A calixarene derivative, 5,11,17,23-tetra（diethoxyphosphoryl）-25,26,27,28-tetraacetoxycalix[4]arene （L）, was studied for the extraction and separation of thorium and rare earths in nitrate medium. Thorium was extracted into the organic phase by a complex of Th（NO3）4·L with the logarithm of the equilibrium constant of 2.77. Thermodynamic functions, AH, AG and AS were calculated to be -2.49, -15.55 kJ/mol and 44.53 J/（mol·K）, respectively. The results indicated that this calixarene derivative might be used to separate thorium from rare earths and the separation factors were larger than 26. However, the salting-out agents affected the separation.
The syntheses, crystal structures, magnetic and luminescent properties of three isomorphous compounds [Ln III 6 (μ 4-O) 2 (C4A) 2-(NO 3 ) 2 (HCOO) 2 (CH 3 O) 2 (DMF) 4 (CH 3 OH) 4 ] (Ln = Gd (1), Tb (2) and Dy (3); H 4 C4A = p-tert-butylcalix[4]arene) are reported. These three compounds are featured with the sandwich-like units constructed by two tail-to-tail calixarene molecules and an in-between Ln III 6 octahedron. The Dy III compound exhibits both single molecule magnet behavior and photoluminescence.
BI YanFengXU GuanChengLIAO WuPingDU ShangChaoDENG RuiPingWANG BingWu
