| Salen-type ligand and its analogues continue to play significant roles in modern coordination chemistry.Because of its potential application value,the research heat has not decreased in recent years.Their metal complexes have been explored to construct supramolecular structures and coordination polymers.Numerous investigations on these compounds,such as catalysis activities,nonlinear optical materials,fluorescent materials and biological activities and etc.In this thesis,a new bis(Salamo)-type tetraoxime ligand(H4L)was designed and synthesized for the first time based on Salamo-type ligand.Since the ligand has two Salamo cavities,each Salamo cavity can chelate with one metal ion,and the ligand will change from a linear molecule to a C-type molecule after complexing with two metal ions,thus forming a larger O4 cavity,which can further coordinate with metal ions to form homonuclear and heteropolynuclear complexes.In this thesis,a trinuclear Zn? complex[Zn3(L)(OAc)2(H2O)]·CH2Cl2(1)was synthesized by the reaction of ligand H4L and Zn(OAc)2·2H2O.Nine novel structural 3d-4f complexes were synthesized by the reactions of ligand H4L,Zn(OAc)2·2H2O and Ln(NO3)·6H2O(Ln=La,Ce,Pr,Nd,Gd,Sm,Eu,Tb and Dy),[Zn4(L)2La(NO3)2(OEt)(H2O)](2),[Zn4(L)2Ce(NO3)2(OMe)(MeOH)](3),[Zn4(L)2Pr(NO3)2(OEt)(EtOH)](4),[Zn4(L)2Nd(NO3)2(OMe)(MeOH)](5),[Zn4(L)2Gd(NO3)2(EtOH)2]NO3·C2H5OH·2CHCl3(6),[Zn4(L)2Sm(NO3)2(EtOH)2]NO3·H2O·2CHCl3(7),[Zn4(L)2Eu(NO3)2(EtOH)2]NO3·C2HSOH·2CHCl3(8),[Zn4(L)2Tb(NO3)2(EtOH)2]NO3·C2H5OH(9)and[Zn4(L)2Dy(NO3)2(EtOH)2]NO3·C2H5OH·2CHCl3(10).Their structures were determined and characterized by single crystal X-ray crystallography.The fluorescence properties of complexes 1-10,and the catalytic activities of complexes 1 and 7 were studied.Complex 1:C39H36Zzn3N4O13CO2,Formula weight,1035.73,Triclinic,P-1,Unit call dimensions:a=15.7572(9)(?),b=16.4079(9)(?),c=16.4852(9)(?),a=90.038(2)°,?=104.887(2)°,?=97.172(2)°,Z=4,V=4084.5(4)(?)3,R1=0.0483,wR2=0.1233;Complex 2:C70H59LaZn4N10O24,Formula weight,1824.66,Monoclinic,C2/c,Unit call dimensions:a=23.8927(11)(?),b=15.5212(7)(?),c=45.813(2)(?),?=90°,?=97.7300(10)°,?=90°,Z=8,V=16835.2(13)(?)3,R1=0.0454,wR2=0.1044;Complex 3:C70H59CeZn4N10O24,Formula weight,1824.86,Monoclinic,C2/c,Unit call dimensions:a=16.9226(7)(?),b=23.3361(10)(?),c=24.4208(13)(?),?=90°,?=109.4290(10)°,?=90°,Z=4,V=9094.8(7)(?)3,R1=0.0448,wR2=0.1059;Complex 4:C72H63PrZn4N10O24,Formula weight,1854.71,Monoclinic,C2/c,Unit call dimensions:a=16.7809(7)(?),b=23.4499(7)(?),c=24.1484(11)(?),?=90°,?=108.736(5)°,?=90°,Z=4,V=8999.1(7)(?)3,R1=0.0412,wR2=0.1007;Complex 5:C70H59NdZn4N10O24,Formula weight,1829.99,Monoclinic,C2/c,Unit call dimensions:a=16.9226(7)(?),b=23.3361(10)(?),c=24.4208(13)(?),?=90°,?=109.4290(10)°,?=90°,Z=4,V=9094.8(7)(?)3,R1=0.0377,wR2=0.0974;Complex 6:C76H72GdZn4N11O28Cl6,Formula weight,2218.87,Monoclinic,C12/c1,Unit call dimensions:a=16.9752(18)(?),b=23.090(2)(?),c=24.837(3)(?),?=90°,?=111.300(2)°,?=90°,Z=4,V=9069.8(16)(?)3,R1=0.0846,wR2=0.1698;Complex 7:C74H68SmZn4N11O28Cl6,Formula weight,2183.92,Monoclinic,C12/c1,Unit call dimensions:a=16.8229(9)(?),b=23.2495(12)(?),c=24.2036(14)(?),?=90°,?=108.673(2)°,?=90°,Z=4,V=8968.3(9)(?)3,R1=0.0501,wR2=0.1291;Complex 8:C76H72EuZn4N11O28Cl6,Formula weight,2213.58,Monoclinic,C12/cl,Unit call dimensions:a=16.8834(9)(?),b=23.1409(12)(?),c=24.3047(12)(?),?=90°,?=108.679(2)°,?=90°,Z=4,V=8995.6(8)(?)3,R1=0.0528,wR2=0.1213;Complex 9:C74H70TbZn4N11O28,Formula weight,1981.81,Monoclinic,P121/cl,Unit call dimensions:a=13.542(3)(?),b=28.886(7)(?),c=19.183(4)(?),?=90°,?=96.675(4)°,?=90°,Z=4,V=7453(3)(?)3,R1=0.0877,wR2=0.2247;Complex 10:C76H72DyZn4N11O28Cl6,Formula weight,2224.12,Monoclinic,C12/c1,Unit call dimensions:a=16.9466(9)(?),b=23.0127(12)(?),c=24.9394(15)(?),?=90°,?=111.278(2)°,?=90°,Z=4,V=9063.0(9)(?)3,R1=0.0492,wR2=0.1196. |
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