Highly efficient N‑pivot tripodal diglycolamide ligands for trivalent f‑cations: Synthesis, extraction, spectroscopy, and density functional theory studies

Seraj A. Ansari, Prasanta K. Mohapatra*, Andrea Leoncini, S. K. Musharaf Ali, Jurriaan Huskens, Willem Verboom*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

4 Citations (Scopus)

Abstract

A series of four N-pivot tripodal diglycolamide (DGA) ligands, where three DGA moieties are attached to the central N atom via spacers of different lengths and with varying alkyl substituents on the amidic nitrogen of DGA (LI−LIV), were studied for their extraction and complexation ability toward trivalent lanthanide/actinide ions, including solvent extraction, complexation using spectrophotometric titrations, and luminescence spectroscopic studies. Introduction of a methyl group on the amidic nitrogen atom gives rise to a 400 fold increase of the Eu distribution (D) value [LIII (NMe) vs LII (NH)] at 1 M HNO3. Enlargement of the spacer length between the pivotal N atom and the DGA moieties with one carbon atom results in a 14 times higher DEu value [LI (C3) vs LII (C2)]. Slope analyses showed that Eu3+ was extracted as a bis-solvated species with all four ligands. The compositions of the Eu3+/L complexes were further confirmed by spectroscopic measurements, its formation constants following the order: LIII > LIV > LI > LII. Luminescence spectroscopy and electrospray ionization mass spectrometry revealed that all four ligands form [Eu(L)2(NO3)3] complexes. Density functional theory and thermodynamic parameters corroborated the existence of [Eu(L)2(NO3)3] complexes.

Original languageEnglish
Pages (from-to)8633-8644
Number of pages12
JournalInorganic chemistry
Volume58
Issue number13
DOIs
Publication statusPublished - 1 Jul 2019

Keywords

  • UT-Hybrid-D

Fingerprint Dive into the research topics of 'Highly efficient N‑pivot tripodal diglycolamide ligands for trivalent f‑cations: Synthesis, extraction, spectroscopy, and density functional theory studies'. Together they form a unique fingerprint.

  • Cite this