Syntheses,Magnetic And Dielectric Properties Of The Azido Coordination Polymers Containing Ammonium As Cationic Guest

The azido coordination polymers（CPs）containing ammonium as cationic guest exhibit diverse structures,owing to various coordination modes of the azide ligand as well as the variation in the size or shape of the cationic templates,which may generate rich and varied physical properties.Recently,the azide anion still remains a popular bridging ligand in the field of molecular magnetism.It has been found that minor varieties of the components within the metal-azido system may dramatically change the structures,and the magnetic behaviors of the metal-azido compounds could be strongly influenced by the composition and structure.Up to now,besides the very few binary azides,most of the reported metal-azide compounds consist of those with a wide variety of coligands,whereas those with anionic metal-azide substructures in combination with charge-balanced cationic templates are somewhat rare.In addition,the small-size cationic templates were used to build three-dimensional perovskite-like azido CPs,which can serve as a model compound to understand and modulate molecular/ionic dynamics of guest molecules in confined space.In this paper,using azide anion as the bridging ligands and some moderate-size organic cation as the templates,we present three new nickel（II）or copper（II）azido CPs,namely,[Ni（N₃）₂（Deeda）]（1）,（DeaH）[Cu₃（N₃）₇]（2）,and（TeaH）[Cu₄（N₃）₉]（3）,where Deeda,（Dea H）⁺and（TeaH）⁺represent N,N-diethylethane-1,2-diamine,diethylammonium and triethylammonium,respectively.Magnetic studies revealed that they exhibit metamagnetism,spin glass and canted ferromagnetism,respectively,induced by different coordination modes of the azide ligands.In addition,we also select small-size cationic templates such as trimenthylammonium cation,affording three new double perovskite-like azido CPs,namely,（Me₃NH）₂[FeNa（N₃）₆]（4）,（Me₃NH）₂[CrNa（N₃）₆]（5）,（Me₃NH）₂[Cr K（N₃）₆]（6）.The guest molecular dynamics within these compounds are investigated by variable-temperature dielectric spectroscopy.Through the study of these compounds,we have a better understanding on the structures and properties of the metal-azido compounds.