【作者】 钟惠萍；

【导师】 黄荣彬； 龙腊生；

【作者基本信息】 厦门大学 ， 无机化学， 2004， 博士

【摘要】 超分子化学是一门新兴科学，是当前的研究热点之一。含氮、硫杂环化合物中的氮、硫是很好的配位原子，可用于组装许多具有新颖结构和特殊功能的超分子配合物，因此是研究生物配体以及超分子化学的优良模型。本论文通过溶液法以及溶剂热法合成了一些硫氮杂环化合物，并采用多种研究方法和实验手段，对超价键、金属-金属相互作用、同质多晶现象、光致变色反应以及阴离子识别作用等现象进行了研究。本论文的主要研究成果如下： 一．以二硫化碳和胺为原料、采用溶剂热方法合成了多个硫氮杂环化合物。此方法具有原料简单易得、反应装置简单、易于操作、产率高等诸多特点，且在合适的条件下产物直接以单晶形式析出，不仅简化了分离纯化步骤，而且能获得产物的直观结构信息。因此，本论文的工作为含氮、硫有机杂环化合物的合成提供了一个新的思路，值得进一步研究。 二．以具N-S-N超价键的2-(2-吡啶亚氨基)-2H-1，2，4-噻二唑并[2，3-a]吡啶(PTP)为研究对象，以单晶X-射线衍射技术为研究手段，考察了亚胺氮原子上质子氢配位键、金属配位键、氢键等作用的形成对N-S-N超价键的影响。PTP配体亚胺氮原子N3上配位键和氢键作用的形成使得N4原子一侧的吸电子能力增强，S1-N4间距离被拉长，而S1-N1键则得到加强，距离缩短。所探讨的几种作用对N-S-N超价键的影响大小如下：质子氢配位键＞金属配位键＞C-H…N氢键。 三．以超价化合物PTP为1，3-双核桥配体，通过溶液法制备了四个双核银(Ⅰ)配合物。单晶X-射线衍射结构分析表明，PTP是一个有效的1，3-双核桥配体，能支持具有较短距离Ag(Ⅰ)-Ag(Ⅰ)相互作用的生成。这四个银(Ⅰ)配合物中的Ag-Ag键长在2.8191(14)至2.8798(9)之间，较单质银中银原子间的距离(2.889A)短.室温下四个银(I)配合物均显示较强的光致发光性质.经分析，在乙睛溶液中配合物的发射产生于配位银原子扰动的配体内的电子跃迁。 四.考察了喳哇琳酮衍生物7一氨基一4一轻基一1护2一哇哇琳硫酮(胡QT)的同质多晶现象、光致变色反应以及对阴离子的识别作用。通过对两个模型化合物的相关性质的研究，探讨了AHQT的光致变色极理及与阴离子的作用方式。改变反应混合溶剂乙醇和水的比例，获得了AHQT的两种具有不同的吸收光谱和发光性质的同质多晶体;胡QT的光致变色反应为一级反应，其机制是基于紫外光照下烯醇式结构转变为酮式结构所引起的吸收光谱和荧光光谱的变化:光照后的产物对场Po4-离子具高度选择识别作用，两者的作用方式为通过氢键作用形成1:1主客体配合物。更多还原

【Abstract】 Supramolecular chemistry is a new and promising subject. A study on the synthesis and supramolecular chemistry of several nitrogen- and sulfur-containing heterocyclic compounds was carried out in this dissertation. The main results are summarized as follows:1. Six nitrogen- and sulfur- containing heterocyclic compounds were synthesized with amine and carbon disulfide by solvothermal reactions, which providing a simple and effective approach to the synthesis of nitrogen- and sulfur- containing heterocyclic compounds.2. A polyheterocyclic hypervalent molecule with N-S-N hypervalent bond , 2-(2-Pyridylimino)-2H-l,2,4-thiadiazolo[2,3-a]pyridine(PTP), was selected to research the effects of protonation, metal-coordination bond and hydrogen bond at imino nitrogen atoms on the strength of N-S-N hypervalent bond. The formation of coordination bond and hydrogen bond at N3 atom in PTP causes the electron-withdrawing ability of the N4 side increase relative to the N1 side. Therefore the S1-N4 bond is elongated and attractive interaction in the N4 side is weakened. In contrast, the S1-N1 attractive interaction of the Nl side is strengthened. The influence of the effects investigated is in the following order: protonation > metal-coordination bond > hydrogen bond.3. With hypervalent molecule PTP as 1,3-bifunctional bidentate ligand, and various carboxylate ancillary ligands, four dinuclear silver(I) complexes were synthesized. X-ray structural analysis shows that PTP can act as a potential 1,3-bifunctional bidentate ligand for spanning short metal-metal interactionsHIbetween Ag(I) ions. The four complexes contain short Ag-Ag separations between 2.8191(14) A and 2.8798(9) A bridged by the ligand. All these complexes show strong blue luminescences at room temperature, which were assigned to silver-perturbed intraligand fluorescence.4. The polymorphism, photochromism and anion recognition properties of 7-amino-4-hydroxy-lH-quinazoline-2-thione(AHQT), a quinazoline derivative, were investigated. AHQT has two polymorphs with different absorption and fluorescence spectra. The UV, fluorescence and 1H NMR analysis of the photochemistry of AHQT showed that the photochromic phenomenon was due to the photoisomerization from enol form to keto form. The photocolored product of AHQT was found to undergo sensitive response to H2PO4 anion in acetonitrile. The response was assumed to result from the formation of 1:1 hydrogen-bonded complex.更多还原