Synthesis Of Benzamidine Supramolecular, Azaβ-diimine Componds And Studies On The Mechanisms Of C-N Bond Cleavage

In the process of human development, the theoretical research and application of material science towards a higher horizontal by the increasing needs to various of material properties and the appearance of new chemical phenomena. The functional materials based on the principle of supramolecular chemistry because of its unique characteristics of high performance meet the practical needs, which solves the new problems in chemical development and is one of the important of science and technology in 21st century. Ionic supramolecular polymeric structure material and organic metal complexes, as one of the branch, were developed quickly in recent years. In the thesis, we designed and synthesized several charge assisted hydrogen bond supramolecular polymeric compounds composed by benzamidine carbocation with various of anions. Structural characterization and fluorescence properties of them were determined.Ten compounds by reactingα-hydrogen-free aryl nitriles with different alkyl amino lithium have been prepared. The molecular structures of compounds 2a,2c, 2d,2b,3a were determined by X-ray crystallography and confirmed by IR, NMR ESI-MS. Compounds 2e,2f,2g,2h were examined by ESI-MS. The main contents are divided into four sections.Part I:The latest development of supramolecular chemistry and functional materials was introduced. What's more, the recent development of cleavage reaction about carbon nitrogen bonds was given.Part II:The compounds of 2a,2b,2c,2d,2e,2f,2g,2h were synthesized by treatment of R2NLi(R=Me,Et) witha-hydrogen-free aryl nitriles, followed the metatheses of chlorodiphenylphosphine or metal chlorides and oxidizing by hydrogen peroxide,2a,2c belongs to benzamidine Ionic supramolecular polymerization,2b,2d were organic compounds. The cleavage phenomenon about C-N bond was found and the mechanism was proposed by the synthesis 2e,2f,2g and 2h. The fluorescence properties of 2a,2c were measured.Part III:Two azaβ-diimine compounds have been prepared by 4-cyanopyridine and 4-nitrobenzonitrile reacting with R.2NLi(R=Me,Et) and chlorodiphenylphosphine. Azaβ-diimine charge assisted hydrogen bond supramolecular polymeric compound 3a was synthesized by exposing in air,while N-P bond cleavage reaction have been not observed in the 3b.The results demonstrated that azaβ-diimine was a stable skeleton and compounds structure were detailed characterized by X-ray crystallography, IR, NMR,ESI-MS.Part IV:The contents of research were summarized. The experimental design about the influence of oxidant in C-N bond cleavage process was submitted. The application of these compounds in materials chemistry was viewed.