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Electronic Conductivity in a Porous Vanadyl Prussian Blue Analogue upon Air Exposure



Mary Anne Manumpil, Carmen Leal-Cervantes, Matthew R. Hudson, Craig Brown, Hemamala I. Karunadasa


Exposure to humid oxygen or ambient air affords a 5-or-der-of-magnitude increase in the electronic conductivity of a new Prussian blue analog incorporation Co(II) and V(IV)-oxo units. Oxidation produces a mixed-valence framework, where the oxygen exposure time controls the V(IV)/V(V) ratio and thereby the material's conductivity. The oxidized framework shows an intervalence charge transfer band at ca. 4200 cm-1, consistent with class II mixed-valence. Electronic conductivity measurements reveal semiconducting behavior in the mixed-valence frameworks with conductivity values of 10^-5^ S &#8226cm-1 at room temperature and 10-4S&#8226-1 at 100 °C, and activation energies of ca. 03 eV. Nitrogen adsorption measurements at 77 K show that these materials posses permanent porosity before and ater oxidation with BET surface areas of 340 m2g-1 and 370 m2g-1, respectively.
Inorganic Chemistry


semiconductor, conductivity, Prussian blue, Crystallography


Manumpil, M. , Leal-Cervantes, C. , Hudson, M. , Brown, C. and Karunadasa, H. (2017), Electronic Conductivity in a Porous Vanadyl Prussian Blue Analogue upon Air Exposure, Inorganic Chemistry, [online], (Accessed June 18, 2024)


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Created November 5, 2017, Updated October 12, 2021