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Title: Cu-PDC-bpa solid coordination frameworks (PDC=2,5-pyrindinedicarboxylate; bpa=1,2-DI(4-pyridil)ethane)): 2D and 3D structural flexibility producing a 3-c herringbone array next to ideal

Abstract

Combination of polycarboxylate anions and dipyridyl ligands is an effective strategy to produce solid coordination frameworks (SCF) which are crystalline materials based on connections between metal ions through organic ligands. In this context, this work is focused on two novel Cu{sup II}-based SCFs exhibiting PDC (2,5-pyridinedicarboxylate) and bpa (1,2-di(4-pyridyl)ethane), being the first structures reported in literature containing both ligands. Chemical formula are [Cu{sub 2}[(PDC){sub 2}(bpa)(H{sub 2}O){sub 2}]·3H{sub 2}O·DMF (1), and [Cu{sub 2}(PDC){sub 2}(bpa)(H{sub 2}O){sub 2}]·7H{sub 2}O (2), where DMF is dimethylformamide. Compounds 1 and 2 have been characterized by means of X-ray diffraction (XRD), infrared spectroscopy (IR), thermogravimetric (TG) analysis, differential thermal analysis (DTA) and dielectric measurements. The crystallographic analysis revealed that compounds 1 and 2 can be described as herringbone-type layers formed by helicoidal Cu-PDC-Cu chains connected through bpa ligands. Solvent molecules are crystallized between the layers, providing the inter-layer connections through hydrogen bonds. Differences between both compounds are attributable to the flexibility of bpa (in 2D) as well as to the 3D packing of the layers which is solvent dependent. This fact results in the fact that compound 2 is the most regular 3-c herringbone array reported so far. The structural dynamism of these networks is responsible formore » the crystalline to-amorphous to-crystalline (CAC) transformation from compound 1 to compound 2. Crystallochemical features for both compounds have also been studied and compared to similar 3-connected herringbone-arrays. - Graphical abstract: Cu-PDC-bpa 3-c herringbone arrays. - Highlights: • The most ideal herringbone array reported so far is a Cu-PDC-bpa SCF. • Conformational freedom of bpa results in 2D and 3D flexibility of the SCFs. • The flexibility of the SCFs is related to a phase transformation. • Dielectric measurements confirm the mobility of guest solvent molecules.« less

Authors:
 [1];  [1];  [1];  [2];
  1. Departamento de Mineralogía y Petrología, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Apdo 644, 48080 Bilbao (Spain)
  2. Departamento de Química Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Apdo 644, 48080 Bilbao (Spain)
Publication Date:
OSTI Identifier:
22486807
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 230; Other Information: Copyright (c) 2015 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; ABSORPTION SPECTROSCOPY; ANIONS; COPPER COMPOUNDS; CRYSTAL STRUCTURE; DIELECTRIC MATERIALS; DIELECTRIC PROPERTIES; DIFFERENTIAL THERMAL ANALYSIS; ETHANE; HYDRATES; HYDROGEN; INFRARED SPECTRA; LAYERS; LIGANDS; MOBILITY; PHASE TRANSFORMATIONS; SOLVENTS; THERMAL GRAVIMETRIC ANALYSIS; X-RAY DIFFRACTION

Citation Formats

Llano-Tomé, Francisco, Bazán, Begoña, BCMaterials Parque Tecnológico de Zamudio, Ibaizabal Bidea, Edificio 500–Planta 1, 48160 Derio, Urtiaga, Miren-Karmele, Barandika, Gotzone, Antonia Señarís-Rodríguez, M., E-mail: tonasr@udc.es, and others, and. Cu-PDC-bpa solid coordination frameworks (PDC=2,5-pyrindinedicarboxylate; bpa=1,2-DI(4-pyridil)ethane)): 2D and 3D structural flexibility producing a 3-c herringbone array next to ideal. United States: N. p., 2015. Web. doi:10.1016/J.JSSC.2015.06.039.
Llano-Tomé, Francisco, Bazán, Begoña, BCMaterials Parque Tecnológico de Zamudio, Ibaizabal Bidea, Edificio 500–Planta 1, 48160 Derio, Urtiaga, Miren-Karmele, Barandika, Gotzone, Antonia Señarís-Rodríguez, M., E-mail: tonasr@udc.es, & others, and. Cu-PDC-bpa solid coordination frameworks (PDC=2,5-pyrindinedicarboxylate; bpa=1,2-DI(4-pyridil)ethane)): 2D and 3D structural flexibility producing a 3-c herringbone array next to ideal. United States. https://doi.org/10.1016/J.JSSC.2015.06.039
Llano-Tomé, Francisco, Bazán, Begoña, BCMaterials Parque Tecnológico de Zamudio, Ibaizabal Bidea, Edificio 500–Planta 1, 48160 Derio, Urtiaga, Miren-Karmele, Barandika, Gotzone, Antonia Señarís-Rodríguez, M., E-mail: tonasr@udc.es, and others, and. 2015. "Cu-PDC-bpa solid coordination frameworks (PDC=2,5-pyrindinedicarboxylate; bpa=1,2-DI(4-pyridil)ethane)): 2D and 3D structural flexibility producing a 3-c herringbone array next to ideal". United States. https://doi.org/10.1016/J.JSSC.2015.06.039.
@article{osti_22486807,
title = {Cu-PDC-bpa solid coordination frameworks (PDC=2,5-pyrindinedicarboxylate; bpa=1,2-DI(4-pyridil)ethane)): 2D and 3D structural flexibility producing a 3-c herringbone array next to ideal},
author = {Llano-Tomé, Francisco and Bazán, Begoña and BCMaterials Parque Tecnológico de Zamudio, Ibaizabal Bidea, Edificio 500–Planta 1, 48160 Derio and Urtiaga, Miren-Karmele and Barandika, Gotzone and Antonia Señarís-Rodríguez, M., E-mail: tonasr@udc.es and others, and},
abstractNote = {Combination of polycarboxylate anions and dipyridyl ligands is an effective strategy to produce solid coordination frameworks (SCF) which are crystalline materials based on connections between metal ions through organic ligands. In this context, this work is focused on two novel Cu{sup II}-based SCFs exhibiting PDC (2,5-pyridinedicarboxylate) and bpa (1,2-di(4-pyridyl)ethane), being the first structures reported in literature containing both ligands. Chemical formula are [Cu{sub 2}[(PDC){sub 2}(bpa)(H{sub 2}O){sub 2}]·3H{sub 2}O·DMF (1), and [Cu{sub 2}(PDC){sub 2}(bpa)(H{sub 2}O){sub 2}]·7H{sub 2}O (2), where DMF is dimethylformamide. Compounds 1 and 2 have been characterized by means of X-ray diffraction (XRD), infrared spectroscopy (IR), thermogravimetric (TG) analysis, differential thermal analysis (DTA) and dielectric measurements. The crystallographic analysis revealed that compounds 1 and 2 can be described as herringbone-type layers formed by helicoidal Cu-PDC-Cu chains connected through bpa ligands. Solvent molecules are crystallized between the layers, providing the inter-layer connections through hydrogen bonds. Differences between both compounds are attributable to the flexibility of bpa (in 2D) as well as to the 3D packing of the layers which is solvent dependent. This fact results in the fact that compound 2 is the most regular 3-c herringbone array reported so far. The structural dynamism of these networks is responsible for the crystalline to-amorphous to-crystalline (CAC) transformation from compound 1 to compound 2. Crystallochemical features for both compounds have also been studied and compared to similar 3-connected herringbone-arrays. - Graphical abstract: Cu-PDC-bpa 3-c herringbone arrays. - Highlights: • The most ideal herringbone array reported so far is a Cu-PDC-bpa SCF. • Conformational freedom of bpa results in 2D and 3D flexibility of the SCFs. • The flexibility of the SCFs is related to a phase transformation. • Dielectric measurements confirm the mobility of guest solvent molecules.},
doi = {10.1016/J.JSSC.2015.06.039},
url = {https://www.osti.gov/biblio/22486807}, journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = 230,
place = {United States},
year = {Thu Oct 15 00:00:00 EDT 2015},
month = {Thu Oct 15 00:00:00 EDT 2015}
}