The Research On The Synthesis And Supermolecule Property Of Pillararene

Pillararenes is a new class of macrocyclic host molecules after crown ethers, cyclodextrins, calixarenes and cucurbiturils since their first introduction in 2008. Common pillararenes have pillar [5] arene, pillar [6] arene and pillar [7] arene, in which pillar[5]arene is the most common one. Owing to their rigid, tubular-shaped electron-rich cavity structures, as well as the regularly positioned alkoxy functionalities, numerous host-guest systems have been developed on the basis of pillararenes. Other important applications of pillararenes include the formation of supramolecular polymers, assembly of mechanically interlocked molecules, construction of artificial transmembrane channels, and various advanced functional materials. This thesis mainly focused on design and synthesis of a new type of tricyclic pillar[5]arene compounds H1, H2 and H3, and studied their host-guest chemistry with the different guest.(1) We have described an improved method of synthesizing pillar[4]arene[1]quinone, pillar[3]arene[2]quinone, pillar[2]arene[3]quinone and pillar[1]arene[4]quinone through partial oxidation of DMP[5], by the oxidative reagent(NH4)2[Ce(NO3)6](CAN)in in a H2O/CH2Cl2 solution. The reported improvement the way towards further selective functionalization of pillar[5]arene compounds, and therefore accelerates the research on pillararenes in supramolecular chemistry.(2) This thesis mainly focused on design and synthesis of a new type of tricyclic pillar[5]arene compounds H1, H2 and H3, and discovered the conformers H1 a and H1 b of H1. We also builded a wide variety of supramolecular system with them. Due to the influence of size of host H2 and H3 crown ether ring cavity, the host H2 and H3 cannot form the supramolecular system with G2(paraquat).(3)First discovered the difference of combining ability of conformers H1 a and H1 b with G2 in a 3:1 CDCl3/DMSO solution, the association constant(Ka) between H1 a and G2 was determined to be(906±78)M-1, the association constant(Ka) between H1 b and G2 was determined to be(262±20)M-1, the association constant(Ka) between 2G1 H1 a and G2 was determined to be(226±17)M-1, the association constant(Ka) between 2G1 H1 b and G2 was determined to be(79±7)M-1. We also discovered the difference of combining ability of conformers H1 a with G2 in different solvent systems.