Thorium(IV) organic frameworks with aromatic polycarboxylate ligands

Yingjie Zhang, Fatima Kadi, Inna Karatchevtseva, Jason R. Price, Timothy Murphy, Richard Wuhrer, Feng Li, Gregory R. Lumpkin

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Contrary to the fairly well established structural chemistry of uranium(VI) with aromatic polycarboxylate ligands, the knowledge on thorium(Th) structural chemistry with this family of ligands is very limited. In this paper, we report the synthesis, spectroscopic and thermal studies, and crystal structures of three Th organic frameworks with 1,2,4,5-benzenetetracarboxylate (btca) or 1,4-benzenedicarboxylate (bdc). Both [Th(btca)(DMF)2(H2O)] (1) and [Th(bdc)2(DMF)2] (2) (DMF = dimethylformamide) have two dimensional (2D) layered structures constructed with 9- (1) or 10- (2) fold coordinated Th polyhedrons and μ4-btca (1) or μ2-bdc (2) ligands, respectively, with two coordinated DMF molecules in cis- (1) or trans- (2) positions on each Th atom. The third phase, [Th(bdc)2] (3), has a 3D pillared framework built with eightfold coordinated Th polyhedrons and μ4-bdc ligands. Their vibrational modes have been investigated and correlated to the structures. VT-PXRD confirmed that 3 is thermally robust to 500 °C and the weight loss at ∼300 °C is due to the loss of water molecules in the solvent accessible voids in the crystal lattice.

Original languageEnglish
Pages (from-to)163-172
Number of pages10
JournalJournal of Inclusion Phenomena and Macrocyclic Chemistry
Volume82
Issue number1-2
DOIs
Publication statusPublished - Jun 2015
Externally publishedYes

Keywords

  • Thorium
  • Polycarboxylate
  • Frameworks
  • X-ray diffraction

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