Network dimensionality and ligand flexibility in lanthanide terephthalate hydrates

Ralph A. Zehnder, Robert A. Renn, Ethan Pippin, Matthias Zeller, Kraig A. Wheeler, Jason A. Carr, Nick Fontaine, Nathan C. McMullen

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

Various lanthanide open framework materials incorporating the terephthalate (TP) entity were prepared using hydrothermal synthesis methods at a moderate temperature of 170 °C. The compounds Nd2(TP)3(H 2O)4(1), Er2(TP)3(H 2O)4(2), Yb2(TP)3(H 2O)2(3), Yb2(TP)3(H 2O)6(4), and Yb2(TP)3(H 2O)8·2H2O (5), were characterized by single crystal structural analysis and FT-IR spectroscopy. While compounds 1 and 2 have been reported before on the basis of powder X-ray diffraction, the structural characterization of any ytterbium terephthalate species is unprecedented. Compounds 1-5 crystallize in triclinic settings with space group P-1. The compounds are compared with their previously reported Er and Tb-counterparts and the reduction of the dimensionality of the resulting networks from 3D over 2D to 1D with increasing level of hydration is discussed. Compounds 1, 2, and 3 with the lowest water content assemble in three-dimensional network lattices. Compounds 4 and 5, however, form 2D layered systems and 1D rod like chains, respectively, which are held together by hydrogen bonds originating from coordinating H2O. The crystal lattices of the 3D networks experience higher levels of tension as can be seen by increasing out-of-plane torsion with regard to the terephthalate carboxylate groups. Moreover, there seems to be a correlation between the level of strain on the aromatic ligands and the reduction of the number of carboxylate oxygen atoms that are part of the coordination polyhedra.

Original languageEnglish (US)
Pages (from-to)109-119
Number of pages11
JournalJournal of Molecular Structure
Volume985
Issue number1
DOIs
StatePublished - Jan 15 2011

Fingerprint

Lanthanoid Series Elements
Hydrates
Ligands
Ytterbium
terephthalic acid
Hydrothermal synthesis
Structural analysis
Crystal lattices
Hydration
Torsional stress
X ray powder diffraction
Water content
Infrared spectroscopy
Hydrogen bonds
Single crystals
Oxygen
Atoms

Keywords

  • Crystal structures
  • Ionic radius
  • Lanthanide coordination polymers
  • Network dimensionality
  • Out-of-plane torsion
  • Terephthalic acid

ASJC Scopus subject areas

  • Analytical Chemistry
  • Spectroscopy
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Zehnder, R. A., Renn, R. A., Pippin, E., Zeller, M., Wheeler, K. A., Carr, J. A., ... McMullen, N. C. (2011). Network dimensionality and ligand flexibility in lanthanide terephthalate hydrates. Journal of Molecular Structure, 985(1), 109-119. https://doi.org/10.1016/j.molstruc.2010.10.030

Network dimensionality and ligand flexibility in lanthanide terephthalate hydrates. / Zehnder, Ralph A.; Renn, Robert A.; Pippin, Ethan; Zeller, Matthias; Wheeler, Kraig A.; Carr, Jason A.; Fontaine, Nick; McMullen, Nathan C.

In: Journal of Molecular Structure, Vol. 985, No. 1, 15.01.2011, p. 109-119.

Research output: Contribution to journalArticle

Zehnder, RA, Renn, RA, Pippin, E, Zeller, M, Wheeler, KA, Carr, JA, Fontaine, N & McMullen, NC 2011, 'Network dimensionality and ligand flexibility in lanthanide terephthalate hydrates', Journal of Molecular Structure, vol. 985, no. 1, pp. 109-119. https://doi.org/10.1016/j.molstruc.2010.10.030
Zehnder, Ralph A. ; Renn, Robert A. ; Pippin, Ethan ; Zeller, Matthias ; Wheeler, Kraig A. ; Carr, Jason A. ; Fontaine, Nick ; McMullen, Nathan C. / Network dimensionality and ligand flexibility in lanthanide terephthalate hydrates. In: Journal of Molecular Structure. 2011 ; Vol. 985, No. 1. pp. 109-119.
@article{e89052e7abf748e4982c8df4e6d3dee9,
title = "Network dimensionality and ligand flexibility in lanthanide terephthalate hydrates",
abstract = "Various lanthanide open framework materials incorporating the terephthalate (TP) entity were prepared using hydrothermal synthesis methods at a moderate temperature of 170 °C. The compounds Nd2(TP)3(H 2O)4(1), Er2(TP)3(H 2O)4(2), Yb2(TP)3(H 2O)2(3), Yb2(TP)3(H 2O)6(4), and Yb2(TP)3(H 2O)8·2H2O (5), were characterized by single crystal structural analysis and FT-IR spectroscopy. While compounds 1 and 2 have been reported before on the basis of powder X-ray diffraction, the structural characterization of any ytterbium terephthalate species is unprecedented. Compounds 1-5 crystallize in triclinic settings with space group P-1. The compounds are compared with their previously reported Er and Tb-counterparts and the reduction of the dimensionality of the resulting networks from 3D over 2D to 1D with increasing level of hydration is discussed. Compounds 1, 2, and 3 with the lowest water content assemble in three-dimensional network lattices. Compounds 4 and 5, however, form 2D layered systems and 1D rod like chains, respectively, which are held together by hydrogen bonds originating from coordinating H2O. The crystal lattices of the 3D networks experience higher levels of tension as can be seen by increasing out-of-plane torsion with regard to the terephthalate carboxylate groups. Moreover, there seems to be a correlation between the level of strain on the aromatic ligands and the reduction of the number of carboxylate oxygen atoms that are part of the coordination polyhedra.",
keywords = "Crystal structures, Ionic radius, Lanthanide coordination polymers, Network dimensionality, Out-of-plane torsion, Terephthalic acid",
author = "Zehnder, {Ralph A.} and Renn, {Robert A.} and Ethan Pippin and Matthias Zeller and Wheeler, {Kraig A.} and Carr, {Jason A.} and Nick Fontaine and McMullen, {Nathan C.}",
year = "2011",
month = "1",
day = "15",
doi = "10.1016/j.molstruc.2010.10.030",
language = "English (US)",
volume = "985",
pages = "109--119",
journal = "Journal of Molecular Structure",
issn = "0022-2860",
publisher = "Elsevier",
number = "1",

}

TY - JOUR

T1 - Network dimensionality and ligand flexibility in lanthanide terephthalate hydrates

AU - Zehnder, Ralph A.

AU - Renn, Robert A.

AU - Pippin, Ethan

AU - Zeller, Matthias

AU - Wheeler, Kraig A.

AU - Carr, Jason A.

AU - Fontaine, Nick

AU - McMullen, Nathan C.

PY - 2011/1/15

Y1 - 2011/1/15

N2 - Various lanthanide open framework materials incorporating the terephthalate (TP) entity were prepared using hydrothermal synthesis methods at a moderate temperature of 170 °C. The compounds Nd2(TP)3(H 2O)4(1), Er2(TP)3(H 2O)4(2), Yb2(TP)3(H 2O)2(3), Yb2(TP)3(H 2O)6(4), and Yb2(TP)3(H 2O)8·2H2O (5), were characterized by single crystal structural analysis and FT-IR spectroscopy. While compounds 1 and 2 have been reported before on the basis of powder X-ray diffraction, the structural characterization of any ytterbium terephthalate species is unprecedented. Compounds 1-5 crystallize in triclinic settings with space group P-1. The compounds are compared with their previously reported Er and Tb-counterparts and the reduction of the dimensionality of the resulting networks from 3D over 2D to 1D with increasing level of hydration is discussed. Compounds 1, 2, and 3 with the lowest water content assemble in three-dimensional network lattices. Compounds 4 and 5, however, form 2D layered systems and 1D rod like chains, respectively, which are held together by hydrogen bonds originating from coordinating H2O. The crystal lattices of the 3D networks experience higher levels of tension as can be seen by increasing out-of-plane torsion with regard to the terephthalate carboxylate groups. Moreover, there seems to be a correlation between the level of strain on the aromatic ligands and the reduction of the number of carboxylate oxygen atoms that are part of the coordination polyhedra.

AB - Various lanthanide open framework materials incorporating the terephthalate (TP) entity were prepared using hydrothermal synthesis methods at a moderate temperature of 170 °C. The compounds Nd2(TP)3(H 2O)4(1), Er2(TP)3(H 2O)4(2), Yb2(TP)3(H 2O)2(3), Yb2(TP)3(H 2O)6(4), and Yb2(TP)3(H 2O)8·2H2O (5), were characterized by single crystal structural analysis and FT-IR spectroscopy. While compounds 1 and 2 have been reported before on the basis of powder X-ray diffraction, the structural characterization of any ytterbium terephthalate species is unprecedented. Compounds 1-5 crystallize in triclinic settings with space group P-1. The compounds are compared with their previously reported Er and Tb-counterparts and the reduction of the dimensionality of the resulting networks from 3D over 2D to 1D with increasing level of hydration is discussed. Compounds 1, 2, and 3 with the lowest water content assemble in three-dimensional network lattices. Compounds 4 and 5, however, form 2D layered systems and 1D rod like chains, respectively, which are held together by hydrogen bonds originating from coordinating H2O. The crystal lattices of the 3D networks experience higher levels of tension as can be seen by increasing out-of-plane torsion with regard to the terephthalate carboxylate groups. Moreover, there seems to be a correlation between the level of strain on the aromatic ligands and the reduction of the number of carboxylate oxygen atoms that are part of the coordination polyhedra.

KW - Crystal structures

KW - Ionic radius

KW - Lanthanide coordination polymers

KW - Network dimensionality

KW - Out-of-plane torsion

KW - Terephthalic acid

UR - http://www.scopus.com/inward/record.url?scp=78649944909&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=78649944909&partnerID=8YFLogxK

U2 - 10.1016/j.molstruc.2010.10.030

DO - 10.1016/j.molstruc.2010.10.030

M3 - Article

AN - SCOPUS:78649944909

VL - 985

SP - 109

EP - 119

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

SN - 0022-2860

IS - 1

ER -