Metal-organic frameworks (MOFs) are a class of nanoporous, crystalline materials composed of metal ions or clusters coordinated to multitopic organic linkers. Due to poor orbital overlap, MOFs are traditionally insulators. However, introduction of redox active guest molecules into the MOF pores can bridge the metal nodes of the MOF, resulting in semiconductive behavior. Infiltration of 7, 7, 8, 8-tetracyanoquinododimethane (TCNQ), a conjugated redox-active guest molecule, into M-MOF-74s (M=Cu, Mn, Mg, Zn), may result in tunable electrical conductivity through coordination of TCNQ to the subunits of the metal nodes. Scanning electron microscopy and powder x-ray diffraction showed the structure of the M-MOF-74s remained retained after TCNQ infiltration without no formation of metal- based TCNQ nanowires. Optical absorbance spectra show charge transfer between TCNQ and M-MOF- 74 (M=Cu, Mn). The TCNQ@Cu-MOF-74 and TCNQ@Mn-MOF-74 materials produced conductivities of up to 5.40 x10<sup>-2</sup> S/m and 5.02 x10<sup>-3</sup> S/m with activation energies of 889.9 meV and 580.7 meV, respectively. Establishing novel semiconducting nanomaterials from MOFs could be implemented in a diverse array of electronic components, including electronic devices, reconfigurable electronics, and sensors.

Doping of metal-organic frameworks towards electronics

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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