Title

Strain Alleviation in an Isomorphous Series of Lanthanide 2-Nitroterephthalates [Ln2(TPNO2)3(H2O)2]·2H2O (Ln = Pr – Lu, except Pm)

Authors

Ralph A. Zehnder, Angelo State University
Nick Fontaine, University of Louisiana at Monroe
Badwi A. Mouawad, University of Louisiana at Monroe
Jacob K. Leonard, University of Louisiana at Monroe
Matthias Zeller, Purdue University
Frank R. Fronczek, Louisiana State University
Daniel T. de Lill, Florida Atlantic UniversityFollow
April Ballard, Florida Atlantic University
Daniel Bonnette, University of Louisiana at Monroe
Aaron Head, University of Louisiana at Monroe
Krishna Ghimire, University of Louisiana at Monroe
Jordan N. Welch, University of Louisiana at Monroe
Elee R. Barber, University of Louisiana at Monroe
Jared M. Murray, University of Louisiana at Monroe
Christian Dempsey, Angelo State University
James Jenkins, Angelo State University
Gregory Jackson, Angelo State University
Mary Tokunboh, University of Louisiana at Monroe
Stevie R. Bach, University of Louisiana at Monroe
Jaimie A. Treadway Harris, University of Louisiana at Monroe

Document Type

Article

Publication Date

10-1-2017

Publication Title

Inorganica Chimica Acta

Keywords

f-Elements, Metal organic frameworks, Lanthanide contraction, Hydrothermal synthesis, Thermogravimetric analysis

ISSN

0020-1693

Volume

467

First Page

276

Last Page

286

Abstract

An extended series of trivalent lanthanide 2-nitroterephthalates, [Ln₂(TPNO₂)₃(H₂O)₂]·2H₂O, (Ln = Pr through Lu, except Pm) were synthesized hydrothermally from Ln₂O₃ and 2-nitroterephthalic acid (H₂TPNO₂) at 170 °C in Teflon lined Parr steel autoclaves, and were characterized via single crystal X-ray diffraction, powder X-ray diffraction, FT-IR spectroscopy, elemental analyses, and thermogravimetric analyses.

All [Ln₂(TPNO₂)₃(H₂O)₂]·2H₂O coordination polymers are isomorphous, crystallizing in the monoclinic crystal system with space group C2/c. The metal centers in all networks possess the coordination number 8, while forming a three-dimensional extended lattice. Two metal centers form Ln₂O₁₄ entities, comprising crystallographically identical LnO₈ polyhedra, connected via edge-sharing, utilizing two carboxylate O-atoms. These Ln₂O₁₄ units are separated along the a- and b-axes by individual 2-nitroterephthalate linkers, while being closely connected along the c-axis via two carboxylate groups on each side.

Compared to small inorganic anions, the rather flexible 2-nitroterephthalate seems to allow for the unobstructed decrease in size of the LnO₈ polyhedra as Ln³⁺ ionic radii decrease towards the heavier Ln elements. Hence, the structural parameters of the crystal lattice adjust gradually without noticeable strain buildup along the series resulting in isomorphous arrangements for all networks. The thermogravimetric and FT-IR measurements seem to confirm the structural features.

Comments

©2017 Elsevier B.V. All rights reserved

Additional Comments

Louisiana Board of Regents contract #s: LEQSF (1999-2000)-ENH-TR-13, LEQSF (2007-10)-RD-A-40; NSF grant #: 0087210; Ohio Board of Regents grant #: CAP-491

NSUWorks Citation

Zehnder, R. A., Fontaine, N., Mouawad, B. A., Leonard, J. K., Zeller, M., Fronczek, F. R., de Lill, D. T., Ballard, A., Bonnette, D., Head, A., Ghimire, K., Welch, J. N., Barber, E. R., Murray, J. M., Dempsey, C., Jenkins, J., Jackson, G., Tokunboh, M., Bach, S. R., & Treadway Harris, J. A. (2017). Strain Alleviation in an Isomorphous Series of Lanthanide 2-Nitroterephthalates [Ln2(TPNO2)3(H2O)2]·2H2O (Ln = Pr – Lu, except Pm). Inorganica Chimica Acta, 467, 276 - 286. https://doi.org/10.1016/j.ica.2017.08.030. Retrieved from https://nsuworks.nova.edu/cnso_chemphys_facarticles/250

ORCID ID

0000-0003-0891-7246

DOI

10.1016/j.ica.2017.08.030