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Chemically Resistant, Shapeable, and Conducting Metal‐Organic Gels and Aerogels Built from Dithiooxamidato Ligand
Author(s) -
VallejoSánchez Daniel,
AmoOchoa Pilar,
Beobide Garikoitz,
Castillo Oscar,
Fröba Michael,
Hoffmann Frank,
Luque Antonio,
Ocón Pilar,
PérezYáñez Sonia
Publication year - 2017
Publication title -
advanced functional materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 6.069
H-Index - 322
eISSN - 1616-3028
pISSN - 1616-301X
DOI - 10.1002/adfm.201605448
Subject(s) - materials science , porosity , oxidizing agent , metal , chemical engineering , conductivity , polymer , nanofiber , supercritical fluid , metal organic framework , ligand (biochemistry) , supercritical drying , nanotechnology , composite material , organic chemistry , metallurgy , chemistry , adsorption , engineering , biochemistry , receptor
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 (M II : 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 MS 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.