两个基于[SMo12O40]2-和冠醚基超分子阳离子的无机-有机杂化晶体的合成及晶体结构（英文）

Two Inorganic-Organic Hybrid Crystals Based on [SMo12O40]2- Polyoxometallates and Supramolecular Cation: Syntheses and Crystal Structures

以18-冠-6和4-碘-苯铵盐,二苯并30-冠-10和3-氟-4-氯-苯铵盐为超分子阳离子构建单元,分别引入到Keggin型[SMo12O40]^2-中,使用H管扩散法和溶剂挥发法合成了无机-有机杂化材料[(4-I-Anis)([18]crown-6)]2[SMo12O40]·CH3CN(1)和[(3-F-4-Cl-Anis)2(DB[30]crown-10)][SMo12O40]·2CH3CN(2)(4-I-Anis=4-碘-苯铵盐;3-F-4-Cl-Anis=3-氟-4-甲基苯铵盐;DB[30]crown-10=二苯并30-冠-10)。通过红外光谱、元素分析、热重分析、固态漫反射光谱和X射线单晶结构分析对化合物进行了表征。结构分析表明,晶体1和2通过非共价键自组装作用构建而成,冠醚基超分子阳离子是通过N-H…O氢键作用形成。晶体1中,在bc平面,每个[SMo12O40]^2-多酸阴离子被6个超分子阳离子(4-I-Anis)([18]crown-6)围绕,形成六边形的结构;晶体2中,在bc平面,每个[SMo12O40]^2-多酸阴离子被4个大的超分子阳离子(3-F-4-Cl-Anis)2(DB[30]crown-10)围绕,形成四边形的结构。热重分析表明,氢键在维持晶体1和2的稳定性上起着主要的作用。固态漫反射光谱表明,[SMo12O40]^2-和冠醚基超分子阳离子之间存在电荷转移作用。

Two inorganic-organic hybrids,[(4-I-Anis)([18]crown-6)]2[SMo12O40]·CH3CN(1)and[(3-F-4-Cl-Anis)2(DB[30]crown-10)][SMo12O40]·2CH3CN(2)(4-I-Anis=4-iodoanilinium;3-F-4-Cl-Anis=3-fluoro-4-chloroanilinium;DB[30]crown-10=dibenzo[30]crown-10)have been synthesized and characterized by infrared spectrum(IR),elemental analysis(EA),powder XRD,thermogravimetric(TG),solid state diffuse reflectance spectra(DRS)and X-ray diffraction.Crystals 1 and 2 are constructed through noncovalent bonding interaction,and the polyoxo-metalates and supramolecular cation arrange alternately.Supramolecular cation forms through the N-H…O hydrogen bonding interaction between the nitrogen atom of anilinium and oxygen atoms of crown ether derivatives.In crystal 1,each polyoxoanion is surrounded by six monovalent supramolecular cations(4-I-Anis)([18]crown-6)and forms hexagonal arrangement in bc plane.In crystal 2,each polyoxoanion is surrounded by four large supramolecular cations(3-F-4-Cl-Anis)2(DB[30]crown-10)and forms tetragonal arrangement in bc plane.TG measurement indicated that hydrogen bonding interaction plays an important role in maintaining the structural stability of crystals 1 and 2.DRS indicated that there exists charge-transfer interaction between[SMo12O40]2-polyoxoanions and crown ether based supramolecular cations in crystals 1 and 2.