双核锌配位化合物[Zn(C15H8O7S)(DMSO)]2•H2O的合成和晶体结构及光致发光性能研究

以白杨素为先导化合物, 对其进行磺化, 磺化衍生物与锌络合, 在含水10%的二甲基亚砜(DMSO)溶液中重结晶, 得双核锌配位化合物[Zn(C₁₅H₈O₇S)(DMSO)]₂•H₂O. 采用IR, ¹H NMR, DSC-TGA, 元素分析和X射线单晶衍射法对标题化合物进行了表征和晶体结构测定. 标题化合物属正交晶系, 空间群Pbcn, Zn(II)的配位数为5, 配位原子均为氧原子, 每个五配位的锌都具有四方锥型的配位构型, 被2个配体5-羟基氧负离子-7-羟基黄酮-6-磺酸根的5-羟基氧负离子桥联, 形成了一个中心Zn₂O₂的菱形平面. 水溶性白杨素黄酮配体与Zn(II)通过氢键、π-π堆积和配位作用自组装形成了一个三维结构的超分子化合物. 差示扫描量热分析(DSC-TGA)结果表明,标题化合物配体骨架分解温度为518.26 ℃. 同时, 标题化合物固体具有较强的光致发光现象, 在λ_ex＝423 nm条件下可发出λ_em＝488 nm的黄色荧光, 并对其发光机制进行了探讨.

Synthesis, Crystal Structure and Photoluminescence of a Dinuclear Zinc Complex [Zn(C15H8O7S)(DMSO)]2•H2O

The sulfonate derivative of chrysin was coordinated with zinc to synthesize a zinc complex [Zn(C₁₅H₈O₇S)(DMSO)]₂•H₂O and the complex was characterized by the method of IR, ¹H NMR, DSC-TGA, elemental analysis and X-ray single crystal diffraction. The complex crystallizes in orthorhombic space group, Pbcn. And in the crystal structure, each five-coordinate zinc atom possesses a square pyramidal geometry with the coordinated atoms to be all oxygen atoms. Two zinc atoms are bridged by two 7-hydroxylflavone-5-oxide-6-sulfonate ligands with their 5-oxide functionalities to form a rhombic plane of Zn₂O₂. Hydrogen bonds, π-π stacking and the coordination interaction exist in the crystal structure, which can lead to assemble supramolecule with a three-dimensional network structure. The result of DSC-TGA curves manifest the decomposition temperature 518.26 ℃ of the ligand of the title complex. And the solid of title complex has the photoluminescent phenomenon. The title complex emits yellow fluorescence at 488 nm when excited at the wavelength of 423 nm and its photoluminescent mechanism was discussed.