Synthesis,Crystal Structures And Properties Of The Complexes With Series N-3-pyridine Sulfonyl Amino Acids

The metal cluster compound with holes has become a current research in the chemical industry.A lot of studies have been conducted,and also create a large number of structural diversity of clusters.The achievements are mostly concentrated in the nitrogen impurity complexes,carboxylic acid clusters,mixed ligand clusters and organophosphorus ligands clusters,but few reports of sulfonic acid type complexes.This paper focuses on study about the synthesis,characterization and properties of coordination compound with the ligand of N-3-Pyridine Sulfonyl amino acids(?-alanine(H2L1),?-alanine(H2L2),threonine(H3L3),glycine(H2L4)).The coordination modes of sulfonyl amino acid have flexibility and diversity,so it is easier to assemble into supramolecular structures.Porous metal cluster based on sulfonic group content research has become one of the current research hotspots,due to it has strong academic and potential application value.Changing of experimental conditions,for example of starting material ratio,pH,solvent,and so on,have built nine unreported metal complexes,The structures of these complexes have been determined by X-ray crystallographic methods and characterized by element analyses and IR spectra.And magnetic properties of some compounds have been briefly investigated.The main work in the paper includes five chapters:Chapter One:We introduce the concept and development of super molecular clusters,the impact conditions of the synthesis of clusters,and briefly introduces research status of the sulfonyl amino acid complexes.Chapter Two:Synthesis of N-3-pyridinesulfonyl amino acid ligands(?-alanine(H2L]),?-alanine(H2L2),threonine(H3L3),glycine(H2L4)).Chaper Three:four Co(?)complexes,namely[Co(HL1)·(H2O)2]n(1),[Co2(HL2)4·H2O]n·4H2O·2EtOH(2),[Co9(H2L3)6(OH)6(CO3)(H2O)6]·CO3·2H2O(3),[Co9(HL1)6(OH)6(CO3)2(CH3COO)2(H2O)2]n·H2O(4)have been synthesized under different conditions.Single-crystal X-ray analysis reveals that complex(1)is One-dimensional chain polymer;complex(2)is dual-core two-dimensional plane polymer.Complex(3)is nine nuclear supramolecular clusters bridged by two ?6-CO32-.Complex(4)is one-dimensional coordination polymer based on Co9 cluster.These four different complexes were by adjusting the starting material ratio and changing solvents.Complex(3)and(4)exhibit weak antiferromagnetic interaction,and complex(3)is accompanied by spin tilt.Chaper Four:four nine nuclear nickel clusters,namely[Ni9(HL4)6(OH)6(CH3COO)2(CO3)2(H2O)2]·7H2O(5),[Ni9(HL2)6(OH)6(CO3)2(H2O)6]·2OH·9H20·2EtOH(6),[Ni9(HL1)6(OH)6(CO3)2(H2O)6]·CO3·7H2O(7),[Ni9(HL])6(OH)7(CH3COO)(CO3)2(H2O)2]n·14H2O(8)have been synthesized.Single-crystal X-ray analysis reveals that complex(5)?(7)are nine nuclear supramolecular clusters bridged by two ?6-CO32-and complex(8)is one-dimensional chain coordination polymer based on Ni9 cluster and induced by solvent.Complex(5)?(8)exhibit weak antiferromagnetic interaction.Chapter Five:one Mn(?)complex,namely Mn(HL1)2(H2O)2]n(9)have been synthesized.Single-crystal X-ray analysis reveals that complex(9)is mononuclear coordination polymer and two-dimensional plane supramolecular structures by hydrogen.