Synthesis And Application Of Rare-Earth Complexes Containing Calix[4]Arene Derivative

Calixarenes,which are basket-shaped macrocyclic compounds with potential interest for host-guest complexation studies,represent the new type of receptors after cyclodextrins and crown ethers,and have strong ability of selective recognition to metal ions,so calixarenes have been extensively focused by chemists from all over the world.In this paper,calix[4]arene 1 was choosen as the main molecule, according to the reports,the lower rings substitution of three types calixarene-based receptors were prepared,which was obtained from the typical kind of reaction between calix[4]arene 1 and acyl halide or halogenated hydrocarbon.Under an appropriate reaction condition,the functional groups which contain lonely couple of electrons has been successfully attached to the calix ring body,They are two kinds of two substituted calix[4]arene derivatives and one kind of fully substituted calix[4]arene derivatives which is shown in the paper as calix[4]arene 2,calix[4]arene 3 and calix[4]arene 4 respectively,these functional calix[4]arenes can be used as the good receptors in the field of ion recognition.The resultant products are characterized by IR,¹HNMR and element analysis.As Rare-earth metal have a widely application in the national industry,the study of separation,enrichment and recycle of rare-erath metal cations is much focused in recent years.Many articles have already reported that the funtionalized calixarene shows a well character of selective ability to the metal ions such as the alkali metals and transition metals.In this article,the extraction behavior of four types of trivalent lanthanide ions is investigated with three types of extractants: calix[4]arene 2,calix[4]arene 3 and calix[4]arene 4;we choose the dichloromethane as the diluent,and dissolve the metal ion into the HNO₃ solution as aqueous layer;the solvent extraction experiment is carried out under the room temperature(about 25℃),and the different distribution rate is observed under various HNO₃ concentration of the three different extractants.On the basis of the extraction experiment,the following conclusion can be made:(1)Under the same environment condition,different substituted groups has different extract ability to lanthanide ions(â…¢),the N donor of quinoline group imparts somepart more effective than O donor of benzoyl group.(2) Increasing the number of the extract groups in the lower ring of calixarene can enhance the ability of extractant to transfer metal ions to organic layer.(3)To the three selected exactants,the distribution ratio is inclined to depend on the concentration of HNO₃ in the aqueous phase.The extract rate is going to a rising trend as the concentration of HNO₃ is getting higher.(4) The radius of rare-earth element also put up to an influence on the extract behavior.From the data,it can be concluded that a well-matched size of the metal and the cave of calix body make for a better extraction rate.In the solvent extraction experiment,it is concluded that calix[4]arene 4 has shown a superior coordinate ability to rare-earth metals.On the basis of it,we choose calix[4]arene 4 as the ligand,and research on its coordinate effect with lanthanide ions.Two kinds of rare-earth complexes are prepared in the diluted organic solvent,that is calix[4]arene-La complex and calix[4]arene-Eu complex.The constitute of the complex was identified by IR,UV absorbtion and element analysis. The thermo gravimetric analysis is also conducted and result show that the ligand is exactly coordinated with rare-earth metal(â…¢) with respect to a stoichiometric 1:1,that is to say the metal ion has already entered the cave of calix body.We have also evaluated the antibacterial ability of the compound by K-B method.After finishing by the two new complexes, the cotton fabrics have an excellent antimicrobial ability to E.coli (ATCC25922),Staphylococcus aureus(ATCC29213) and Pseudomonas aeruginosa(ATCC27853).The ultimate goal of the project is to find a new application for the novel antibacterial material based on calixarene and rare earth element in the textile chemistry.