二苯基氧化磷芳基脒超分子聚合结构化合物的合成及结构功能

项目名称： 二苯基氧化磷芳基脒超分子聚合结构化合物的合成及结构功能

项目编号： No.20872084

项目类型： 面上项目

立项/批准年度： 2009

项目学科： 化学工业

项目作者： 郭建平

作者单位： 山西大学

项目金额： 33万元

中文摘要： 利用不同的分子间作用力进行超分子聚合物的设计及合成，进一步研究其作为功能材料的性质是当前发展非常迅速的研究领域，长程静电力和氢键有机超分子聚合结构的设计及合成是其中的一个分支。本研究以腈类物质为起始原料，经过加成和取代合成氮膦类化合物，再通过氮膦类化合物的氧化裂分得到12个含有二苯基氧化磷负离子脒碳正离子的静电力和氢键有机超分子聚合物以及12个亚胺类有机化合物。用核磁共振、元素分析及红外光谱进行了详细的表征，并用X-射线单晶分析方法测定了这些化合物的晶体结构，晶体结构显示，脒基正离子和二苯基氧化膦负离子组成了一类新的合成子。测定了超分子聚合物的固体及液体荧光性质，由于脒碳正离子和氧化磷负离子通过长程静电力和氢键连接起来，具有较大的共轭体系及刚性，因此表现出特殊的荧光性质。进一步通过中间产物分析及DFT计算等方法，推测了各种加成及键的氧化裂分机理。

中文关键词： 脒；氧化裂分；合成子；长程静电力和氢键；光学性质

英文摘要： Design, synthesis and structure of supramolecular polymeric network depend strongly on properties of building blocks and the strength and directional characteristics of the interactions among these components. The compounds with charge assisted hydrogen bond supramolecular network appear to have excellent electrical conducting, magnetic, structure and bio-active properties from the co-interaction of electrostatic force and hydrogen bond. The interaction of nitriles with LiNR2 followed by the addition of various phosphorus compounds gave phosphorus-nitrogen compounds. From the oxidative cleavage of these compounds, twelve compounds with self-assembly polymeric network of amidinium cations and diphenylphosphinate anions and twelve imido compounds could be formed. All of the new products were characterized by NMR, EA and IR, and ascertained by X-ray single crystal diffraction. The crystal structures revealed that each one of the positive amidinium groups provides four acidic N-H protons pointing outwardly and thus is capable of donating four hydrogen bonds in a trihapto mode and the anion affords oxygen as acceptor for the hydrogen bond. This is a featured type of synthon. Due to the rigidity and conjugation of stronger charge assisted hydrogen bond, the products showed the distinctive fluorescence properties. By results of DFT calculations and experimental verification of intermediate, the various addition and oxidative cleavage mechanism were suggested.

英文关键词： amidinium; oxidative cleavage; synthon; charge assisted hydrogen bond; fluorescence