Chemically Resistant,Shapeable, and Conducting Metal‐Organic Gels and Aerogels Built from Dithiooxamidato Ligand |
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Authors: | Daniel Vallejo‐Sánchez Pilar Amo‐Ochoa Garikoitz Beobide Oscar Castillo Michael Fröba Frank Hoffmann Antonio Luque Pilar Ocón Sonia Pérez‐Yáñez |
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Affiliation: | 1. Departamento de Química Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco, Bilbao, Spain;2. Departamento de Química Inorgánica y Química Física, Universidad Autónoma de Madrid, Madrid, Spain;3. Institute of Inorganic and Applied Chemistry, University of Hamburg, Hamburg, Germany |
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Abstract: | Metal‐organic gels (MOGs) appear as a blooming alternative to well‐known metal‐organic frameworks (MOFs). Porosity of MOGs has a microstructural origin and not strictly crystalline like in MOFs; therefore, gelation may provide porosity to any metal‐organic system, including those with interesting properties but without a porous crystalline structure. The easy and straightforward shaping of MOGs contrasts with the need of binders for MOFs. In this contribution, a series of MOGs based on the assembly of 1D‐coordination polymer nanofibers of formula [M(DTA)]n (MII: Ni, Cu, Pd; DTA: dithiooxamidato) are reported, in which properties such as porosity, chemical inertness, mechanical robustness, and stimuli‐responsive electrical conductivity are brought together. The strength of the M? S bond confers an unusual chemical resistance, withstanding exposure to acids, alkalis, and mild oxidizing/reducing chemicals. Supercritical drying of MOGs provides ultralight metal‐organic aerogels (MOAs) with densities as low as 0.03 g cm?3 and plastic/brittle behavior depending on the nanofiber aspect ratio. Conductivity measurements reveal a semiconducting behavior (10?12 to 10?7 S cm?1 at 298 K) that can be improved by doping (10?5 S cm?1). Moreover, it must be stressed that conductivity of MOAs reversibly increases (up to 10?5 S cm?1) under the presence of acetic acid. |
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Keywords: | aerogels metal‐organic frameworks metal‐organic gel porosity stimuli‐responsive material |
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