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Water-free proton conduction in discotic pyridylpyrazolate-based Pt(II) and Pd(II) metallomesogens

AuthorsCuerva, Cristián; Campo, José A.; Cano, Mercedes; Sanz, J.; Sobrados, Isabel ; Díez-Gómez, Virginia ; Rivera-Calzada, Alberto; Schmidt, Rainer
Issue Date18-Jul-2016
PublisherAmerican Chemical Society
CitationInorganic Chemistry 55(14): 6995-7002 (2016)
AbstractIn this work we report on water-free proton conductivity in liquid-crystal pyridylpyrazolate-based Pt(II) and Pd(II) complexes [M(pz)] (pz = 3-(3,5-dialkyloxyphenyl)-5-(pyridin-2-yl)pyrazolate, R(n,n) = CH(OCH); n = 4, 12, 16, M = Pd; n = 12, M = Pt) with potential application as electrolyte materials in proton exchange membrane fuel cells. The columnar ordering of the complexes in the liquid-crystalline phase opens nanochannels, which are used for fast proton exchange as detected by impedance spectroscopy and NMR. The NMR spectra indicate that the proton conduction mechanism is associated with a novel C-H···N proton transfer, which persists above the clearing point of the material. The highest conductivity of ∼0.5 μS cm at 180 °C with an activation energy of 1.2 eV is found for the Pt(II) compound in the mesophase. The Pd(II) complexes with different chain length (n = 4, 12, and 16) show lower conductivity but smaller activation energies, in the range of 0.74-0.93 eV.
Publisher version (URL)https://doi.org/10.1021/acs.inorgchem.6b00728
Identifiersdoi: 10.1021/acs.inorgchem.6b00728
e-issn: 1520-510X
issn: 0020-1669
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