双核锌配合物[Zn(dna)(phen)(H_2O)]的合成、结构及性质

以5,5'-二硫代双(2-硝基苯甲酸)(H2dna)和1,10-邻菲啰啉(phen)为配体在水热条件下合成了标题配合物,并利用元素分析、傅里叶变换红外光谱、X射线单晶衍射、X射线粉末衍射以及热重分析等技术手段对该配合物进行了结构和性质表征。晶体结构分析表明:配合物为单斜晶系,P2_1/n空间群,a=1.5312(3)nm,b=1.16054(18)nm,c=1.5609(3)nm,β=110.451(2)°,V=2.5990(7)nm~3,Z=4。该配合物为环状双核结构。基于氢键作用邻近的双核分子相连形成一维超分子链。而邻近超分子链又基于S幆O和CH幆π的弱相互作用扩展形成三维超分子网结构。该配合物失水后的产物保持相对稳定,直到245~450℃配体才开始分解,表现出良好的热稳定性。配合物在波长为280 nm的光源激发下,在440 nm有较强的荧光发射峰,且发射峰的形状与H2dna配体相似,但配合物的荧光强度相比H2dna配体有了明显的增强。

Synthesis,Structure and Properties of Binuclear Zinc Complex [Zn(dna)(phen)(H2O)]

A new complex Zn(dna)(phen)(H₂O)] based on 5,5'-dithiobis(2-nitrobenzoic acid)(H₂dna) and 1,10- phenanthroline(phen), has been hydrothermally synthesized and structurally characterized by elemental analysis, Fourier transform infrared spectrometer, X-ray single crystal diffraction and powder X-ray diffraction. Crystal structural analysis reveals that it crystallizes in monoclinic, space group P2₁/n, a=1.5312(3) nm, b=1.16054(18) nm, c=1.5609(3) nm, β=110.451(2)°, V=2.5990(7) nm³, Z=4. There is a binuclear ring structure in the complex, and the neighboring binuclear rings are linked into 1D supramolecular chain through hydrogen bonding interaction. The adjacent supramolecular chains are further interconnected by S????O and C—H????π weak interactions resulting a 3D supramolecular structure. The complex after dehydration remains relatively stable until 245 ~450 ℃. Then ligands begin to decompose, which shows good thermal stability. The complex displays a strong fluorescence emission maximum at ca. 440 nm upon excitation at 280 nm. The emission peaks of H₂dna ligand and the complex are similar. Compared with H₂dna ligand, the fluorescence intensity of complex is significantly enhanced.