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Thorium(IV) organic frameworks with aromatic polycarboxylate ligands

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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 µ 4-btca (1) or µ 2-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 µ 4-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.

Graphical Abstract

Thorium(IV) organic frameworks (TOC): Three new thorium organic frameworks with aromatic polycarboxylate ligands have been synthesized and characterized. 2D layered structures are favored at room temperature and a thermal robust, 3D thorium organic framework has been made under hydrothermal conditions. Their vibrational modes and thermal stabilities have been further investigated.

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Acknowledgments

The authors would like to thank Dr. J. Cejka for his advice on IR and Raman assignments, Mr. N. Scales for TG/DTA measurements, Dr. M. Bhadbhade for the help with the structure refinement of 1, Advanced Materials Characterisation Facility (AMCF), University of Western Sydney for VT-PXRD measurements. The crystallographic data for 1-3 were collected on MX2 beamline at the Australian Synchrotron, Victoria, Australia.

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The authors declare that they have no conflict of interest.

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Authors and Affiliations

  1. Australian Nuclear Science and Technology Organisation, Locked Bag 2001, Kirrawee DC, NSW, 2232, Australia

    Yingjie Zhang, Fatima Kadi, Inna Karatchevtseva & Gregory R. Lumpkin

  2. Australian Synchrotron, 800 Blackburn Road, Clayton, VIC, 3168, Australia

    Jason R. Price

  3. Advanced Materials Characterisation Facility, University of Western Sydney, Locked Bag 1797, Penrith, NSW, 2751, Australia

    Timothy Murphy & Richard Wuhrer

  4. School of Science and Health, University of Western Sydney, Locked Bag 1797, Penrith, NSW, 2751, Australia

    Feng Li

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  1. Yingjie Zhang
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  2. Fatima Kadi
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Correspondence to Yingjie Zhang.

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10847_2015_506_MOESM1_ESM.docx

SEM and optical images, EDS spectra, crystallographic data for 1-3 (CIF files), PXRD patterns (1 and 3), VT-PXRD patterns for 3. This material is available free of charge via the Internet at http://pubs.acs.org. The crystallographic data for 1-3 have been deposited at the Cambridge Crystallographic Data Centre with CCDC 964656 (1), 1033540 (2) and 1033541 (3). Supplementary material 1 (DOCX 3196 kb)

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Zhang, Y., Kadi, F., Karatchevtseva, I. et al. Thorium(IV) organic frameworks with aromatic polycarboxylate ligands. J Incl Phenom Macrocycl Chem 82, 163–172 (2015). https://doi.org/10.1007/s10847-015-0506-y

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