含有冠醚及偶氮苯基团的铂基菱形大环化合物的合成

Synthesis of Rhomboidal Organoplatinum(Ⅱ) Metallacycle Containing Crown Ethers and Azobenzene Groups

亚硝基苯与对氨基苯甲醇反应生成偶氮苯衍生物2,衍生物2经溴代反应得到化合物3和3,5-二溴苯酚发生亲核取代反应得到化合物4,化合物4与4-乙炔基吡啶盐酸盐发生Sonogashira偶联反应得到化合物5。以3,6-二溴-9,10-菲醌为原料,先后经还原反应和亲核取代反应得到化合物7,化合物7与四(三乙基磷)铂反应生成有机金属铂配体8。化合物5和化合物8通过配位驱动自组装方法合成铂基菱形大环化合物1,其结构经核磁、质谱和紫外可见吸收光谱表征。

The compound 2 was obtained by the reaction of nitrosobenzene with 4-hydroxymethylaniline. The hydroxyl group of 2 was replaced by bromine to obtain compound 3. Compound 4 was synthesized by nucleophilic substitution of 3,5-dibromophenol and 3. Compound 5 was obtained by Sonogashira coupling reaction between compound 4 and 4-ethynylpyridine hydrochloride. 3,6-Dibromo-9,10-phenanthroquinone was used as raw material, the compound 7 was successfully synthesized by reduction reaction and nucleophilic substitution reaction successively. The substitution reaction of compound 7 with tetra-(triethyl phosphorus) platinum resulted in organometallic platinum ligand 8. A rhomboidal organoplatinum(Ⅱ) metallacycle 1 from a 60organoplatinum(Ⅱ)-acceptor 8 and a 120azobenzene-functionalized donor 5 has been formed via coordination driven self-assembly. The metallacycle 1 was characterized by NMR, MS and UV-Vis spectrum.