Synthesis And Properies Of Cup-Like Macrocyclic Molecules

Cup-like macrocyclic molecules,as an important class of supramolecular host compound, play a special role in the host- guest chemistry and gathered in the solution and other fields because of its special three-dimensional structure. It has potential applications in the areas of organic nano-materials and devices. In this paper, We designed and synthesised a cup-like macrocyclic molecule consists of six flexible chain bridged,through 1H-NMR, 13C-NMR and MALDI-TOF and other means its structure was confirmed. We used fluorescence emission spectra, UV absorption spectroscopy and Scanning Tunneling Microscopy to study its supramolecular behavior. The results show that:1、Electron-rich systems of Cup-like macrocyclic molecules 12 with C60 can form host- guest inclusion complexes by double logarithmic regression curve to calculate the binding constant Ka(lg Ka=7.8093) and complexation proportion(n=1.6). We obtained TM and C60 in toluene Job’s titration curve by fluorescence emission spectra,, indicating that TM and C60 is 2: 3 complex, and n values calculated in line. We also studies the interaction between 12 and C70 by UV- fluorescence, the findings also can be complexed. The results show that: the ratio of 12 and C70 complex is 2: 3, which is basically consistent with the calculated values(n = 1.54), lg Ka = 6.5193.2. Electron-rich systems of Cup-like macrocyclic molecules 12 can play a role with Mg2+,Hg2+,Cu2+,Ba2+,Na+,Ag+,Sn2+,K+,Ca2+,Fe3+and so on, which cause a decrease in fluorescence intensity.3. In order to determine the position of TM and C60 complexation, we have done UV- fluorescence test about triangular ring 9 and C60 and do a Job’s plot: The study found the ratio of 9 and C60 complex is 1: 1. And it also proves that the TM and C60 complexation may also occur in the side of the triangular cavity.4. Using Scanning Tunneling Microscope(STM) researched supramolecular behavior of triangle ring 9. 9 ’, which is from 9 removed the protecting group and put on highly oriented pyrolytic graphite(HOPG) surface, can be found gathered into an ordered lamellar structure. Observation showed that: Compound 9’ ordered by inclusive staggered way, and the alkyl chain stacked staggeredly down from the direction of the ether chain bridge.