Charge Delocalization and Bulk Electronic Conductivity in the Mixed-Valence Metal–Organic Framework Fe(1,2,3-triazolate)2(BF4)x

Metal–organic frameworks are of interest for use in a variety of electrochemical and electronic applications, although a detailed understanding of their charge transport behavior, which is of critical importance for enhancing electronic conductivities, remains limited. Herein, we report isolation of the mixed-valence framework materials, Fe­(tri)2(BF4)x (tri– = 1,2,3-triazolate; x = 0.09, 0.22, and 0.33), obtained from the stoichiometric chemical oxidation of the poorly conductive iron­(II) framework Fe­(tri)2, and find that the conductivity increases dramatically with iron oxidation level. Notably, the most oxidized variant, Fe­(tri)2(BF4)0.33, displays a room-temperature conductivity of 0.3(1) S/cm, which represents an increase of 8 orders of magnitude from that of the parent material and is one of the highest conductivity values reported among three-dimensional metal–organic frameworks. Detailed characterization of Fe­(tri)2 and the Fe­(tri)2(BF4)x materials via powder X-ray diffraction, Mössbauer spectroscopy, and IR and UV–vis-NIR diffuse reflectance spectroscopies reveals that the high conductivity arises from intervalence charge transfer between mixed-valence low-spin FeII/III centers. Further, Mössbauer spectroscopy indicates the presence of a valence-delocalized FeII/III species in Fe­(tri)2(BF4)x at 290 K, one of the first such observations for a metal–organic framework. The electronic structure of valence-pure Fe­(tri)2 and the charge transport mechanism and electronic structure of mixed-valence Fe­(tri)2(BF4)x frameworks are discussed in detail.