Research On The Synthesis And Structure Of Bicyclooxaazacalixarene And Its Metal Complexes

The quick development of Supramolecular Chemistry has aroused great attention of scientists from the fields of Chemistry, Crystallography, Materials Science and Biology. The design and synthesis of the host molecules and the self-assembly research of the host molecules is an important part of'host-guest'chemistry. Currently, the'host'molecules are limited to a few kinds of compounds. It is necessary to design and synthesize new types of host molecules to recognize specific "guest" molecules (ions). In this paper, we have designed and synthesized a new kind of bicyclooxaazacalixarene, and have done some exploratory research on the ability of this nitrogen containing oxacalixarene to coordinate with metal ions, and the resulting supramolecular complexes.1. After the designing of a new series of'O'bridged asymmetric'calixarene', We synthesized a bicyclooxaazacalixarene compound (5,17,25,27,32,36-hexaaza-2,8,14,20,29,35-hexaoxabicyclocalix[4]arene) by employing phloroglucinol and aza aromatic rings with two substitutions as precursor, the structure has been confirmed.2. Some studies on the possible formation of'supramolecular structures'by this nitrogen containing calixarene have been carried out, and we found it can coordinate with Ag+, Cu2+, Zn2+ ions.The as-synthesized oxacalixarene can form different types of complexes, and it was found to form a three-dimensional coordination network with AgNO3; a planar network supramolecular complex with Cu(NO3)2; an one-dimensional-linear supramolecular coordination complex with Zn(NO3)2; a discrete complex, with Cu(OAc)2.We found that this oxacalixarene can form different types of complexes at different solvent systems. A planar network supramolecular coordination compound formed in the tetrahydrofuran - acetonitrile with Cu(NO3)2, however it can react with Cu(NO3)2 to form a one-dimensional-linear supramolecular coordination compound in the benzene-acetonitrile.Among supramolecular coordination compounds formed, some of them have certain cages. The supramolecular complexes formed by Cu (NO3)2 (tetrahydrofuran-acetonitrile) and AgN03 have specific cages in space. The study on the capacity of the cages in capturing guest molecules is currently in progress.