Experimental manifestation of redox-conductivity in metal-organic frameworks and its implication for semiconductor/insulator switching

Electric conductivity in metal-organic frameworks (MOFs) follows either a band-like or a redox-hopping charge transport mechanism. While conductivity by the band-like mechanism is theoretically and experimentally well established, the field has struggled to experimentally demonstrate redox conductivity that is promoted by the electron hopping mechanism. Such redox conductivity is predicted to maximize at the mid-point potential of the redox-active units in the MOF, and decline rapidly when deviating from this situation. Herein, we present direct experimental evidence for redox conductivity in fluorine-doped tin oxide surface-grown thin films of Zn(pyrazol-NDI) (pyrazol-NDI = 1,4-bis[(3,5-dimethyl)-pyrazol-4-yl]naphthalenediimide). Following Nernstian behavior, the proportion of reduced and oxidized NDI linkers can be adjusted by the applied potential. Through a series of conductivity measurements, it is demonstrated that the MOF exhibits minimal electric resistance at the mid-point potentials of the NDI linker, and conductivity is enhanced by more than 10000-fold compared to that of either the neutral or completely reduced films. The generality of redox conductivity is demonstrated in MOFs with different linkers and secondary building units, and its implication for applications that require switching between insulating and semiconducting regimes is discussed.