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Title: Hydrothermal chemistry of Th(IV) with aromatic dicarboxylates: New framework compounds and in situ ligand syntheses

Abstract

A novel thorium (IV) coordination polymer, Th(C{sub 5}H{sub 2}N{sub 2}O{sub 4}){sub 2}(H{sub 2}O){sub 2} (1), has been prepared under the hydrothermal reaction of thorium nitrate tetrahydrate and 3,5-pyrazoledicarboxylic acid (H{sub 3}pdc). Compound 1 (orthorhombic, P2{sub 1}2{sub 1}2{sub 1}, a=6.9362(5) A, b=10.7806(8) A, c=17.9915(14) A, Z=2, R{sub 1}=0.0210, wR{sub 2}=0.0470) consists of thorium metal centers connected via H{sub 3}pdc linkages to form an overall three-dimensional structure containing {pi}-{pi} interactions between the pyrazole rings. 2,3-Pyrazinedicarboxylic acid (H{sub 2}pzdc) was explored as well to (1) study the effect of the location of the carboxylic groups around the aromatic ring and (2) produce heterometallic compounds. Thorium (IV) and copper (II) were combined with H{sub 2}pzdc, resulting in an interesting decomposition reaction characterized though the isolation of Th(C{sub 2}O{sub 4}){sub 2}(H{sub 2}O){sub 2}.2H{sub 2}O (2) (monoclinic, C2/c, a=13.8507(12) A, b=7.8719(7) A, c=10.7961(16) A, {beta}=118.0310(10){sup o}, Z=2, R{sub 1}=0.0160, wR{sub 2}=0.0349), Cu(C{sub 6}H{sub 2}N{sub 2}O{sub 4}) (3) (monoclinic, C2/c, a=11.499(3) A, b=7.502(2) A, c=7.402(2) A, {beta}=93.892(5){sup o}, Z=4, R{sub 1}=0.0472, wR{sub 2}=0.0745) and Cu(C{sub 5}H{sub 3}N{sub 2}O{sub 2})(NO{sub 3})(H{sub 2}O) (4). The capture of these species provides mechanistic evidence for the formation of the oxalate anions observed in 2 via the decarboxylation of H{sub 2}pzdc tomore » yield the linker in 4: 2-pyrazinecarboxylate anions. - Graphical abstract: 3,5-Pyrazoledicarboxylic and 2,3-pyridinedicarboxylic acid were utilized in synthesizing two novel thorium (IV) coordination polymers. Attempts to synthesize a Th-Cu bimetallic compound with 2,3-pyridinedicarboxylic acid resulted in a triphasic mixture (2, 3 and 4, respectively). The oxalate anion observed in Th(C{sub 2}O{sub 4}){sub 2}(H{sub 2}O){sub 2}.2H{sub 2}O (2) is theorized to result from decarboxylation of 2,3-pyridinedicarboxylic acid as supported by the organic linker, 2-pyrazinecarboxylate, observed in Cu(C{sub 5}H{sub 3}N{sub 2}O{sub 2})(NO{sub 3})(H{sub 2}O) (4)« less

Authors:
 [1]; ;  [2];  [2]
  1. Department of Chemistry and Biochemistry, DePauw University, Greencastle, IN 46135 (United States)
  2. Department of Chemistry, George Washington University, Washington, DC 20052 (United States)
Publication Date:
OSTI Identifier:
21043901
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 181; Journal Issue: 2; Other Information: DOI: 10.1016/j.jssc.2007.12.008; PII: S0022-4596(07)00514-2; Copyright (c) 2008 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANIONS; DECARBOXYLATION; HYDROTHERMAL SYNTHESIS; LIGANDS; MONOCLINIC LATTICES; ORTHORHOMBIC LATTICES; OXALATES; POLYMERS; PYRAZOLES; THORIUM COMPLEXES; THORIUM NITRATES; WATER

Citation Formats

Ziegelgruber, Kate L, Department of Chemistry, The George Washington University, Washington, DC 20052, Knope, Karah E, Frisch, Mark, Cahill, Christopher L, and Geophysical Laboratory, Carnegie Institution of Washington, Washington, DC 20015. Hydrothermal chemistry of Th(IV) with aromatic dicarboxylates: New framework compounds and in situ ligand syntheses. United States: N. p., 2008. Web. doi:10.1016/j.jssc.2007.12.008.
Ziegelgruber, Kate L, Department of Chemistry, The George Washington University, Washington, DC 20052, Knope, Karah E, Frisch, Mark, Cahill, Christopher L, & Geophysical Laboratory, Carnegie Institution of Washington, Washington, DC 20015. Hydrothermal chemistry of Th(IV) with aromatic dicarboxylates: New framework compounds and in situ ligand syntheses. United States. https://doi.org/10.1016/j.jssc.2007.12.008
Ziegelgruber, Kate L, Department of Chemistry, The George Washington University, Washington, DC 20052, Knope, Karah E, Frisch, Mark, Cahill, Christopher L, and Geophysical Laboratory, Carnegie Institution of Washington, Washington, DC 20015. 2008. "Hydrothermal chemistry of Th(IV) with aromatic dicarboxylates: New framework compounds and in situ ligand syntheses". United States. https://doi.org/10.1016/j.jssc.2007.12.008.
@article{osti_21043901,
title = {Hydrothermal chemistry of Th(IV) with aromatic dicarboxylates: New framework compounds and in situ ligand syntheses},
author = {Ziegelgruber, Kate L and Department of Chemistry, The George Washington University, Washington, DC 20052 and Knope, Karah E and Frisch, Mark and Cahill, Christopher L and Geophysical Laboratory, Carnegie Institution of Washington, Washington, DC 20015},
abstractNote = {A novel thorium (IV) coordination polymer, Th(C{sub 5}H{sub 2}N{sub 2}O{sub 4}){sub 2}(H{sub 2}O){sub 2} (1), has been prepared under the hydrothermal reaction of thorium nitrate tetrahydrate and 3,5-pyrazoledicarboxylic acid (H{sub 3}pdc). Compound 1 (orthorhombic, P2{sub 1}2{sub 1}2{sub 1}, a=6.9362(5) A, b=10.7806(8) A, c=17.9915(14) A, Z=2, R{sub 1}=0.0210, wR{sub 2}=0.0470) consists of thorium metal centers connected via H{sub 3}pdc linkages to form an overall three-dimensional structure containing {pi}-{pi} interactions between the pyrazole rings. 2,3-Pyrazinedicarboxylic acid (H{sub 2}pzdc) was explored as well to (1) study the effect of the location of the carboxylic groups around the aromatic ring and (2) produce heterometallic compounds. Thorium (IV) and copper (II) were combined with H{sub 2}pzdc, resulting in an interesting decomposition reaction characterized though the isolation of Th(C{sub 2}O{sub 4}){sub 2}(H{sub 2}O){sub 2}.2H{sub 2}O (2) (monoclinic, C2/c, a=13.8507(12) A, b=7.8719(7) A, c=10.7961(16) A, {beta}=118.0310(10){sup o}, Z=2, R{sub 1}=0.0160, wR{sub 2}=0.0349), Cu(C{sub 6}H{sub 2}N{sub 2}O{sub 4}) (3) (monoclinic, C2/c, a=11.499(3) A, b=7.502(2) A, c=7.402(2) A, {beta}=93.892(5){sup o}, Z=4, R{sub 1}=0.0472, wR{sub 2}=0.0745) and Cu(C{sub 5}H{sub 3}N{sub 2}O{sub 2})(NO{sub 3})(H{sub 2}O) (4). The capture of these species provides mechanistic evidence for the formation of the oxalate anions observed in 2 via the decarboxylation of H{sub 2}pzdc to yield the linker in 4: 2-pyrazinecarboxylate anions. - Graphical abstract: 3,5-Pyrazoledicarboxylic and 2,3-pyridinedicarboxylic acid were utilized in synthesizing two novel thorium (IV) coordination polymers. Attempts to synthesize a Th-Cu bimetallic compound with 2,3-pyridinedicarboxylic acid resulted in a triphasic mixture (2, 3 and 4, respectively). The oxalate anion observed in Th(C{sub 2}O{sub 4}){sub 2}(H{sub 2}O){sub 2}.2H{sub 2}O (2) is theorized to result from decarboxylation of 2,3-pyridinedicarboxylic acid as supported by the organic linker, 2-pyrazinecarboxylate, observed in Cu(C{sub 5}H{sub 3}N{sub 2}O{sub 2})(NO{sub 3})(H{sub 2}O) (4)},
doi = {10.1016/j.jssc.2007.12.008},
url = {https://www.osti.gov/biblio/21043901}, journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = 2,
volume = 181,
place = {United States},
year = {Fri Feb 15 00:00:00 EST 2008},
month = {Fri Feb 15 00:00:00 EST 2008}
}