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Coordination polymers incorporating Bi(III) and 2,4,6-pyridine tricarboxylic acid and its derivatives: Synthesis, structure and topology


Senior, Levi; Linden, Anthony (2020). Coordination polymers incorporating Bi(III) and 2,4,6-pyridine tricarboxylic acid and its derivatives: Synthesis, structure and topology. Polyhedron, 184:114564.

Abstract

Bi(III) as its oxide combined with 2,4,6-pyridine tricarboxylic acid, H2pdc-COOH, and various pyridine-derived additives in dimethylformamide (dmf) under solvothermal conditions produced three novel bismuth coordination polymers, {[Bi(μ-pdc-COO)2][NH2Me2]3}n, 1, {[Bi(μ-pdc-COO)2][C5H7N2]3·C5H6N2}n, 2, and {[Bi2(μ-pdc-COO)2(μ-pdc-COOH)(pdc-COOH)][NH2Me2]4·2dmf·NHMe2}n, 3. The anionic coordination network topologies are two-dimensional, chains-of-loops and ladders, respectively, but the local 8-coordinate environments about the bismuth(III) centres are in each case between that of a square antiprism and that of a hexagonal bipyramid. When the 4-carboxy substituent in H2pdc-COOH is replaced by another potentially coordinating substituent to give 4-R-2,6-pyridine dicarboxylic acid, H2pdc-R (R = OH, NH2, Cl), the salts obtained contain discrete centrosymmetric dinuclear 8-coordinate bismuth anions with either double O-bridges between the metal centres, [Bi2(μ-pdc-R)2(pdc-R)2(dmf)2][NH2Me2]2 (R = OH, NH2), 4 and 5, or double carboxylate bridges with one long Bi–O bond, [Bi2(μ-pdc-NMe2)2(pdc-NMe2)2(dmf)2][NH2Me2]2, 6 (R = Cl, but replaced by dimethylamine during the reaction). The structures and supramolecular networks of 1–6 are described and compared as an exploration of alternatives to the conventional carboxylate-based organic linking units.

Abstract

Bi(III) as its oxide combined with 2,4,6-pyridine tricarboxylic acid, H2pdc-COOH, and various pyridine-derived additives in dimethylformamide (dmf) under solvothermal conditions produced three novel bismuth coordination polymers, {[Bi(μ-pdc-COO)2][NH2Me2]3}n, 1, {[Bi(μ-pdc-COO)2][C5H7N2]3·C5H6N2}n, 2, and {[Bi2(μ-pdc-COO)2(μ-pdc-COOH)(pdc-COOH)][NH2Me2]4·2dmf·NHMe2}n, 3. The anionic coordination network topologies are two-dimensional, chains-of-loops and ladders, respectively, but the local 8-coordinate environments about the bismuth(III) centres are in each case between that of a square antiprism and that of a hexagonal bipyramid. When the 4-carboxy substituent in H2pdc-COOH is replaced by another potentially coordinating substituent to give 4-R-2,6-pyridine dicarboxylic acid, H2pdc-R (R = OH, NH2, Cl), the salts obtained contain discrete centrosymmetric dinuclear 8-coordinate bismuth anions with either double O-bridges between the metal centres, [Bi2(μ-pdc-R)2(pdc-R)2(dmf)2][NH2Me2]2 (R = OH, NH2), 4 and 5, or double carboxylate bridges with one long Bi–O bond, [Bi2(μ-pdc-NMe2)2(pdc-NMe2)2(dmf)2][NH2Me2]2, 6 (R = Cl, but replaced by dimethylamine during the reaction). The structures and supramolecular networks of 1–6 are described and compared as an exploration of alternatives to the conventional carboxylate-based organic linking units.

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Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Physical and Theoretical Chemistry
Physical Sciences > Inorganic Chemistry
Physical Sciences > Materials Chemistry
Uncontrolled Keywords:Physical and Theoretical Chemistry, Inorganic Chemistry, Materials Chemistry, Bismuth, 2,4,6-pyridine tricarboxylic acid, 2,6-pyridine dicarboxylic acid, Framework, MOF, Structural characterization
Language:English
Date:1 July 2020
Deposited On:20 May 2020 09:00
Last Modified:03 May 2021 15:29
Publisher:Elsevier
ISSN:0277-5387
OA Status:Hybrid
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1016/j.poly.2020.114564
Project Information:
  • : FunderUZH, Department of Chemistry
  • : Grant ID
  • : Project Title

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