NDLI: Binding of pyrazine-functionalized calix[4]arene ligands with lanthanides in an ionic liquid: thermodynamics and coordination modes

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Zhang, Zhicheng Rao, Linfeng Mohapatra, Prasanta K. Gibson, John K. Dau, Phuong D. Verboom, Willem Ansari, Seraj A.
Description	Author Affiliation: Ansari SA ( Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA. LRao@lbl.gov.)
Abstract	The complexation of representative lanthanides with three calix[4]arenes functionalized with four pyrazine pendent arms containing different substituents such as carbamoyl dioctyl $(L_{I}),$ diisopropyl phosphonate $(L_{II}),$ and diphenyl phosphoryl $(L_{III})$ was investigated in water-saturated 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide $(BumimTf_{2}N)$ by absorption spectroscopy, luminescence spectroscopy, and microcalorimetry. All three ligands form 1:1 ML complexes (M = $Eu^{3+}$ and L = ligand), and the stability constants (logβ) follow the order: $L_{I}$ (−1.38 ± 0.66) ≪ $L_{II}$ (3.71 ± 0.02) < $L_{III}$ (7.47 ± 0.03), similar to the trend in the metal distribution coefficients in solvent extraction using these ligands as extractants. The enthalpy of complexation, determined by microcalorimetry, shows that the complexation of lanthanides with these bulky ligands is exothermic, and proceeds via replacement of water molecules from the primary coordination spheres. The 1:1 stoichiometry of the ML complexes was confirmed by electrospray ionization mass spectrometry. Results from optical absorption, luminescence and $^{31}P-NMR$ spectroscopy suggest that, out of four pendent arms on the rigid calixarene platform, only two arms coordinate with the lanthanide ion and each arm is tridentate. The influence of structural features of the ligand on the complexation of lanthanides is explained with the help of thermodynamic parameters.
ISSN	14779226
Issue Number	14
Journal	Dalton Trans.
Volume Number	44
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2015-04-14
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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