以杂多钼酸盐为构筑单元的微孔结构化合物和稀土化合物的合成、晶体结构及性质

题名:以杂多钼酸盐为构筑单元的微孔结构化合物和稀土化合物的合成、晶体结构及性质
作者:张新方
学位授予单位:河南大学
关键词:结构化合物:5456,配阳离子:3695,杂多阴离子:3407,晶胞参数:3030,空间群:2893,河南大学:2682,晶体结构:2386,化学专业:2327,晶Block neodymium magnet体学数据:2250,硕士研究生:2008
摘要:
 本论文主要分为两部分,第一部分以饱和Keggin结构杂多阴离子[XMo_(12O_(40)]~(n-)(X=Si~Ⅳ,Ge~Ⅳ,n=4;X=P~Ⅴ,n=3)和配阳离子[M_3O(OOCR)_6(H_2O)_3]~+(M=Fe~Ⅲ,Cr~Ⅲ;R=CH_3,C_2H_5)为基本构筑单元,通过分子设计与组装,采用常规合成法,在一定条件下制备出一系列具有孔道结构的化合物,并用红外光谱、X-射线单晶衍射、紫外-可见光谱、TG、XPS等手段对化合物进行了结构研究和表征;第二部分以Anderson结构杂多阴离子[CrMo_6O_(24)H_6]~(3-)为基本构筑单元,选择合适的实验条件,与稀土离子及有机分子作用,采用常规的水溶液合成法制备了三个Anderson结构阴离子稀土化合物,并利用红外光谱、X-射线单晶衍射、紫外光谱、荧光光谱等对化合物进行了表征Block neodymium magnet和结构研究。化合物的组成和晶体学数据如下:
 1.KH_2[Fe_3O(Ac)_6(H_2O)_3][SiMo_(12)O_(40)]·8.5H_2O(Ac=CH_3COO~-):单斜晶系,P2_1/n空间群.晶胞参数:a=15.161(2)(?),b=18.254(3)(?),c=29.198(4)(?),β=91.910(3)°,V=8076(2)(?),D_c=2.069 g/cm~3,Z=4,R_1=0.0457,wR_2=0.1374[I＞2σ(I)].
 2.[Fe_3O(Ac)_6(H_2O)_3]H_2[PMo_(12)O_(40)]·7H_2O:单斜晶系,P2_1/n空间群.晶胞参数:a=9.5721(3)(?),b=13.7893(4)(?),c=33.0607(13)(?),β=94.0280(10)°,V=4353(2)(?),D_c=2.406 g/cm~3,Z=2,R_1=0.0479,wR_2=0.1366[I＞2σ(I)].
 3.Na_2H[Cr_3O(Ac)_6(H_2O)_3][GeMo_(12)O_(40)]·2.75H_2O:单斜晶系,P2_1/n空间群.晶胞参数:a=15.104(5)(?),b=18.086(6)(?),c=28.967(10)(?),β=91.944(4)°,V=7908(4)(?),Dc=2.702 g/cm~3,Z=4,R_1=0.0801,wR_2=0.2065[I＞2σ(I)].
 4.K_(1.5)[Cr(H_2O)_6]_(0.5)[Cr_3O(Ac)_6(H_2O)_3][SiMo_(12)O_(40)]·6.75H_2O:单斜晶系,P2_1/n空间群.晶胞参数:a=15.1311(7)(?),b=18.1715(8)(?),c=28.8237(13)(?),β=91.8810(10)°,V=7920.9(6)(?),D_c=2.209 g/cm~3,Z=4,R_1=0.0374,wR_2=0.1193[I＞2σ(I)].
 5.[Cr_3O(Ac)_6(H_2O)_3]_2H[PMo_(12)O_(40)]·2H_2O:单斜晶系,P2_1/n空间群.晶胞参数:a=9.5758(3)(?),b=13.7971(5)(?),c=32.9483(12)(?),β=93.7950(10)°,V=4343.5(3)(?),D_c=2.412 g/cm~3,Z=2,R_1=0.0468,wR_2=0.1134[I＞2σ(I)].
 6.K_2[Cr_3O(OOCC_2H_5)_6(H_2O)_3]_2[SiMo_(12)O_(40)]·1.5(HAc)·6H_2O:三斜晶系,P-1(2)空间群.晶胞参数:a=12.9964(5)(?),b=12.9964(5)(?),c=20.9026(8)(?),α=76.4060(10)°,β=74.1260(10)°,γ=79.6580(10)°,V=5148.3(3)(?),D_c=2.192 g/cm~3,Z=2,R_1=0.0519,wR_2=0.1399[I＞2σ(I)].
 7.(C_6H_4NO_2)_2Er(H_2O)_6(CrMo_6O_(24)H_6)·2(C_6H_5NO_2)·7H_2O:三斜晶系,P-1(2)空间群.晶胞参数:a=12.7974(5)(?),b=12.9271(5)(?),c=18.1908(7)(?),α=93.43(0)°,β=105.63(0)°,γ=113.06(0)°,V=2619.69(173)(?),D_c=2.342 g/cm~3,Z=2,R_1=0.0319,wR_2=0.0865[I＞2σ(I)].
 8.(C_6H_4NO_2)_2Dy(H_2O)_6(CrMO_6O_(24)H_6)·2(C_6H_5NO_2)·7H_2O:三斜晶系,P-1(2)空间群.晶胞参数:a=12.7867(4)(?),b=12.8920(4)(?),c=18.1606(3)(?),α=93.4270(3)°,β=105.60°,γ=112.76°°,V=6490.3(6)(?),D_c=2.393 g/cm~3,Z=2,R_1=0.0285,wR_2=0.0776[I＞2σ(I)].
 9.(C_6H_4NO_2)_2Sm(H_2O)_6(CrMo_6O_(24)H_6)·2(C_6H_5NO_2)·6H_2O:三斜晶系,P-1(2)空间群.晶胞参数:a=12.7893(4)(?),b=12.9166(9)(?),c=18.1585(5)(?),α=93.46(3)°,β=105.61(3)°,γ=113.06(3)°,V=2611.45(14)(?),D_c=2.356 g/cm~3,Z=2,R_1=0.0347,wR_2=0.0995[I＞2σ(I)].
 10.[Ni(dmf)_3(H_2O)][HPMo_(12)O_(40)]·(dBlock neodymium magnetmf)·2H_2O:三斜晶系,P-1(2)空间群.晶胞参数:a=13.0307(13)(?),b=13.4994(13)(?),c=14.9265(15)(?),α=95.4260(10)°,β=98.0060(10)°,γ=101.6670(10)°,V=2525.9(4)(?),D_c=2.930 g/cm~3,Z=2,R_1=0.0276,wR_2=0.0736[I＞2σ(I)].
学位年度:2009