3)(CH3O)2](CH3OH)2(10)11.[Co4(L)2(NO3)(CH3O)2](CH3OH)2(11)12.[Ni4(L)2(CH3O)2(CH3OH)4](ClO4)2(12)13.[Co4(L)2(CH3O)2(CH3O)4](ClO4)2(13)14.[Cu4(L)2(O)(DMF)4](ClO4)3(14)15.[Yb2Ni2(L)2(AC)4(CH3O)2](15)16.[Mn5(L)3(NO3)2(OH)](CH3OH)3(16)The complexes of(10)and(11)are homeomorphism in which L22-ligand performs as a tridentate mode to chelate one M2+ion(M=Ni,10;Co,11)to form a[M(L)]fragment,while two[M(L)]fragments are alternatively bridged by two additional M2+via M-Ophenolate bond,resulting in a M406 tetranuclear based on "cutaway cubane" structure,?3-MeOH are connected by two bridging M2+and one chelating M2+,nitrate performs as a bidentate mode to chelate one M2+ ion by two oxygen atoms.Four metal atoms are six-coordinated with Octahedron.The complexes of(12)and(13)(M=Ni,12;Co,13)are also homeomorphism,their coordination mode and configuration are similar to complexes(10)and(11),two methanol coordinated to chelating M2+instead of two oxygen atoms on nitrate.In the complex(14),L22-ligand performs as a tridentate mode to chelate one Cu2+ion to form a[Cu(L)]fragment,as DMF coordinated to one of Cu2+,resulting in two different fragments.While two different fragments are alternatively bridged by two additional Cu2+ via Cu-Ophenolate bond,resulting in a M4O5 tetranuclear based on"cutaway cubane" structure,p3-OH are connected by two bridging Cu2+and one chelating Cu2+,the coordination mode of the ligand is similar to complexes(10)-(13),the difference is that DMF coordinated to Cu atom instead of nitrate and methanol,the number of coordination to four Cu atoms is different,resulting in the coordination mode of four Cu atoms change,and configuration of complex(14)also changes a little.Four Cu atoms are one four-coordinated with parallelogram,one five-coordinated with tortile quadrangular pyramid and two six-coordinated with Octahedron,The complex of(15)is hybrid tetranuclear complex[Yb2Ni2(L)2(AC)4(CH3O)2],L22-ligand performs as a tridentate mode to chelate one Ni2+ion to form a[Ni(L)]fragment,while two[Ni(L)]fragments are bridged by two additional Yb3+via Yb-Ophenolate bond and acetate,resulting in a Ni2Yb206 tetranuclear based on "cutaway cubane"structure,?3-MeOH are connected by two bridging Yb3+and one chelating Ni2+.Two Ni atoms are six-coordinated with Octahedron and two Yb atoms are eight-coordinated with a square antiprism geometry.In the complex(16),L22-ligand performs as a tridentate mode to chelate one Mn2+ ion to form a[Mn(L)]fragment,while three[Mn(L)]fragments are alternatively bridged by two additional Mn2+ via Mn-Ophenolate bond and nitrate,resulting in a double cap three prism Mn506 structure,?3-OH are connected by three chelating Mn2+.Five Mn atoms are six-coordinated with Octahedron.