| Metal organic ccomplexes and MOFs have attracted extensive attention due to the potential applications in adsorption,catalytic,photoluminescence,magnetism and proton conductivity.So it is of great significance to design and synthesize novel organic acid and metallic ccomplexes,to explore the relationship between structure and performance and to select new materials with practical application value.In this paper,two kinds of organic phosphonicacidligands,namely,?benzylazanediyl?bis?methylene?-diphosphonicacid?H4L?and?benzene-1,3,5-triyltris?methylene??triphosphonicacid?H6bmt?,andapolycarboxylicacidligand,1,3,5-triazine-2,4,6-triamine hexaacetic acid?H6TTHA?were synthesized.The synthetic ligands were characterized by 1HNMR.Based on the three ligands,twenty new complexes with single crystal structures were obtained.And relative properties,such as magnetism,adsorption,proton conductivity,fluorescence etc,have been studied according to their structural characters.The main research contents are as follows:?1?Hydrothermal reactions of H4L or H6bmt with Fe?III?/Cu?II?nitrate result in five new metal phosphonates,namely,[FeHL?H2O?]n?1?,{[Cu2L?4,4?-bipy?0.5?H2O?]·0.25H2O}n?2?,[Cu2H2bmt?4,4?-bipy??H2O?2]n?3?,[CuH4bmt?2,2?-bipy?]n?4?and[Cu2?H4bmt?2?2,2?-bipy?2?H2O?4]?5?,respectively.X-ray structural analysis indicates that 2 and 3 feature 3D framework structures with 3,3,3,4-connected and 4,5-connected topology,respectively;1 and 4 display 1D chain structures,while 5 has a dimer structure.The di-or trisphosphonate ligands?H4L and H6bmt?in the five complexes adopt different coordination modes and the introduction of auxiliary ligands?4,4?-bipy and 2,2?-bipy?controls the dimensionality of the final complexes.The superoxide dismutase?SOD?activities of 2-5 were assessed by modified nitrobluetetrazolium?NBT?assay.The IC500 values of2-5 are 1.84,2.02,6.95 and 1.70?M,respectively,demonstrating better activity than most of the Cu-SOD mimic enzymes reported in literatures.Among them,2 and 3 have good stability and reusability under the simulative physiological conditions.The dismutation of 4 and 5 toward superoxide anion radicals can be attributed to the synergistic effect of the decomposition products.The magnetic properties of complexes 1-4 were also investigated,indicating the presence of magnetic exchange between metal ions.Among them,the complexes 1 and 3 exhibit antiferromagnetic interactions,while 2and 4 show ferromagnetic interactions between metal centres.?2?Six new transition metal phosphonates,[Cd?H2L??H2O?]n?6?,[Cd2?H2L?2?H2O?]n?7?,[Cd4?H2bmt?2?H2O?]n?8?,{[Cd2?H4bmt?2?2,2?-bipy?2]·4H2O}?9?,[Zn?H4bmt??2,2?-bipy?]n?10?and[Zn3?bmt??4,4?-bipy?2]n?11?,have been synthesized by H4L or H6bmt as well as auxiliary ligands under hydrothermal conditions and characterized by elemental analysis,IR,XRD as well as single-crystal X-ray diffraction.Structural analysis indicates that complexes 6-11 feature 0D-3D structures.The introduction of auxiliary ligands including 4,4'-Vinylenedipyridine,4-Cyanopyridine,4,4?-bipy,2,2?-bipy and H6TTHA increases the crystallinity and controls the dimensionality of the final complexes.The fluorescence emission properties of 6-11 and the free ligands were investigated in the solid state at room temperature.Moreover,the fluorescence lifetime???and quantum yield??f?were measured to further characterize the fluorescence properties.The results are compared to illustrate the influence of the auxiliary ligands and structure difference on the fluorescence properties.?3?Twonewtransitionmetalphosphonates,[Ni?4,4?-bipy?2?H3O?2?H2O?2]·2H4bmt·9H2O?12?and[Co?4,4?-bipy??H2O?4]·[Co?4,4?-bipy?2?H3O?2?H2O?2]·2H4bmt·6H2O?13?,have been synthesized by H6bmt and 4,4?-bipy.In these two complexes,the metal ions coordinate with 4,4?-bipy,while the phosphoric acid ligands connect to the adjacent oxygen atoms through O-H…O.There are abundant H-bonds in the structures.Base on these,the proton conduction properties of 12 and 13 have been investigated,and the influence of temperature on conduction is mainly discussed.?4?Threeflexiblearmscontainingtriazine-basedpolycarboxylate coordination polymers,{[Mn6?TTHA?2?4,4?-bipy?3?H2O?10]?3H2O}n?14?,{[Co3?H3TTHA?2?4,4?-bipy?5?H2O?8]?12H2O}n?15?and{[Zn4?TTHA??4,4?-bipy?2?OH?2]·2H2O}n?16?,have been synthesized under hydrothermal condition and structurally characterized by infrared spectroscopy,elemental analysis,XRD and X-ray single-crystal diffraction.Structure analysis indicates that 14 and 15 feature 3D framework structures with 2,3,4,4-net and 4,6-connected topology,while 15 displays a 2D plane structure with alternant rectangle structures of 22.695?11.485?2 in it.The investigation of the water vapor adsorption of 14-16 shows that the adsorption capacity of 15is comparable to the best water vapour adsorption material of MCM-41 with73.86%?41.03 mmol/g?of water uptake at 90%RH.Moreover,15 also displays good CO2 adsorption property with 31.5 cm3 g-11 uptake at 298 K and750 mm Hg.Based on the structural characters of 14 and 15,high water content and hydrophilic units as well as abundant of hydrogen-bonding networks in the complexes,the proton conductivities of the two complexes were measured.The results indicate that the highest proton conductivities of the complexes at 297 K and 98%RH are 1.188×10-44 S·cm-11 for 14 and5.87×10-44 S·cm-11 for 15,respectively.The higher Arrhenius activation energy indicate vehicle mechanism of proton conduction for these two complexes.To the best of our knowledge,15 is the first example which has excellent performances in CO2 and water adsorption as well as proton conduction.Moreover,the molecular magnetism of 14 and 15 was investigated and quantitatively calculated by PHI program.Additionally,the fluorescence emission properties,fluorescence lifetime???and quantum yield??f?of 16and the free ligands were investigated in the solid state at room temperature.?5?Four rare earth coordination polymers,{[Tb4?TTHA?2?H2O?4]·7H2O}n?17?,{[Ce2?TTHA??H2O?4]·4H2O}n?18?,{[Tb2?TTHA??H2O?2]·7H2O}n?19?and{[Eu2?TTHA??H2O?2]·11H2O}n?20?,have been synthesized by H6TTHA.Among them,the complexes 19 and 20 have same connection type,however,the H-bonds in two complexes are different.There are infinite water chain in19 and two different forms of water clusters in 20,namely,?H2O?6 and?H2O?17.The complexes 18-20 have the same 4,4-connected topology structures.It indicates that the complex 17 exhibits proton conductivities over10-22 S·cm-11 at 295-358 K and 98%relative humidity,which is higher than the conductivities of most MOFs materials. |
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