Syntheses,Crystal Structures And Properties Of Transition/rare Earth Metal Complexes Constructed By A Flexible Tricarboxylate Ligand

The coordination polymers(CPs)have been increasingly accelerated developed and sustained with extensively studies on potential applications,including gas storage and separation,catalysis,luminescence,magnetism and so on.In particular,of great interest is the exploration of highly symmetrical multi-topic ligands,which connect the metal ions into generate multidimensional frameworks through the coordinated bonds and supramolecular interactions.In this paper we synthesized a flexible tricarboxylate ligand 2,2',2''-[1,3,5-triazine-2,4,6-triyltris(thio)] tris-acetic acid(H3TTTA)based on cyanuric acid three sodium salt(Na3TMT)and chloroacetic acid.A series of coordination polymers were synthesized by added 1,10-phenanthroline and the metal of Co(?),Mn(?)and Gd(III)et al,respectively.The syntheses,structures and properties of the complexes studied.The results are show as follows:1.By hydrothermal method,three transition mental complexes Co(HTTTA)(phen)(H2O)3(1),Ni(HTTTA)(phen)(H2O)3(2),Zn(HTTTA)(phen)(H2O)3(3)have been synthesized through the reaction of Co(?),Ni(?)and Zn(?)ions with H3 TTTA and phenanthroline.Elemental analysis,IR,XRD powder diffraction and CCD were used to confirm the crystal structures of the complexes.The photoluminescence,thermostability and heterogeneous catalysis of complexes 1-3were studied.Notably,the fluorescence response of Zn(?)complex is very obvious and the effect of 1-3 on the catalytic reaction of benzaldehyde is remarkable.In the cyanosilylation reactions,the complex 1 shows more activity than the other complexes.2.Through solvent adjustment,two different kinds of Mn(?)coordination polymers[Mn2(TTTA)(OH)(phen)2]n(4),[Mn3(TTTA)2(phen)2]n(5)were obtained from the flexible ligand H3 TTTA and phenanthroline.Elemental analysis,IR,XRD powder diffraction and CCD were used to confirm the crystal structures of the complexes.The photoluminescence,thermostability and heterogeneous catalysis of complexes 4-5were studied.For both composites,obvious decreased PL intensities can be observed and the complexes 4 shows the lower PL intensity.Moreover,significant effect can be obserbed in complexes 4-5 on the catalytic reaction of benzaldehyde and4-chlorobenzaldehyde,and the complex 5 can act as an efficient Lewis acid catalyst for the cyanosilylation of aldehydes.3.Two kinds of Gd(III)coordination polymers {[Gd(TTTA)(H2O)2]2H2O}n(6),[Gd(TTTA)DMF]n(7)were obtained from the flexible ligand H3 TTTA and the transition metal Gd(III)in different solvents.Elemental analysis,IR,XRD powder diffraction and CCD were used to confirm the crystal structures of the complexes.The photoluminescence,thermostability and heterogeneous catalysis of complexes 6-7were studied.Greatly decreased PL intensity can be obtained in Gd complex compare ligand.Also,catalytic results indicate that both complexes show excellent activities for the cyanosilylation of benzaldehyde,as well as its derivatives.