| Coordination polymers,which consist of metal ions or metal clusters connected by organic ligand,have become research hotspots in multiple disciplines such as coordination chemistry,crystallography,physical chemistry,and materials science.In this article,eleven new coordination polymers were constructed by assembling formic acid or oxalic acid,3,2,3-tetramine,bis(3-aminopropyl)amine,N,N'-Dimethyl-1,3-propanediamine,N-methyl-1,3-propanediamine,benzylamine,triethylamine,(R)-1-phenylethanamine,2,2,2-tetramine and metal ions.The crystal structure the magnetic,electronic conduction,and proton conduction of the complexes were studied.According to the different ligands,it can be divided into two parts.In the first part,four cases of metal formate[ETP][Fe5?Fe?(?3-O)2(?-O2CH)15](1),[ATP]0.5[Fe6?(?3-O)2(?-O2CH)15](2),[NH3(CH2)3NH3(CH2)2NH3(CH2)3NH3]x/4[Fe?1-xFex?(HCOO)3](3),[CH3NH3(CH2)3NH3CH3][Fe?Fex?Co?2-x(HCOO)9](4)were reported.ETP is 3,3'-(ethane-1,2-diyl)bis(3,4,5,6-tetrahydropyrimidin-1-ium)generated by the in situ reaction of N,N'-bis(3-aminopropyl)ethylamine with formic acid,ATP is 3-(3-ammoniopropyl)-3,4,5,6-tetrahydropyrimidine-1-ium generated by the in situ reaction of 3,3'-diaminodipropylamine with formic acid.The structural analysis shows that 1 and 2 have three nuclear cluster base one-dimensional chain structure,3 and 4 have three dimensional metallic formic acid structure,the topologies of 3 is single node(49·66),and the topological of 4 is binodal(49·66)2(412·63)nickel arsenide.The magnetic test results show that all the compounds1,3 and 4 exhibit spin-canting behavior,and there is strong antiferromagnetic coupling between metal ions.1 exhibits magnetic ordering behavior between 2 K and25 K.The electrical conductivity at 20?is 1.16×10-6 S/cm.Rising with temperature,reaching 2.95×10-5 S/cm at 160?.In the second part,seven cases of metal oxalate[NH3(CH2)3NH2CH3]3[Fe2?Fe2?(C2O4)4(SO4)4(H2O)4]·(H2O)2(5),[CH3NH2(CH2)3NH2CH3]3[Fe2?Fe2?(C2O4)4(SO4)4(H2O)4]·(H2O)2(6),(C6H5CH2NH3)Fe(C2O4)(SO4)(7),(C6H5CH2CH3NH3)Fe(C2O4)(SO4)(8),[(CH3CH2)3NH]2Fe?Fe?(C2O4)2.5(SO4)(9),[PEA][Fe2(C2O4)3]·H2O(10),[CH3NH2(CH2)3NH2CH3]2Fe2(C2O4)(H2O)2Cl8(11)were reported.PEA is 2,2'-(piperazine-1,4-diy)bis(ethan-1-aminium)generated by the in situ reaction of 2,2,2-tetramine with oxalic acid.Structural analysis shows that 5 and 6 are one-dimensional chains of mixed valence metal oxalic acid,7,8 and 9 are three-dimensional frames with oxalate ions and sulfate ions as bridging ligands,10 is two-dimensional honeycomb oxalic acid layer,11 is binuclear iron oxalate structure.Magnetic results show that 5 and 6 exhibit spin-canting behavior.The field-cooling curves in different magnetic field intensity show that the two compounds are magnetized,and the magnetic phase transition temperatures are 8.5K and 9K.The four metal oxalic acid compounds 7,8,9 and 11 are typical antiferromagnets.The proton conductivity of 5 and 6 pressure plates at RH100%at different temperatures and 80?at different relative humidity was investigated.The results of show that the proton conductivity of 5 and 6 is 0.29 S/cm and 0.261 S/cm at RH100%and 80?,respectively.With the decrease of temperature and relative humidity,the proton conductivity also decreases.Their activation energies Ea are 0.62e V and 0.28e V,respectively,based on the variational proton conductivity. |
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