新型含多氮杂环双缩二氨基硫脲类席夫碱的合成、催化性能及离子响应行为研究

During the past decade on the synthesis of various types of Schiff base complexes have become the focus of intense research efforts in synthetic organic chemistry. The synthesis of Schiff base ligands and their complexes, crystal structure, catalytic properties and ion response behavior have attracted much attention in various research fields such as organic and inorganic chemistry as well as materials science. We recently synthesizd some kinds of multinitrogen-containing heterocyclic bisthiocarbonohydrazone Schiff base ligands, and the zinc multinitrogen-containing heterocycle bisthiocarbonohydrazone Schiff base complexes was also successfully applied to catalyze Friedel-Crafts reaction. Moreover, containing quinoxaline ring bisthiocarbonohydrazone Schiff base ligand has also proven to be detect cadmium ions by naked eye with a characteristic absorbance bands at 570 nm. Therefore, in order to further study catalytic properties and ion response behavior of the multi-nitrogen heterocyclic bisthiocarbonohydrazone Schiff bases. Schiff base complexes will be synthesized from the reaction of metal salt with some new Schiff base ligands derived from the condensations of 2-phenyl-2H-[1,2,3]triazole-4-carbaldehyde, quinoxaline-2-carbaldehyde, oxadiazole ketone, containing triazole ring or imidazole ring ketone and fused heterocyclic aldehydes with 1,3-diaminothiourea, and the single crystal of ligands and complexes will be culture, the catalytic properties and ion response behavior of the ligands and complexes will be studied. Meanwhile, the reaction mechanisms, the impact of the different groups for ion response behavior and the law to eliminate the anti-interfering capability will be explore by the study of structure of the liangds and complexes. The study for understanding the structure, catalytic properties and ion response behavior of multi-nitrogen heterocyclic bisthiocarbonohydrazone Schiff bases ligands and their complexes, which have important theoretical and practical significance.

近年来对合成各种类型的席夫碱配合物的研究异常活跃，席夫碱配体及配合物的合成、晶体结构、催化性能及离子响应行为的研究已成为有机、无机和材料化学领域中最感兴趣的课题之一。项目申请者已合成几种含多氮杂环双缩二氨基硫脲席夫碱配体，发现其锌配合物能够有效催化Friedel-Crafts反应，同时发现含喹喔啉环的双缩二氨基硫脲对镉离子有很好的响应行为。项目拟以2-芳基-1,2,3-三唑醛、喹喔啉醛、噁二唑酮、含三唑环或咪唑环的酮及稠杂环醛与二氨基硫脲缩合，制备新型含多氮杂环双缩二氨基硫脲类席夫碱配体及其配合物，对配体和配合物的结构进行研究，同时进行催化性能研究和离子响应行为研究；通过对配体和配合物的晶体结构的研究，探讨催化有机反应的机理和不同基团对离子响应行为的影响及提高其选择性的规律。此研究对于了解多氮杂环双缩二氨基硫脲类席夫碱配体及配合物的结构、催化性能和离子响应行为等方面都有重要的理论和现实意义

近年来对合成各种类型的席夫碱化合物的研究异常活跃，席夫碱的合成及离子响应行为的研究已成为有机、无机和材料化学领域中最感兴趣的课题之一。因此，为了研究杂环类缩氨基硫脲席夫碱化合物的离子响应行为，通过2-苯基-2H-[1,2,3]三唑-4-甲醛、喹喔啉醛、三唑和稠杂环醛与二氨基硫脲、氨基硫脲和氨基脲缩合得到目标席夫碱化合物，并用红外、核磁、质谱进行了确证。这些席夫碱化合物通过紫外和荧光光谱研究发现有些席夫碱具有聚集体诱导发光效应和对汞离子的荧光响应行为。检测铝离子的酰腙类席夫碱显示出非常好的选择性和抗干扰能力，不像所报道的能被铜、铁离子干扰。杂环亚甲基丙二腈类化合物通过杂环醛和丙二腈的脑文格尔缩合制备，由于氰基与探针发生了亲核加成反应使这类化合物对氰基非常敏感，并且选择性很好。同时通过核磁滴定、高分辨质谱和Job's曲线对可能的机理进行了研究，探究了席夫碱结构和测试环境对响应行为和消除干扰的影响。此研究对于了解多氮杂环缩双缩二氨基硫脲、缩氨基硫脲、酰腙类席夫碱和杂环亚甲基丙二腈化合物的结构和离子响应行为等方面有重要的理论和现实意义。