Studies On The Synthesis,Structure And Properties Of Complexes Of 1,3,5-Benzenetricarbonyltrivaline And 1,3,5-Benzenetricarboxylate

In recent years,chiral materials and chiral compounds have received extensive attention of the chemical researchers due to their vigorous development and the potential application in various fields and their commercial values.In this paper,nine complexes were prepared,the components and structures of which were determined by IR,single crystal X-ray diffraction analysis,thermogravimetric(TG),elemental analysis,CD and PXRD.Their fluorescent and magnetic properties were also investigated.T he main work is listed below.1.A pair of chiral organic ligands 1,3,5-Benzenetricarbonyltri(L-valine)(L-TMTVH3)and 1,3,5-Benzenetricarbonyl(D-valine)(D-TMTVH3)were synthesized from the reactions of trimesoyl chloride with L-valine and D-valine respectively,which were characterized through IR,MS,1H NMR and 13C NMR.2.The reactions of L-TMTVH3 or D-TMTVH3 with Zn(NO3)2-6H2O or Cd(NO3)2·6H2O gave a pair of chiral complexes[Zn2(OH)(L-TMTV)(phen)(H2O)]4·9H2O(1)and[Zn2(OH)(D-TMTV)(phen)(H2O)]4·9H2O(2),and[Cd3Na6(BTC)4(CH3OH)4(H2O)8](3),respectively.The two kinds od Zn(Ⅱ)ions in complexes(1)and(2)are four-and five-coordinated in tetrahedral geometries,respectively.The carboxylate groups in L-TMTV3-and D-TMTV3-adopt single and sys,syn-briding modes.Two adjacent Zn(Ⅱ)are bridged by one μ2-OH-ligand and one sys,syn-briding carboxylate group to form a dinuclear Zn2 secondary building unit.Each L-TMTV3-or D-TMTV3-ligand bridges three such units and each dinuclear unit was linked to another three ones by three L-TMTV3-or D-TMTV3-ligands,leading to the construction of a two dimensional framework.When Cd(NO3)2·6H2O was used in the reaction,it gave complex(3).L-TMTV3-and D-TMTV3-decomposed into 1,3,5-Benzenetricarboxylate(BTC3-)in these reactions.Cdl and Cd2 in complex(3)are eight-and six-coordinated in square pyramidal and octahedral geometries,respectively.Each carboxylate group of the BTC3-ligand bridge one Cd2+and two Na+ cations with two of them acting as chelating-bridging modes and the other one behaving as syn,syn-brdging mode.Three Na+ are linked by four water molecules to form a trinuclear[Na3(μ-H2O)4(CH3OH)]3+ unit.The Cd2+ ions and such trinuclear units are linked by BTC3-to construct a 3D structure.The fluorescent studies of complex(1)and(3)revealed intraligand and ligang to metal charge transfer.3.The reactions of L-TMTVH3 or D-TMTVH3 with Co(NO3)2·6H2O,Ni(NO3)2·6H2O,Cu(NO3)2·6H2O and CuCl2·6H2O gave[(CH3)2NH2]2[Co3O(L-TMTV)2(H2O)3]·10H2O(4),[(CH3)2NH2]2[Co3O(D-TMTV)2(H2O)3]·10H2O(5),[(CH3)2NH2]2[Ni3O(L-TMTV)2(H2O)3]·8H2O(6),[(CH3)2NH2]2[Ni3O(D-TMTV)2(H2O)3]·8H2O(7),[Cu3(L-TMTV)2(H2O)9]·3H2O(8)and[Cu12(L-TMTV)8(H2O)12]·nH2O(9).Complexes 4-7 are isomorphic.Their metal ions are all six-coordinated in octahedral geometries.All carboxylato groups in L-TMTV3-and D-TMTV3in complexes 4-7 adopt syn,syn-bridging modes.Three M(Ⅱ)ions in complexes 4-7 are consolidated by one μ3-O2-and six carboxylato groups from six L-TMTV3-or D-TMTV3ligands to form a triangular trinuclear unit[M3(μ3-O)(COO)6]2-.Each L-TMTV3-and D-TMTV3-bridges three triangular units and each trinuclear unit was linked to another six ones by L-TMTV3-and D-TMTV3-ligands,which leads to the construction of a two dimensional framework.In complex(8),all carboxylate group of the L-TMTV3-ligand adopt monodentate coordination modes.Each L-TMTV3-ligand bridges three Cu(Ⅱ)ions and each Cu(Ⅱ)ions was linked to another four ones by two L-TMTV3-ligands,leading to the construction of a two dimensional framework.In complex(9),the L-TMTV3-ligands adopt,μ6:η6-bridging modes,connecting six Cu(Ⅱ)ions.Two adjacent Cu(Ⅱ)ions are bridged by four syn,syn-bridging carboxylate groups to build a[Cu2(COO)4(H2O)2]unit.Six such units are consolidated by eight L-TMTV3-ligands,constructing a octahedral nanospheric ball.The magnetic studies revealed antiferromagnetic interactions between metal ions for cmplexes(4)and(8),and ferromagnetic interactions between transition metal ions for complex(6).