双(取代水杨醛)间苯二甲酰腙有机锡配合物的一锅溶剂热法合成、结构和荧光性质

以间苯二甲酰肼、取代水杨醛和有机锡前体化合物进行一锅溶剂热法反应,合成了5个双（取代水杨醛）间苯二甲酰腙有机锡配合物m-Ph （CONH-N=CH （o-O） PhR¹）（SnR²）₂：R¹=Naphth,R²=Cy （1）; R¹=3-t-Bu,R²=n-Bu （2）; R¹=5-F,R²=Ph （3）; R¹=4-Cl,R²=Ph （4）; R¹=3-t-Bu,R²=Ph （5）。经元素分析、红外光谱、（¹H、¹³C和¹¹⁹Sn）核磁共振谱表征,并用X射线衍射方法确证了配合物1~5的晶体分子结构。配合物1~4为三斜晶系P1空间群,配合物5为单斜晶系P2₁空间群。中心锡与配位原子组成五配位畸形三角双锥构型。将水杨醛酰腙链与有机锡配位形成远离中心苯环的构型称为"反式",将与中心苯环取向相同的构型称为"顺式"。通过C1-C2或C4-C8单键旋转,中心苯环上的2个配位链发生构型翻转。配合物1形成"反-反"式构型,配合物2形成"顺-顺"式构型,配合物3、4和5形成"顺-反"式构型。荧光研究表明,配合物具有发光性能,特别是配合物1和4的有机溶液具有很强的荧光性能。

One-Pot Solvothermal Synthesis, Structure, and Fluorescence Properties of Bis(substituted salicylaldehyde) m-Phthaloylhydrazone Organotin Complexes

Five bis(substituted salicylaldehyde) m-phthaloylhydrazone organotin complexes, m-Ph(CONH-N=CH (o-O)PhR¹)(SnR²)₂, were synthesized by one-pot solvothermal reaction of benzene-1,3-dicarbohydrazide, substituted salicylaldehydes and organotin precursors, respectively, where R¹=Naphth, R²=Cy (1); R¹=3-t-Bu, R²=n-Bu (2); R¹=5-F, R²=Ph (3); R¹=4-Cl, R²=Ph (4); R¹=3-t-Bu, R²=Ph (5). Their structures were characterized by elemental analysis, IR and ¹H, ¹³C, ¹¹⁹Sn NMR, and the crystal structures of complexes 1-5 were confirmed by X-ray diffraction. Complexes 1-4 belong to the triclinic P1 space group and complex 5 crystallizes in the monoclinic P2₁ space group. The central tin and the coordinated atom form a five-coordinated distorted triangular bipyramids configuration. By C1-C2 or C4-C8 single bond rotation, the configuration of the two coordination chains on the central benzene ring is reversed. Here, it is defined that the configuration of salicylaldehyde acylhydrazone chain coordinated with organotin to form far from the central benzene ring is called "trans", and the configuration with the same orientation as the central benzene ring is called "cis". Therefore, complex 1 forms a "trans-trans" configuration, complex 2 forms a "cis-cis" configuration, and complexes 3, 4 and 5 form a "cis-trans" configuration. Fluorescence studies showed that the complexes had luminescence properties, especially the organic solutions of 1 and 4 had strong fluorescence properties.