An organic-inorganic polymer with Dawson-type polyoxometalates as building blocks: synthesis,characterization and crystal structure of [{Pr(DMF)_6}{Pr(DMF)_7}(P_2W_(18)O_(62))]_n

An organic-inorganic polymer of [{Pr(DMF)6}{Pr(DMF)7}(P2W18O62)]n has been synthesized in acetonitrile-water (5:2, volume ratio) mixed solvent. Single-crystal X-ray structural analysis indicates that the title compound crystallizes in a monoclinic lattice, P21/C, with a = 1.8574(4), b = 2.3907(5), c = 2.4222(5) nm, B= 99.48(3), Z= 4, V= 10.609(4) nm3, Dc = 3.501 Mg/m3, F(000) = 9972, R1 = 0.0654 and wR2= 0.1098. The result of crystal structure analysis reveals that Pr3+(1) complex ion is eight-coordinated with a distorted bicapped trigonal prismatic environment, which is combined with the heteropolyanion by terminal oxygen atom, whereas Pr3+(2) complex ion is also eight-coordinated with a distorted square antiprismatic environment, which is linked to the heteropolyanion by terminal oxygen atom. Adjacent structure units of [{Pr(DMF)6}{Pr(DMF)7}(P2W18O62)] are bridged through W-O-Pr1-O-W links to form an unprecedented one-dimensional zigzag linear chain by alternate polyanions and cationic units in the po     

一例含有八核钴簇的锗钨酸盐的合成、结构及性质

以K_8Na_2[A-α-Ge W_9O_(34)]·25H_2O,Co(NO_3)_2·6H_2O和K_2CO_3等为原料,利用常规水溶液法合成了一例基于三缺位Keggin型多金属氧簇{Ge W_9O_(34)}的高核过渡金属衍生物K_(10.5)Cs_4H_(1.5){[Co_8(OH)_6(H_2O)_2](CO_3)_3(Ge W_9O_(34))_2}·12H_2O(1),并通过红外光谱、元素分析、热重分析和X射线单晶衍射等分析手段对其进行了表征。化合物1含有一个V型的多酸阴离子簇{[Co_8(OH)_6(H_2O)_2](CO_3)_3(Ge W_9O_(34))_2}~(16-),该阴离子进一步通过K~+和Cs~+离子连接形成二维结构。磁学性质研究表明,化合物1中Co~(2+)离子之间主要为反铁磁性耦合。     

[Zn(DMF)6]H2SiW12O40·(CH3)2NH的合成,晶体结构及性质

The title compound [Zn(DMF)₆]H₂SiW₁₂O₄₀·(CH₃)₂NH was synthesized in mixed solvent of aqueous and acetonitrile, and its crystal structure had been determined using single crystal X-ray diffraction. The crystal belongs to monoclinic, space group C2/m, a=2.0654(4)nm, b=1.3306(3)nm, c=1.3194(3)nm, β=119.59(3)°, V=3.1531(11)nm³, D_c=3.606Mg·m^-3, Z=2, R=0.0462, R_w=0.0836. The title compound comprises of a [Zn(DMF)₆]²⁺ unit, a polyanion and a free (CH₃)₂NH molecule. The ESR spectrum of the title compound shows that charge-transfer between organic groups and polyanion takes place under irradiation of the sunlight in solid state. The TG study of the title compound shows that it had four stages of the weight loss, and the increase of the de-composition temperature for the polyanion shows that the stability of the polyanion was enhanced due to the influence of Zn²⁺ ion. CCDC:175866.     

Keggin结构钼硅酸铵、钨硅酸铵纳米颗粒的室温固相合成、结构及性能研究

采用室温固相法合成了钼硅酸铵、钨硅酸铵两种纳米颗粒 ,用元素分析确定其分子组成 ,它们的结构、性质、颗粒大小、表面形状分别用红外光谱、X -射线粉末衍射、透射电镜和热分析进行了研究 .结果表明 ,两种纳米颗粒的大小分别在 30nm和 4 0nm左右 ,长期放置易发生团聚 ,在水和无水乙醇中呈乳液分布 ,形成纳米颗粒后 ,两种杂多阴离子的热稳定性均明显降低     

多钼酸盐[4,4''-H2 bipy]2[β-Mo8O26]的水热合成和晶体结构

利用水热合成方法制备了化合物[4,4'-H2bipy]2[β-Mo8O26],用元素分析、X射线单晶衍射和电子顺磁共振对其结构进行了表征.结构解析表明标题化合物是由β型[Mo8O26]4-多阴离子与质子化的4,4'-联吡啶通过氢键作用形成的三维结构超分子化合物.     

多钼酸盐[4,4-′H_2bipy]_2 [β-Mo_8O_(26)]的水热合成和晶体结构

利用水热合成方法制备了化合物[4,4′-H2b ipy]2[-βMo8O26],用元素分析、X射线单晶衍射和电子顺磁共振对其结构进行了表征.结构解析表明标题化合物是由β型[Mo8O26]4-多阴离子与质子化的4,4′-联吡啶通过氢键作用形成的三维结构超分子化合物.     

混合型杂多化合物M_x[GaW_9M_3O_(40)]·nH_2O的合成和性质

本文报道了M_x[GaW_9M_3~′O_(40)]nH_2O(M′=Mo,V,Ti,Fe(Ⅲ),Co(Ⅱ),Ni(Ⅱ),Mn(Ⅱ);M=k,Na,Gua,Me_4N,Et_4N,Bu_4N)的合成。通过元素分析,阴离子电荷的确定,极谱、IR及UV光谱、可见光谱、ESR、磁化率测定对其进行了表征。并研究了它们在水溶液中对酸碱的稳定性及热稳定性。     

N-甲基吡咯烷酮与H_nXW_(12)O_(40)·mH_2O(X=P,Si,Ge)电荷转移盐的合成、表征及非线性光学性质研究

由N -甲基吡咯烷酮和HnXW1 2 O40 ·mH2 O(X =P ,Si,Ge)合成了具有非线性光学性质的电荷转移盐 ,(NMPH) 3PW1 2 O40 ·CH3CN(I) ,(NMPH) 4 SiW1 2 O40 ·CH3CN(Ⅱ )和 (NMPH) 4 GeW1 2 O40 ·CH3CN(Ⅲ ) .并由元素分析 ,红外光谱 ,漫反射电子光谱进行了表征。结果表明杂多酸形成电荷转移盐后其阴离子结构未变 ;N -甲基吡咯烷酮通过N原子与酸中的质子H+结合成阳离子而成盐 ,光激发下阴阳离子之间可以发生电荷转移 ,非线性光学性性质研究表明 ,电荷转移盐的倍频效应强度分别为I2ωⅠ =0 .6IKDP,I2ωⅡ =0 .85和I2ωⅢ =0 .41IKDP,三阶非线性系数分别为 χ(3)Ⅰ =1 .60× 1 0 - 1 2 esu ,χ(3)Ⅱ =3.6× 1 0 - 1 2 esu ,χ(3)Ⅲ =1 .2× 1 0 - 1 1 esu .     

磷钨酸-PVA复合体系膜的制备和光色性研究

用旋转涂布法制得了PVA -H3PW1 2 O40 复合体系的光敏膜。研究了膜对光的响应情况 ,发现复合体系对光的响应情况与体系内各成份的浓度无关。光敏性的产生源于体系内PVA的 OH与钨磷酸阴离子中Oc的相互作用。     

以[α-P2W18O62]^6-阴离子为构筑块的一维链状稀土配位聚合物[Nd（DMF）6（H2O）2][Nd（DMF）6（H2O）]P2W18O62的合成﹑结构及性质研究

以Nd2O3,DMF和α-H6P2W18O62·nH2O等为原料合成了Dawson结构杂多阴离子有机-无机配位聚合物[Nd(DMF)6(H2O)2][Nd(DMF)6(H2O)]P2W18O62,并对其进行了IR,UV光谱表征及电化学性质研究。X-射线衍射单晶结构分析结果表明,晶体属单斜晶系,Cc空间群,晶胞参数:a=1.8991(3)nm,b=2.2047(3)nm,c=2.6448(4)nm,β=102.272(3)°,并有Z=4,R1=0.0438,wR2=0.1107。聚合物中存在2种构型的Nd配离子,Nd(1)以九配位的三加冠三棱柱结构通过端氧与[P2W18O62]6-阴离子赤道位的W相连,Nd(2)以九配位畸变的单加冠四方反棱柱结构通过端氧与[P2W18O62]6-阴离子极位的W相连,从而构成分子结构单元[{Nd(DMF)6(H2O)2}{Nd(DMF)6(H2O)}(P2W18O62)],毗邻的结构单元又通过W-O-Nd(1)-O-W桥联形成一维锯齿无限链状结构。