NDLI: Binary lanthanide(III)/nitrate and ternary lanthanide(III)/nitrate/chloride complexes in an ionic liquid containing water: optical absorption and luminescence studies

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Rao, Linfeng Ansari, Seraj A. Liu, Lisheng
Description	Author Affiliation: Ansari SA ( Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA. LRao@lbl.gov.)
Abstract	The formation of binary Ln(III)/nitrate and ternary Ln(III)/nitrate/chloride complexes in a water-saturated ionic liquid, 1-butyl-3-methyl imidazolium bis(trifluoromethanesulfonyl)imide (denoted $BumimTf_{2}N),$ was investigated by absorption spectrophotometry and luminescence spectroscopy. Four successive binary complexes, $Nd(NO_{3})^{2+},$ $Nd(NO_{3})_{2}^{+},$ $Nd(NO_{3})_{3},$ and $Nd(NO_{3})_{4}^{−},$ were identified, and their stability constants in water-saturated $BumimTf_{2}N$ are several orders of magnitude higher than those in aqueous solutions, but much lower than those observed in dry $BumimTf_{2}N.$ The complexation of lanthanides with nitrate in wet $BumimTf_{2}N$ proceeds via the replacement of water molecules by bidentate nitrate anions from the inner solvation spheres of $Ln^{3+}$ cations. In the absence of nitrate, the precipitation of Ln(III)/chloride complex(es) occurs at low ratios of $C_{Cl}/C_{Ln}$ (<6) in $BumimTf_{2}N,$ which precludes the determination of stability constants of binary Ln(III)/chloride complexes by spectrophotometry or luminescence spectroscopy. However, using a competition approach, the formation of two ternary complexes, $Ln(NO_{3})_{3}Cl_{2}^{2−}$ and $Ln(NO_{3})_{2}Cl_{4}^{3−},$ has been observed and their stability constants in wet $BumimTf_{2}N$ were determined. Data indicate that both nitrate and chloride are stronger ligands than water for lanthanides in $BumimTf_{2}N.$
ISSN	14779226
Issue Number	6
Journal	Dalton Trans.
Volume Number	44
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2015-02-14
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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