Synthesis And Anionic Assembly Of Alkyl Bisbury Receptors

This thesis discusses the design and synthesis of the four cases of bis-bisurea ligands. And these ligands differ in the spacers and substituent groups in the end of the ligands. We studied the solid and solution prpperties of these ligands with various of anions. The full text is divided into four chapters, and the first chapter is the introduction. In this chapter, we summarizes the origin and development of anionic coordination chemistry, research methods of the anion coordination chemistry, the general research situation of anion receptors, the recent research status of dihydrogen phosphate polmers, and the significance of this subject. The second chapter, chapter 3 and chapter 4 described the research content listed by different anion ligands, and the main research results are as follows:1. We designed and synthesized 1,1’-(butane-1,4-diyl)bis(3-(2-(3-(4-nitrophenyl)ureido) phenyl)urea) (L3), and explored their binding properties with H2PO4- and Cl-. We can see from the anion response experiment that the receptor L3 has well binding properties with tetrahedron anion H2PO4-and halogen Cl-, and can both form coordination of 1:2 mode. The crystal structure showed that the ligand can form two different complexes with H2PO4-. In one of the two complexes, two H2PO4- bind with four urea in one molecule of L3 through eight hydrogen bonds. In addition, adjacent H2PO4-connect with each other by two hydrogen bonds forming a one dimension infinite chain. In another crystal structure, four terminal H2PO4-bind with eight urea of two molecules of ligand through 16 hydrogen bonds. However, the H2PO4- located in the centre do not bind with L3 but with the terminal H2PO4-and H2O, thus forming a discrete (H2PO4-)6 hexamer. Further more, in complex 2 there are four molecule of H2O surrounding the (H2PO4-)6, with one H2O binding with H2PO4- by two hydrogen bonds.2. We designed and synthesized 1,1’-(propane-1,4-diyl)bis(3-(2-(3-(butyl)ureido) phenyl)urea) (L4), and explored their binding properties with H2PO4- and C1-.By trying various methods to gain complexes, we finally obtained the crystals of the ligand with H2PO4-and Cl-. In the structure of complex 5, two molecule of H2PO4-bind with six of the total eight NH in one molecule of L4 through 6 hydrogen bonds. In addition, adjacent H2PO4-connect with one another and there are hydrogen bonds among water molecules. The complex 4 arranges in a line, and the (H2PO4-)4 polymer sandwiched between two ligands.3. We also designed and synthesized a pair of enantiomers which spacer is chiral and the terminal substituent group is nitrobenzene. We expect to get different anion complexes by changing the spacer to chiral group. Various attempts had been made to get crystals of anion complexes, we finally gained crystal structure of ligand L-L2 with C1-. The complex adopted a binding mode of host:guest= 3:1. And the combination of D-L2 with Cl-and other anions is in further study.