Design, Synthesis Of New Calix [4] Arene Derivatives And Their Spectral Recognition Performances To Metal Ions

The environmental risk of heavy metal pollution is among one of the pollutants, which cause severe threats to humans and the environment. As the third generation of supramolecular parent, calix[4]arene possesses a electron-rich structure and a number of reactive sites, so a series of functional compounds can be derived from it. In this paper, new calix[4]arene derivatives has been designed and synthesized, and their spectral recognition performances to some metal ions were studied.1.5,11,17,23-four naphthylmethyl-26,28-two (carbomethoxy)-calix[4]arene (compound7) has been synthesized by reaction of derivative of25,27-dihydroxy-26,28-di-(ethoxycarbonyl-methoxy)-calix[4]arene (compound6) with2-hydroxyl-1-naphth. Synthsis of5,11,17,23-four (o-hydroxyphenyl)-calix[4]arene Schiff base (Compound10). Using25,27-dihydroxy-26,28-di (ethoxycarbonyl-methoxy) p-tert-butyl-calix [4] arene (compound4) as a raw material, formylation generating Calix [4] arene derivatives (Compound11), and then bonding with coumarin hydrazide derivatives to produce a new type of Calix [4] arene hydrazone (compound12). The synthesis conditions, separation and purification methods were explored and the IR,1H NMR is used to determine their structures.2. The recognition performance of compound7, compound10and compound12to Cu2+, Zn2+, Cd2+, Pb2+, Mg2+, Fe3+, Co2+, Ni2+, Mn2+, Ce3+, Ag+metal ion in DMF was studied by using UV-vis spectra. The results showed that the compound7has the ability to identify Ce3+. At8℃, after adding Ce3+ion the absorption maximum wavelength of compound7hypochromatic shift25nm. After heating preservation at40℃for5h, the absorbance of the solution reduced significantly. Compound10has the ability to identify Ce3+, Co2+and Mn2+. After adding Ce3+the maximum absorption wavelength red shift14nm and the absorbance of compound10increased. After adding Co2+absorbance of the solution decreased. After heat preservation at40℃for5h, maximum absorption wavelength of compound10red shift4nm and absorbance increased than before heat preservation after adding Mn2+. At8℃, after puting different metal ions into the compound12, the solution added Fe3+and Ce3+has the larger change in absorbance. And the are enhanced respectively. The situation after heat preservation at40℃for5h was the same with the situation at8℃. 3. The recognition performance of compounds7, compound10and compound12to Cu2+, Zn2+, Cd2+, Pb2+, Mg2+, Fe3+, Co2+, Ni2+, Mn2+, Ce3+, Ag+ions was studied using fluorescence spectrum. The results showed that the compound7has the ability to identify Mg2+and Ce3+. At8℃, the fluorescence intensity of the solution had increased after adding Mg2+. After heat preservation at40℃for5h, the fluorescence intensity of the solution after adding Ce3+had improved than it was at8℃. After adding Cu2+, Zn2+, Cd2+, Pb2+, Mg2+, Fe3+, Co2+, Ni2+, Mn2+, Ce3+, Ag+ions into the compound10, the fluorescence intensity did not change significantly, and so was it after heat preservation at40℃for5h. The fluorescence spectrum showed that, fluorescence intensity of compound12all has a certain degree of enhancement after adding various ions except the Ni2+ion (the fluorescence intensity decreased by adding Ni2+ion). After heat preservation at40℃for5h, the fluorescence intensity of the solution did not have much difference. So Ni2+has fluorescence quenching to compound12at both8℃and40℃, that is to say that compound12has the specific recognition ability to Ni2+.