锑离子帽式修饰的α-Keggin结构杂多钼酸盐的合成、结构及性质研究
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摘要
用钼酸钠、二氧化硅、二氧化锑做原料,在水热条件下合成了2种新的锑离子帽修饰的α-Keggin型多金属氧酸盐(HC_5H_5N)_3SiMo_5~ⅤMo_7~(Ⅵ)Sb_2O_(40) (1)和[Cu(C_(10)H_8N_2)_3](HC_5H_5N)[SiMo_5~ⅤMo_7~(Ⅵ)Sb_2O_(40)]·7H_2O(2)(C_5H_5N=吡啶;C_(10)H_8N_2=2,2′-联吡啶).通过元素分析、红外光谱和X射线衍射方法确定了2种化合物的结构.结果表明:化合物1属于单斜晶系,C2/c空间群,晶胞参数a=4.500 2(3)nm,b=1.401 48(9)nm,c=1.527 17(4)nm,β=103.579 0(10)°,V=9.362 6(10)nm3,Z=8,R_1=0.062 0,wR_2=0.136 2;化合物2属于单斜晶系,P2(1)/n空间群,晶胞参数a=1.572 03(6)nm,b=2.171 07(9)nm,c=2.706 79(11)nm,β=94.659 0°,V=9.207 7(6)nm~3,Z=4,R_1=0.121 9,wR_2=0.163 4.
Two new(HC_5H_5N)_3SiMo_(12)Sb_2O_(40)(1)and [Cu(C_(10)H_8N_2)_3](HC_5H_5N)[SiMo_(12)Sb_2O_(40)]·7H_2O(2)based on Sb-bicappedα-Keggin type polyoxometalates are synthesized under hydrothermal conditions by utilizing Na_2MoO_4 ·2H_2O,SiO_2,Sb_2O_3,2,2′-bipyridine and Cu(CH_3COO)_2 as raw materials.And the compounds are structurally characterized by elemental analysis,IR and single crystal X-ray diffractions.The two compounds both crystallize in the monoclinic system.For 1,space group C2/c,a=4.500 2(3)nm,b=1.401 48(9)nm,c=1.527 17(4)nm,β=103.579 0(10)°,V=9.362 6(10)nm~3,Z=8,R_1=0.062 0,wR_2=0.136 2.For 2,space group P2_1/n,a=1.572 03(6)nm,b=2.171 07(9)nm,c=2.706 79(11)nm,β=94.659 0°,V=9.207 7(6)nm~3,Z=4,R_1=0.121 9,wR_2=0.163 4.
Two new(HC_5H_5N)_3SiMo_(12)Sb_2O_(40)(1)and [Cu(C_(10)H_8N_2)_3](HC_5H_5N)[SiMo_(12)Sb_2O_(40)]·7H_2O(2)based on Sb-bicappedα-Keggin type polyoxometalates are synthesized under hydrothermal conditions by utilizing Na_2MoO_4 ·2H_2O,SiO_2,Sb_2O_3,2,2′-bipyridine and Cu(CH_3COO)_2 as raw materials.And the compounds are structurally characterized by elemental analysis,IR and single crystal X-ray diffractions.The two compounds both crystallize in the monoclinic system.For 1,space group C2/c,a=4.500 2(3)nm,b=1.401 48(9)nm,c=1.527 17(4)nm,β=103.579 0(10)°,V=9.362 6(10)nm~3,Z=8,R_1=0.062 0,wR_2=0.136 2.For 2,space group P2_1/n,a=1.572 03(6)nm,b=2.171 07(9)nm,c=2.706 79(11)nm,β=94.659 0°,V=9.207 7(6)nm~3,Z=4,R_1=0.121 9,wR_2=0.163 4.
引文
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[2]MULLER A,KOGERLER P.Erratum to“from simple building blocks to structures with increasing size and complexity”[J].Goord Chem Rev,2000,199:335-341.
[3]ZHANG J,HAO J,WEI Y G,et al.Nanoscale chiral rod-like molecular triads assembled from achiral polyoxometalates[J].JAm Chem Soc,2010,132:14-15.
[4]王博恩,胡长文,许林,多酸化学导论[M].北京:化学工业出版社,1998:1-109.
[5]YUAN M,LI Y G,WANG E B,et al.Modified polyoxometalates:hydrthermal syntheses and crystal structures of three novel reduced and capped Keggin derivatives decorated by transition metal complexes[J].Inrog Chem,2003,42(11):3670-3676.
[6]SUN C Y,LIU S X,LIANG D D,et al.Highly stable crystalline catalysts based on a microporous metal-organic framework and polyoxometalates[J].J Am Chem Soc,2009,131:1883-1888.
[7]BI L H,WANG E B,HUANG R D,et al.Room temperature synthesis and structural characterization of(NH4)15Co0.5(NH3)3[Co(NH3)4NaSb9W21O86]·15H2O-a novel chain-like inorganic cryptate[J].J Mol Struct,2000,553:167-174.
[8]LOOSE I,DROSTE E,B9SING M,et al.Heteropolymetalate clusters of the subvalent main group elements Bi(Ⅲ)and Sb(Ⅲ)[J].Inorg Chem,1999,38:2688-2694.
[9]史振雨,彭军.[Ni(2,2-bpy)2(H2O)]2[PMoⅥ7MoⅤ5V2ⅣO42]的水热合成与晶体结构[J].东北师大学报(自然科学版),2011,43(1):77-80.
[10]KORTZ U,SAVELIE M G,BASSIL B S,et al.Synthesis and characterization of iron(Ⅲ)-substituted,dimeric polyoxotungstates,[Fe4(H2O)10(β-XW9O33)2]n,(n=6,X=As(Ⅲ),Sb(Ⅲ);n=4,X=Se(Ⅳ),Te(Ⅳ)[J].Inorg Chem,2002,41:783-789.
[11]PANG H J,PENG J,ZHANG C J,et al.A polyoxometalate-encapsulated 3Dporous metal-organic pseudo-rotaxane framework[J].Chem Commun,2010,46:5097-5099.