Temperature-dependent 3D structures of lanthanide coordination polymers based on dicarboxylate mixed ligands

Kittipong Chainok, Nutcha Ponjan, Chatphorn Theppitak, Phailyn Khemthong, Filip Kielar, Winya Dungkaew, Yan Zhou, Stuart R. Batten

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Abstract

Fourteen three-dimensional (3D) lanthanide coordination polymers (CPs) with dicarboxylate mixed ligands, [Ln(fum) 1.5 (H 2 O) 2 ]·0.5(H 2 bdc)·H 2 O (Ln = Sm (1), Tb (2)), [Ln 2 (fum) 2 (bdc)(H 2 O) 4 ]·2H 2 O (Ln = Sm (3), Eu (4), Tb (5), Er (6)), [Ln(fum) 0.5 (bdc)] (Ln = Sm (7), Eu (8), Tb (9), Er (10)), and [Ln 2 (bdc) 2 (ox)(H 2 O) 4 ]·0.7H 2 O (Ln = Sm (11), Gd (12), Tb (13), Dy (14)), have been synthesized hydrothermally from the self-assembly of lanthanide(iii) ions (Ln 3+ ), fumaric acid (H 2 fum), and terephthalic acid (H 2 bdc) in the presence of potassium hydroxide at different temperatures. The compounds fall into four classes. Compounds 1 and 2 were isolated from hydrothermal reactions performed at a relatively low temperature of 100 °C and found to crystallize in the triclinic space group P1. The 3D framework is assembled from 2D layers of [Ln(fum)(H 2 O) 2 ] units pillared by the chelating fum ligands and has 1D rhombic channels templated by H 2 bdc and lattice H 2 O molecules. The framework presents a binodal (4,5)-connected tcs topology with the point symbol (4 4 ·6 2 )(4 4 ·6 6 ). Raising the reaction temperature to 140 °C resulted in the formation of compounds 3-6. These materials crystallize in the monoclinic system with the polar space group P2 1 and feature a 3D network constructed from dinuclear {Ln 2 (OCO) 6 (H 2 O) 4 } units interlinked by fum and bdc ligands, showing a uninodal 6-connected two-fold interpenetrated pcu topology. The small channels of the framework are occupied by lattice H 2 O molecules. Further increase of the reaction temperature to 160 °C gave rise to the formation of compounds 7-10, crystallizing in the orthorhombic space group Pbca. The 3D framework is generated from 2D corrugated sheets of [Ln(fum)] 2+ bound by bdc ligands and contains no intercalated H 2 O molecules in the lattice. The framework possesses a trinodal (4,6,7)-connected net with the point symbol (4 2 ·6 4 ) 2 (4 6 ·6 8 ·8)(4 12 ·6 9 ) 2 . Finally, compounds 11-14 contained an in situ generated oxalate (ox) ligand formed under hydrothermal conditions conducted at a high reaction temperature of 180 °C. These compounds crystallize in the monoclinic space group P2 1 /c and possess a 3D open framework consisting of a dinuclear [Ln 2 (ox)(H 2 O) 4 ] 2+ unit linked by bridging bdc ligands and has small void channels occupied by lattice H 2 O molecules. The frameworks were topologically simplified as a binodal (4,5)-connected tcj/hc net with a total point symbol of (4 2 ·5 2 ·7 2 )(4 2 ·5 3 ·7 5 ). In the solid state at room temperature, the Tb (2, 5, 9, and 13) and Eu (4 and 8) compounds emit green and red light, respectively.

Original languageEnglish
Pages (from-to)7446-7457
Number of pages12
JournalCrystEngComm
Volume20
Issue number46
DOIs
Publication statusPublished - 14 Dec 2018

Cite this

Chainok, Kittipong ; Ponjan, Nutcha ; Theppitak, Chatphorn ; Khemthong, Phailyn ; Kielar, Filip ; Dungkaew, Winya ; Zhou, Yan ; Batten, Stuart R. / Temperature-dependent 3D structures of lanthanide coordination polymers based on dicarboxylate mixed ligands. In: CrystEngComm. 2018 ; Vol. 20, No. 46. pp. 7446-7457.
@article{a37bef79c1bb4b28b138c8232b5b5699,
title = "Temperature-dependent 3D structures of lanthanide coordination polymers based on dicarboxylate mixed ligands",
abstract = "Fourteen three-dimensional (3D) lanthanide coordination polymers (CPs) with dicarboxylate mixed ligands, [Ln(fum) 1.5 (H 2 O) 2 ]·0.5(H 2 bdc)·H 2 O (Ln = Sm (1), Tb (2)), [Ln 2 (fum) 2 (bdc)(H 2 O) 4 ]·2H 2 O (Ln = Sm (3), Eu (4), Tb (5), Er (6)), [Ln(fum) 0.5 (bdc)] (Ln = Sm (7), Eu (8), Tb (9), Er (10)), and [Ln 2 (bdc) 2 (ox)(H 2 O) 4 ]·0.7H 2 O (Ln = Sm (11), Gd (12), Tb (13), Dy (14)), have been synthesized hydrothermally from the self-assembly of lanthanide(iii) ions (Ln 3+ ), fumaric acid (H 2 fum), and terephthalic acid (H 2 bdc) in the presence of potassium hydroxide at different temperatures. The compounds fall into four classes. Compounds 1 and 2 were isolated from hydrothermal reactions performed at a relatively low temperature of 100 °C and found to crystallize in the triclinic space group P1. The 3D framework is assembled from 2D layers of [Ln(fum)(H 2 O) 2 ] units pillared by the chelating fum ligands and has 1D rhombic channels templated by H 2 bdc and lattice H 2 O molecules. The framework presents a binodal (4,5)-connected tcs topology with the point symbol (4 4 ·6 2 )(4 4 ·6 6 ). Raising the reaction temperature to 140 °C resulted in the formation of compounds 3-6. These materials crystallize in the monoclinic system with the polar space group P2 1 and feature a 3D network constructed from dinuclear {Ln 2 (OCO) 6 (H 2 O) 4 } units interlinked by fum and bdc ligands, showing a uninodal 6-connected two-fold interpenetrated pcu topology. The small channels of the framework are occupied by lattice H 2 O molecules. Further increase of the reaction temperature to 160 °C gave rise to the formation of compounds 7-10, crystallizing in the orthorhombic space group Pbca. The 3D framework is generated from 2D corrugated sheets of [Ln(fum)] 2+ bound by bdc ligands and contains no intercalated H 2 O molecules in the lattice. The framework possesses a trinodal (4,6,7)-connected net with the point symbol (4 2 ·6 4 ) 2 (4 6 ·6 8 ·8)(4 12 ·6 9 ) 2 . Finally, compounds 11-14 contained an in situ generated oxalate (ox) ligand formed under hydrothermal conditions conducted at a high reaction temperature of 180 °C. These compounds crystallize in the monoclinic space group P2 1 /c and possess a 3D open framework consisting of a dinuclear [Ln 2 (ox)(H 2 O) 4 ] 2+ unit linked by bridging bdc ligands and has small void channels occupied by lattice H 2 O molecules. The frameworks were topologically simplified as a binodal (4,5)-connected tcj/hc net with a total point symbol of (4 2 ·5 2 ·7 2 )(4 2 ·5 3 ·7 5 ). In the solid state at room temperature, the Tb (2, 5, 9, and 13) and Eu (4 and 8) compounds emit green and red light, respectively.",
author = "Kittipong Chainok and Nutcha Ponjan and Chatphorn Theppitak and Phailyn Khemthong and Filip Kielar and Winya Dungkaew and Yan Zhou and Batten, {Stuart R.}",
year = "2018",
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Chainok, K, Ponjan, N, Theppitak, C, Khemthong, P, Kielar, F, Dungkaew, W, Zhou, Y & Batten, SR 2018, 'Temperature-dependent 3D structures of lanthanide coordination polymers based on dicarboxylate mixed ligands', CrystEngComm, vol. 20, no. 46, pp. 7446-7457. https://doi.org/10.1039/c8ce01430b

Temperature-dependent 3D structures of lanthanide coordination polymers based on dicarboxylate mixed ligands. / Chainok, Kittipong; Ponjan, Nutcha; Theppitak, Chatphorn; Khemthong, Phailyn; Kielar, Filip; Dungkaew, Winya; Zhou, Yan; Batten, Stuart R.

In: CrystEngComm, Vol. 20, No. 46, 14.12.2018, p. 7446-7457.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Temperature-dependent 3D structures of lanthanide coordination polymers based on dicarboxylate mixed ligands

AU - Chainok, Kittipong

AU - Ponjan, Nutcha

AU - Theppitak, Chatphorn

AU - Khemthong, Phailyn

AU - Kielar, Filip

AU - Dungkaew, Winya

AU - Zhou, Yan

AU - Batten, Stuart R.

PY - 2018/12/14

Y1 - 2018/12/14

N2 - Fourteen three-dimensional (3D) lanthanide coordination polymers (CPs) with dicarboxylate mixed ligands, [Ln(fum) 1.5 (H 2 O) 2 ]·0.5(H 2 bdc)·H 2 O (Ln = Sm (1), Tb (2)), [Ln 2 (fum) 2 (bdc)(H 2 O) 4 ]·2H 2 O (Ln = Sm (3), Eu (4), Tb (5), Er (6)), [Ln(fum) 0.5 (bdc)] (Ln = Sm (7), Eu (8), Tb (9), Er (10)), and [Ln 2 (bdc) 2 (ox)(H 2 O) 4 ]·0.7H 2 O (Ln = Sm (11), Gd (12), Tb (13), Dy (14)), have been synthesized hydrothermally from the self-assembly of lanthanide(iii) ions (Ln 3+ ), fumaric acid (H 2 fum), and terephthalic acid (H 2 bdc) in the presence of potassium hydroxide at different temperatures. The compounds fall into four classes. Compounds 1 and 2 were isolated from hydrothermal reactions performed at a relatively low temperature of 100 °C and found to crystallize in the triclinic space group P1. The 3D framework is assembled from 2D layers of [Ln(fum)(H 2 O) 2 ] units pillared by the chelating fum ligands and has 1D rhombic channels templated by H 2 bdc and lattice H 2 O molecules. The framework presents a binodal (4,5)-connected tcs topology with the point symbol (4 4 ·6 2 )(4 4 ·6 6 ). Raising the reaction temperature to 140 °C resulted in the formation of compounds 3-6. These materials crystallize in the monoclinic system with the polar space group P2 1 and feature a 3D network constructed from dinuclear {Ln 2 (OCO) 6 (H 2 O) 4 } units interlinked by fum and bdc ligands, showing a uninodal 6-connected two-fold interpenetrated pcu topology. The small channels of the framework are occupied by lattice H 2 O molecules. Further increase of the reaction temperature to 160 °C gave rise to the formation of compounds 7-10, crystallizing in the orthorhombic space group Pbca. The 3D framework is generated from 2D corrugated sheets of [Ln(fum)] 2+ bound by bdc ligands and contains no intercalated H 2 O molecules in the lattice. The framework possesses a trinodal (4,6,7)-connected net with the point symbol (4 2 ·6 4 ) 2 (4 6 ·6 8 ·8)(4 12 ·6 9 ) 2 . Finally, compounds 11-14 contained an in situ generated oxalate (ox) ligand formed under hydrothermal conditions conducted at a high reaction temperature of 180 °C. These compounds crystallize in the monoclinic space group P2 1 /c and possess a 3D open framework consisting of a dinuclear [Ln 2 (ox)(H 2 O) 4 ] 2+ unit linked by bridging bdc ligands and has small void channels occupied by lattice H 2 O molecules. The frameworks were topologically simplified as a binodal (4,5)-connected tcj/hc net with a total point symbol of (4 2 ·5 2 ·7 2 )(4 2 ·5 3 ·7 5 ). In the solid state at room temperature, the Tb (2, 5, 9, and 13) and Eu (4 and 8) compounds emit green and red light, respectively.

AB - Fourteen three-dimensional (3D) lanthanide coordination polymers (CPs) with dicarboxylate mixed ligands, [Ln(fum) 1.5 (H 2 O) 2 ]·0.5(H 2 bdc)·H 2 O (Ln = Sm (1), Tb (2)), [Ln 2 (fum) 2 (bdc)(H 2 O) 4 ]·2H 2 O (Ln = Sm (3), Eu (4), Tb (5), Er (6)), [Ln(fum) 0.5 (bdc)] (Ln = Sm (7), Eu (8), Tb (9), Er (10)), and [Ln 2 (bdc) 2 (ox)(H 2 O) 4 ]·0.7H 2 O (Ln = Sm (11), Gd (12), Tb (13), Dy (14)), have been synthesized hydrothermally from the self-assembly of lanthanide(iii) ions (Ln 3+ ), fumaric acid (H 2 fum), and terephthalic acid (H 2 bdc) in the presence of potassium hydroxide at different temperatures. The compounds fall into four classes. Compounds 1 and 2 were isolated from hydrothermal reactions performed at a relatively low temperature of 100 °C and found to crystallize in the triclinic space group P1. The 3D framework is assembled from 2D layers of [Ln(fum)(H 2 O) 2 ] units pillared by the chelating fum ligands and has 1D rhombic channels templated by H 2 bdc and lattice H 2 O molecules. The framework presents a binodal (4,5)-connected tcs topology with the point symbol (4 4 ·6 2 )(4 4 ·6 6 ). Raising the reaction temperature to 140 °C resulted in the formation of compounds 3-6. These materials crystallize in the monoclinic system with the polar space group P2 1 and feature a 3D network constructed from dinuclear {Ln 2 (OCO) 6 (H 2 O) 4 } units interlinked by fum and bdc ligands, showing a uninodal 6-connected two-fold interpenetrated pcu topology. The small channels of the framework are occupied by lattice H 2 O molecules. Further increase of the reaction temperature to 160 °C gave rise to the formation of compounds 7-10, crystallizing in the orthorhombic space group Pbca. The 3D framework is generated from 2D corrugated sheets of [Ln(fum)] 2+ bound by bdc ligands and contains no intercalated H 2 O molecules in the lattice. The framework possesses a trinodal (4,6,7)-connected net with the point symbol (4 2 ·6 4 ) 2 (4 6 ·6 8 ·8)(4 12 ·6 9 ) 2 . Finally, compounds 11-14 contained an in situ generated oxalate (ox) ligand formed under hydrothermal conditions conducted at a high reaction temperature of 180 °C. These compounds crystallize in the monoclinic space group P2 1 /c and possess a 3D open framework consisting of a dinuclear [Ln 2 (ox)(H 2 O) 4 ] 2+ unit linked by bridging bdc ligands and has small void channels occupied by lattice H 2 O molecules. The frameworks were topologically simplified as a binodal (4,5)-connected tcj/hc net with a total point symbol of (4 2 ·5 2 ·7 2 )(4 2 ·5 3 ·7 5 ). In the solid state at room temperature, the Tb (2, 5, 9, and 13) and Eu (4 and 8) compounds emit green and red light, respectively.

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Chainok K, Ponjan N, Theppitak C, Khemthong P, Kielar F, Dungkaew W et al. Temperature-dependent 3D structures of lanthanide coordination polymers based on dicarboxylate mixed ligands. CrystEngComm. 2018 Dec 14;20(46):7446-7457. https://doi.org/10.1039/c8ce01430b