Study On Synthesis Of The Polydentated N, S-containing Ligands And Selective Recognition Of Metal Ions

As the third generation supramolecular hosters, calixarenes have similar cavity with cyclodextrins and crown ethers, and their size can be accommodated by the control of phenol numbers. Many kinds of calixarene derivatives with versatile properties can be obtained by modifying the upper-rim and the lower-rim of the calixarenes. Calixarenes have been attracted much attentions and have versatile applications in supramolecular chemistry such as molecular recognition, molecular devices, self-assembly, nano materials and complex extraction. In this thesis, calixarenes, phloroglucinol and cyanuric chloride were chosen as the chemical plateform, a series of functionalized compounds as well as N, S-conataining polydentated ligands were successfully prepared and their crystal structures, complexing properties and ionic recogniations for transition common metal ions were investigated. Some interesting research results are as follows:1.p-tert-Butylcalix[4]arene-1,3-dialdehydes were firstly obtained by two step alkylations of p-tert-butylcalix[4]arene with alkylene dihalide and hydroxyl-substituted benzaldehydes. Then p-tert-butylcalix[n]arene1,3-disubstituted phenanthrolines were successfully prepared by condensation of active calixarene dialdehydes with1,10-phenanthroline-5,6-dione. The structures of the prepared hosters were characterized with IR, NMR, and HRMS spectra. The recogination of calixarene1,3-disubstituted phenanthrolines for metal ions were studied with UV-Vis spectroscopy. A great affinity for Ag+ions that can be clearly detected by naked eye was obtained.2.p-tert-Butylthiacalix[4]arene and p-tert-butylcalix[4]arene were alkylated with versatile dibromoalkane with potassium carbonate as base to give tetrabromoalkylthiacalix[4]arenes and1,3-dibromoalkylcalix[4]arenes, respectively. Then by reaction of these bromoalkylcalixarenes with potassium thioacetate, two kinds of calixarene tetrathiols and dithiols were prepared in good yields. The structures of the prepared calixarene tetrathiols and dithiols were characterized with IR, NMR, and HRMS spectra and were confirmed by determination of three single crystals. The recogination of calixarene thiols for metal ions were studied with UV-Vis spectroscopy. A great affinity for Co2+ions that can be clearly detected by naked eye was obtained.3. Phloroglucinol with three functional aldehyde groups were successfully prepared by two-step alkylation reactions of phloroglucinol with dibromoalkanes and p-hydroxybenzaldehydes. Then through the condensation reaction of salicyhydrazide and pyridinecarbohydrazide, a series of phloroglucinol-based acylhydrazone derivatives were obtained. On the other hand through the ammonolysis of phloroglucinol ether ester derivatives with ethylenediamine, phloroglucinol amides with terminal free amino groups were also prepared. Then by the condensation reaction of the latters with substituted salicylaldehyde, a series of phloroglucinol Schiff base ligands have been prepared efficiently. Under the similar reaction conditions cyanuric chloride was first reacted with salicylaldehyde or p-hydroxybenzaldehyde, and then through the condensation reaction of salicyhydrazide with pyridinecarbohydrazide, a series of cyanuric-based Schiff base ligands have been prepared efficiently. The recogination of Schiff base ligands for metal ions were studied with UV-Vis spectroscopy. A great affinity for Cu2+ions was obtained.