Studies On The Syntheses And Inclusion Properties Of Calix[4]arene Derivatives

In this thesis, ten novel calix[4]arene derivatives have been designed and synthesized, in which m-(alkoxycarbonyl)benzyl or w-(carboxy)benzyl are substituted on the lower rim of the calix[4]arenes. The inclusion behavior of the these calix[4]arene derivatives with tetrabutyl ammonium cation and neutral organic molecules has been studied. In addition, the sensitizing luminesence of Tb3+ by them was also studied. The main results obtained are as follows.1. Ten novel calix[4]arene derivateves were designed and synthesized. All of them were characterized by elemental analysis, IR, 1H and 13CNMR . Their conformations are in cone or 1,3-alternate.2. The inclusion complex between 4 and tetrabutyl ammonium bromide(TBAB), L4-TBAB has been obtained and characterized by DTA-TG and XRD analyses. The results obtained indicate that L4-TBAB can be considered as anintramolecular inclusion complex. The PVC membrane ion-selective electrode based on compound 4 as carrier and DOS as plastizer exhibits near Nerstain response characteristic towards quaternary ammonium cation with high selectivity.3. The properties of sensitizing luminescence of Tb3+ by compounds 4-13 were studied and compared with those of compounds 14-17. The results obtained indicate that the compounds 7,12,13 containing phenyl carboxy group have the most remarkable effect on the sensitizing luminescence of Tb3+ among the nine compounds. It could be assumed that the phenyl carboxy group and calix backbone can absorb the energy of ultraviolet and then effectively transmit it to Tb3+. The sensitizing luminescence by O-[w-(carboxyl)benzyl] substituted calix[4]arenes were much better than that by 0-[o-( carboxyl) benzyl] substituted calix[4]arenes. The efficiency of sensitizing luminescence is related to both the steric hindrance of the ligands and the stability of the complexes of Tb3+.4. The crystal structures of intramolecular inclusion complexes L4-CH3CN L4 CH3NO2 L5-CH3CN L9-CH3N02 and compound 10 were determined. The x-ray crystallographic analysis shows that not only the hosts with C4 symmetry but also with C2 symmetry can be bound stably with the guests containing CH group in the intramolecular inclusion complexes. The CH-7t interactions between the CH group of the guest and the phenyl rings of the calix backbone have been proved to be able to stabilize the intramolecular inclusion complexes formed, but it is independent of the acidity of the guest. The x-ray structrual analysisindicates that one ethyl group in the O-substitutents of each molecule of compound 10 enters into another cavity formed by the phenyl rings of the calix backbone in an orderly way. The CH-u interaction exists between the methyl group and the phenyl ring of the calix backbone which makes the compound 10 has a specially regular arrangement in the crystal packing by self-inclusion.