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Synthesis,Crystal Structure And Properties Of Salamo-based 3d And 3d-s Metal(?)Complexes

Posted on:2022-01-08Degree:MasterType:Thesis
Country:ChinaCandidate:T FengFull Text:PDF
GTID:2481306341979489Subject:Inorganic Chemistry
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In recent years,with the rapid development of modern coordination chemistry,the synthesis and properties of metal complexes have also attracted extensive attention.In the field of modern coordination chemistry,Salen type ligands and their derivatives play a very important role.The complex units formed by them can construct a variety of polymer structures,supramolecular structures and coordination polymers,which have been deeply studied in catalysis,optical materials and biology.Based on the study of Salen type ligands and their derivatives,researchers modified the[-C=N-]part of Salen type ligands and developed a class of Salamo type ligands containing R-CH=N-O-(CH2)n-O-N=CH-R structure.Salamo ligands have excellent flexibility and stability,and are easy to form stable metal complexes with a variety of metal ions.Moreover,Salamo ligands with two or more coordination cavities have the potential to form metal complexes with more abundant structures.Their metal complexes have evolved from simple mononuclear to polynuclear and more complex heterometal polynuclear complexes.Three Salamo type ligands HL1,H2L2 and H2L3 were synthesized.In this thesis,three different Ni(?)complexes[Ni2(L1)2(NCS)2](1),[Ni2(L1)2(N3)2](2)and[Ni(L1)(dca)]n(3)were synthesized by the reaction of the ligand HL1 with Ni(OAc)2·4H2O,and then adding different auxiliary ligands KSCN,Na N3 and dca(dca=dicyanamide)to the mixed solution.For the ligand H2L2,single crystals of the ligand H2L2was obtained.The ligand H2L2 was reacted with Co(NO3)2·6H2O,and then 4,4'-bipy was added to the mixed solution to obtain the Co(II)complex[{Co(L2)}2(4,4'-bipy)](4).The ligand H2L2 reacted with Cu(OAc)2·H2O to obtain the Cu(II)complex[{Cu(L2)}2](5).The ligand H2L2 was reacted with Ni(OAc)2·4H2O,and then pyridine and Na N3 were added to the mixedsolution.Unexpectedly,theNi(II)complex[Ni6(Py)6(?2-?2-N3)4(?3-?3-N3)2(?2-OAc)4(?3-CH3O)2(CH3OH)2](6)was obtained,in which the ligand H2L2 did not participate in the coordination.Two new 3d-s complexes[{Zn(L3)(?2-OAc)}2Sr]·0.33CH3OH·H2O(7)and[{Zn(L3)(?2-OAc)}2Ba](8)were synthesized by the reaction of H2L3 with Zn(OAc)2·2H2O and M(OAc)2·H2O(M=Sr and Ba),respectively.The structures of these complexes were determined by X-ray crystallographic analyses.The complexes 1-8 were characterized by UV-vis and IR spectra.In addition,the properties of the complexes 1-8 were also studied.Complex 1:C34H32N8Ni2O8S2,Mr=862.21,Monoclinic,P21/c;Complex 2:C32H32N12Ni2O8,Mr=830.21,Monoclinic,P21/n;Complex 3:C18H16N6Ni O4,Mr=439.08,Monoclinic,P21/n;Ligand H2L2:C24H32N2O4,Mr=412.51,Monoclinic,C 2/m;Complex 4:C58H68Co2N6O8,Mr=1095.04,Tetragonal,I 41/a;Complex 5:C48H60Cu2N4O8,Mr=948.08,Monoclinic,P 21/c;Complex 6:C42H56N24Ni6O12,Mr=1441.36,Monoclinic,P 21/c;Complex 7:C40.33H45.33N4O17.33Sr Zn2,Mr=1081.83,Trigonal,P 31;Complex 8:C40H42Ba N4O16Zn2,Mr=1102.85,Orthorhombic,Aea2.
Keywords/Search Tags:Salamo type ligand, Metal(?) complex, Crystal structure, Hirshfeld surface analysis, DFT calculation
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