2D→3D polycatenated and 3D→3D interpenetrated metal–organic frameworks constructed from thiophene-2,5-dicarboxylate and rigid bis(imidazole) ligands

Journal Article · Sat Feb 15 00:00:00 EST 2014 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/J.JSSC.2013.11.036· OSTI ID:22274225

Erer, Hakan ^[1]; Arıcı, Mürsel ^[1]; Keskin, Seda ^[2]; Büyükgüngör, Orhan ^[3]

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1. Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey)
2. Department of Chemical and Biological Engineering, Koç University, İstanbul (Turkey)
3. Department of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, 55139 Samsun (Turkey)

Hydrothermal reactions of rigid 1,4-bis(imidazol-1-yl)benzene (dib) and 1,4-bis(imidazol-1-yl)-2,5-dimethylbenzene (dimb) with deprotonated thiophene-2,5-dicarboxylic acid (H{sub 2}tdc) in the presence of Zn(II) and Cd(II) salts in H{sub 2}O produced three new metal–organic frameworks, namely, [Zn(µ-tdc)(H{sub 2}O)(µ-dib)]{sub n} (1), [Cd(µ-tdc)(H{sub 2}O)(µ-dib)]{sub n} (2), and ([Cd{sub 2}(µ{sub 3}-tdc){sub 2}(µ-dimb){sub 2}]·(H{sub 2}O)){sub n}(3). These MOFs were characterized by FT-IR spectroscopy, elemental, thermal (TG, DTA, DTG and DSC), and single-crystal X-ray diffraction analyses. Isomorphous complexes 1 and 2 reveal polycatenated 2D+2D→3D framework based on an undulated (4,4)-sql layer. Complex 3 exhibits a new 4-fold interpenetrating 3D framework with the point symbol of 6{sup 6}. Molecular simulations were used to assess the potentials of the complexes for H{sub 2} storage application. Moreover, these coordination polymers exhibit blue fluorescent emission bands in the solid state at room temperature. - Graphical abstract: In this study, hydrothermal reactions of rigid 1,4-bis(imidazol-1-yl)benzene (dib) and 1,4-bis(imidazol-1-yl)-2,5-dimethylbenzene (dimb) with deprotonated thiophene-2,5-dicarboxylic acid (H{sub 2}tdc) in the presence of Zn(II) and Cd(II) salts in H{sub 2}O produced three new metal–organic frameworks. Isomorphous complexes 1 and 2 reveal polycatenated 2D+2D→3D framework based on an undulated (4,4)-sql layer. Complex 3 exhibits a new 4-fold interpenetrating 3D framework with the point symbol of 6{sup 6}. Molecular simulations were used to assess the potentials of the complexes for H{sub 2} storage application. These coordination polymers exhibit blue fluorescent emission bands in the solid state at room temperature. Display Omitted - Highlights: • Complexes 1 and 2 display polycatenated 2D+2D→3D framework. • Complex 3 exhibits a new 4-fold interpenetrating 3D framework. • Complex 1 adsorbs the highest amount of H{sub 2} at 100 bar and 298 K. • Complexes display blue fluorescent emission bands.

• OSTI ID: 22274225
• Journal Information: Journal of Solid State Chemistry, Vol. 210, Issue 1; Other Information: Copyright (c) 2013 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BENZENE
CALORIMETRY
DICARBOXYLIC ACIDS
DIFFERENTIAL THERMAL ANALYSIS
FLUORESCENCE
FOURIER TRANSFORMATION
HYDROGEN
HYDROGEN STORAGE
HYDROTHERMAL SYNTHESIS
INFRARED SPECTRA
LAYERS
LIGANDS
MONOCRYSTALS
POLYCYCLIC SULFUR HETEROCYCLES
POLYMERS
SIMULATION
SOLIDS
THIOPHENE
X-RAY DIFFRACTION