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Title: Anion-induced structural transformation of a sulfate-incorporated 2D Cd(II)–organic framework

Abstract

A Cd(II)–organic framework {[Cd_2(tpim)_4(SO_4)(H_2O)_2]·(SO_4)·21H_2O}{sub n} (1) was synthesized by reacting CdSO{sub 4}·8/3H{sub 2}O and 2,4,5-tri(4-pyridyl)imidazole (tpim) under hydrothermal conditions. A structural analysis showed that compound 1 adopts a layered structure in which the [Cd(tpim){sub 2}]{sub n} chains are linked by sulfate anions. These 2D layers are further packed into a 3D supramolecular framework via π–π interactions. The structure contains two types of SO{sub 4}{sup 2−} anions, i.e., bridging SO{sub 4}{sup 2−} and free SO{sub 4}{sup 2−} anions, the latter of which are included in the large channels of the framework. Compound 1 exhibits interesting anion exchange behavior. In the presence of SCN{sup −} anions, both the bridging and free SO{sub 4}{sup 2−} anions in 1 were completely exchanged by SCN{sup −} ligands to form a 1D species [Cd(tpim){sub 2}(SCN){sub 2}] (1A), in which the SCN{sup –} moieties function as a monodentate ligand. On the other hand, when compound 1 was ion exchanged with N{sub 3}{sup −} anions in aqueous solution, the bridging SO{sub 4}{sup 2−} moieties remained intact, and only the free guest SO{sub 4}{sup 2−} were replaced by N{sub 3}{sup −} anions. The gas adsorption behavior of the activated compound 1 was also investigated. - Highlights: • An interestingmore » anion-induced structural transformation of a sulfate-incorporated 2D Cd(II)–organic framework is reported. • The sulfate-incorporated 2D layer compound exhibits very different anion exchange behavior with respect to SCN{sup −} and N{sub 3}{sup −}. • Both the bridging and free SO{sub 4}{sup 2−} anions in the 2D structure were completely exchanged by SCN{sup −} ligands, resulting in the formation of a 1D species. However, in the case of N{sub 3}{sup −} anions, only the free guest SO{sub 4}{sup 2−} in the structure was replaced.« less

Authors:
 [1];  [1];  [2]; ;  [3];  [4];  [5];  [1]
  1. Institute of Chemistry, Academia Sinica, Taipei 115, Taiwan (China)
  2. Department of Bioscience and Biotechnology, National Taiwan Ocean University, Keelung 202, Taiwan (China)
  3. Department of Chemistry, National Taiwan University, Taipei 107, Taiwan (China)
  4. Department of Chemistry, Fu Jen Catholic University, New Taipei City 242, Taiwan (China)
  5. Institute of Materials Science and Engineering, National Central University, Taoyuan 320, Taiwan (China)
Publication Date:
OSTI Identifier:
22584137
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 239; Other Information: Copyright (c) 2016 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; ADSORPTION; ANIONS; AQUEOUS SOLUTIONS; CADMIUM SULFATES; CRYSTAL STRUCTURE; CRYSTALS; IMIDAZOLES; INTERACTIONS; ION EXCHANGE; LAYERS; LIGANDS; SCANDIUM NITRIDES; THIOCYANATES; WATER

Citation Formats

Lee, Li-Wei, Institute of Materials Science and Engineering, National Central University, Taoyuan 320, Taiwan, Luo, Tzuoo-Tsair, Wang, Chih-Min, Lee, Gene-Hsiang, Peng, Shie-Ming, Liu, Yen-Hsiang, Lee, Sheng-Long, and Lu, Kuang-Lieh. Anion-induced structural transformation of a sulfate-incorporated 2D Cd(II)–organic framework. United States: N. p., 2016. Web. doi:10.1016/J.JSSC.2016.03.046.
Lee, Li-Wei, Institute of Materials Science and Engineering, National Central University, Taoyuan 320, Taiwan, Luo, Tzuoo-Tsair, Wang, Chih-Min, Lee, Gene-Hsiang, Peng, Shie-Ming, Liu, Yen-Hsiang, Lee, Sheng-Long, & Lu, Kuang-Lieh. Anion-induced structural transformation of a sulfate-incorporated 2D Cd(II)–organic framework. United States. doi:10.1016/J.JSSC.2016.03.046.
Lee, Li-Wei, Institute of Materials Science and Engineering, National Central University, Taoyuan 320, Taiwan, Luo, Tzuoo-Tsair, Wang, Chih-Min, Lee, Gene-Hsiang, Peng, Shie-Ming, Liu, Yen-Hsiang, Lee, Sheng-Long, and Lu, Kuang-Lieh. Fri . "Anion-induced structural transformation of a sulfate-incorporated 2D Cd(II)–organic framework". United States. doi:10.1016/J.JSSC.2016.03.046.
@article{osti_22584137,
title = {Anion-induced structural transformation of a sulfate-incorporated 2D Cd(II)–organic framework},
author = {Lee, Li-Wei and Institute of Materials Science and Engineering, National Central University, Taoyuan 320, Taiwan and Luo, Tzuoo-Tsair and Wang, Chih-Min and Lee, Gene-Hsiang and Peng, Shie-Ming and Liu, Yen-Hsiang and Lee, Sheng-Long and Lu, Kuang-Lieh},
abstractNote = {A Cd(II)–organic framework {[Cd_2(tpim)_4(SO_4)(H_2O)_2]·(SO_4)·21H_2O}{sub n} (1) was synthesized by reacting CdSO{sub 4}·8/3H{sub 2}O and 2,4,5-tri(4-pyridyl)imidazole (tpim) under hydrothermal conditions. A structural analysis showed that compound 1 adopts a layered structure in which the [Cd(tpim){sub 2}]{sub n} chains are linked by sulfate anions. These 2D layers are further packed into a 3D supramolecular framework via π–π interactions. The structure contains two types of SO{sub 4}{sup 2−} anions, i.e., bridging SO{sub 4}{sup 2−} and free SO{sub 4}{sup 2−} anions, the latter of which are included in the large channels of the framework. Compound 1 exhibits interesting anion exchange behavior. In the presence of SCN{sup −} anions, both the bridging and free SO{sub 4}{sup 2−} anions in 1 were completely exchanged by SCN{sup −} ligands to form a 1D species [Cd(tpim){sub 2}(SCN){sub 2}] (1A), in which the SCN{sup –} moieties function as a monodentate ligand. On the other hand, when compound 1 was ion exchanged with N{sub 3}{sup −} anions in aqueous solution, the bridging SO{sub 4}{sup 2−} moieties remained intact, and only the free guest SO{sub 4}{sup 2−} were replaced by N{sub 3}{sup −} anions. The gas adsorption behavior of the activated compound 1 was also investigated. - Highlights: • An interesting anion-induced structural transformation of a sulfate-incorporated 2D Cd(II)–organic framework is reported. • The sulfate-incorporated 2D layer compound exhibits very different anion exchange behavior with respect to SCN{sup −} and N{sub 3}{sup −}. • Both the bridging and free SO{sub 4}{sup 2−} anions in the 2D structure were completely exchanged by SCN{sup −} ligands, resulting in the formation of a 1D species. However, in the case of N{sub 3}{sup −} anions, only the free guest SO{sub 4}{sup 2−} in the structure was replaced.},
doi = {10.1016/J.JSSC.2016.03.046},
journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = 239,
place = {United States},
year = {2016},
month = {7}
}