一个簇基无机-有机杂化材料的合成与表征

对簇基无机-有机杂化材料的制备方法及表征手段进行了研究。利用水热合成技术制备了一个具有新颖结构的簇聚物(H_2en)_2(H_3O)_(12)Si_2Mo_(14)~(VI)Mo_2~VV_2~VV_(10)~(IV)O_(84)](1,en=乙二胺),采用元素分析、红外光谱、X射线光电子能谱、电子顺磁共振、TG及X射线单晶衍射等技术对晶体结构进行了分析。结构分析显示,簇基杂化材料是由两个高还原态的二帽Keggin型簇阴离子Si(1)Mo_6~(VI)Mo_2~VV_6~(IV)O_(42)]~(10-)和Si(2)Mo_8~(VI)V_2~VV_4~(IV)O_(42)]~(6-)通过(μ_2-O)_2双桥氧原子连接成以簇阴离子二聚体为结构单元的1-D链,相邻的1-D链再经质子化的水分子通过氢键连接成新颖的3-D簇阴离子超分子网络,质子化的乙二胺和水分子填充于网络之中。磁性研究表明化合物1金属离子间存在反铁磁性相互作用。

Hydrothermal Synthesis,Structure and Characterization of a Inorganic-organic Hybrid Materials with Metalic Oxygen Cluster

In this paper,the crystal synthesis and performance of inorganic-organic hybrid materials with metallic oxy-gen cluster were studied. A new cluster-polymers(H2en)2(H3O)12Si2MoVI14MoV2VV2VIV10O84]1(en=ethylenediamine) has been hydrothermally synthesized and characterized by elemental analysis,IR,XPS,ESR spectrum,TG and sin-gle-crystal X-ray diffraction analysis. Compound 1 is possessed of 1D chain-like structure which was built up dimer with two bicapped Keggin polyoxoanionsSi(1)MoVI6MoV2VIV6O42]10- andSi(2)MoVI8VV2VIV4O42]6-,which were further in-terconnected via(μ2-O)2 terminal oxygen atoms. Furthermore,through hydrogen bond contacts with water and adjacent 1D cluster polyoxoanion chains,extended 3D polyoxoanions supramolecular networkwas formed in the solid of 1. The protonated H2en2+ and H3O+ cation is located in the holes of the network. The magnetic susceptibility of 1 demonstrated the presence of antiferromagnetic interactions.