Synthesis And Characterization Of Transition Metal (cr, Co, Fe) And Main Group Elements (ga, In), Boron Phosphate And Phosphate System Compounds

Syntheses and characterizations of new compounds in transition metal (Cr, Fe, Co) and main group elements (Ga, In) borophosphate and phosphatesystemsAbstractOpen-framework borophosphates and phosphates are two kinds of potential materials for the catalysis, ion-exchangers or molecular sieves. More and more material scientists and chemists focus on them.In this thesis, several synthesis and characterization methods were employed to explore some new transition metal, Indium and Gallium borophosphates and phosphates. For this purpose mild hydrothermal and high-temperature solid state methods were introduced. X-ray powder and single crystal diffraction, chemical analysis. SEM, EDX, FT-IR, TG-DTA and magnetic susceptibility measurement methods were applied to characterize the new compounds.In the borophosphates studying, four new compounds were synthesized and characterized. In the phosphate systems, three new compounds were synthesized and characterized. Three of them have new type of structure.Cr,[BP3Ol2], the first Cr-based borophosphate. was synthesized by high-temperature solid state methods, using CrPO4 ?4H2O + BPO4 ?xH2O or Cr2O, + BPO4 as reagents, the structure was solved by ab initio X-ray powder diffractionmethods and refined by Rietveld methods, obtaining the structure data: Trigonal, P3 (No. 143), a=7.95419(6)A, c=7.36130(l)A, F=403.4A3, Z=2, R(P)=0.123, wR(P)=0.115, R(I)=0.049. Its structure contains two crystallographically independent oligomeric {[BP3O,2]6"} anions which are built up by a central trigonal planar BO3 group sharing common corners with three phosphate tetrahedra, the oligomeric anions linked via Cr2O9 octahedral dimers leading to three dimensional structure. It is stable up to 1015.7癈 and have the typical Cr -Cr dimer anti-ferromagnetic ordering with J=-28.9K. The optical property measurement showed that it has non-linear optical property with the intensity of 0.13 times of urea.(NH4)04Fe1I055Fe!II05(H2O)2[BP2O8] ?0.6H2O was synthesized under mild hydrothermal condition, the crystal structure was determined by single-crystal X-ray investigations (hexagonal, P65 (No. 170), a=9.483(4)A, c=15.697(5)A, F=1222.5(8)A3, Z=6, Rl=0.0261, wR2=0.0620, GooF=1.066). Its structure is characterized by corner-sharing PO4 and BO4 tetrahedra. leading to helical J{[BP2O8]3"} ribbons, which are connected by FeO4(H20)2 coordination octahedra. An additional trigonal bipyramidal FeO2(H2O)3 coordination polyhedron shares common corners and edges with three FeO4(H2O)2 coordination octahedra, leading to tetrameric unit. Helical channels, running along [001], are statistically occupied by H2O molecules and NH4+ ions. The temperature dependence of the magnetic susceptibility of this compound follows the Curie-Weiss law in the temperature ranging from 2K to 350K. The different effective magnetic moment Ueff of the pale gray (5.69uB) and black crystal (5.58u.B), both between the typical high-spin Fe2~ and Fe3", showed that the oxidation state of iron has a remarkable flexibility. The statistic test method after Yeates showed that the crystal has the high/wettdo-meroheric twinning.NH4Fe[BP2O8(OH)] was obtained as a by-product during the preparation of (NH4)04Fe"055Fein05(H20)2[BP2O8] ?0.6H2O. The single crystal data (monoclinic, P2,/c (No. 14), a=9.370(l) A, 6=8.309(2)A, c=9.680(l)A, /M 02.05(1)? F=737.0(2)A3, Z=4, Rl=0.04125 wR2=0.0596) was determined by single crystal X-ray diffraction. The crystal structure is characterized by an open-branched vierer-single infinite chain J{[BP,OS(OH)]4"}, connected by Fe04(H2O), coordination octahedra and leading to an one-dimensional channel system, occupied by NH4~ ions. The magnetic measurement of this compound showed that it has an anti-ferromagnetic ordering at TN ~ 17K, a weak ferromagnetic component of ~\0'2\jiB/Fe-atom is demonstrated by the size and the field dependence of the magnetization below TN.NaGa[BP2O7(OH)3] was synthesized under mild hydrothermal condition at 135癈. It is the first Ga-based borophosphate. The crysta...