Physicochemical Properties and Theoretical Modeling of Actinide Complexes with a para-tert-Butylcalix[6]arene Bearing Phosphinoyl Pendants. Extraction Capability of the Calixarene toward f Elements

摘要: The coordination ability of the hexaphosphinoylated p-tert-butylcalix[6]arene $B_6bL^6$ toward actinides is established, as well its good separation actinide ions $UO_2 ^{2+}$ and Th(IV) over trivalent rare earths such La(III), Eu(III), Y(III). Spectrophotometric titration uranyl with in $CH_3CN$ yields $\log\beta_{11}= 7.1$ $\log\beta_{12}= 12.5$ for 1:1 1:2 ($UO_2 ^{2+}/B_6bL^6$) species, respectively. Actinide complexes (M/L) stoichiometries are isolated characterized by elemental analysis, IR, UV-vis. Compounds 1 3 fulfill their $CN = 8$ just $B_6bL^6$, while compounds 2 4 require coordinated nitrates and/or water molecules. luminescence spectra parameters FWMH, vibronic spacing ($\upsilon_{sp}$), U-O bond length, lifetimes, permit understanding chemistry these calixarene complexes. Energy transfer from ligand to ion demonstrated be relevant compound $Q_{abs} 2.0%$. complex emission reveals a biexponential decay $\tau_s$ 210 220 μs $\tau_L$ 490 650 3, liquid-liquid extraction results demonstrate capability but not at room temperature. extracted species keeps 1(cation)/1(calixarene) ratio ^{2+}$, $Th^{4+}$, $Eu^{3+}$ ions. A capacity $Th^{4+}$ using aqueous phase containing even up 0.3 M thorium nitrate an organic $2.47 \cross 10^{-4} M$ chloroform found. spectroscopic properties studies reveal uranophilic nature $B_6bL^6$. molecular modeling agreement experimental findings.