Micropore filling and temperature dependent electrical transport aspects of poly(3,4-ethylenedioxythiophene) polymerized Zr-based metal-organic framework

This work reports the polymerization of poly(3,4-ethylenedioxythiophene) (PEDOT) within a metal-organic framework (MOF), namely UiO-66 containing pores of tetrahedral and octahedral geometry. Partial filling of micropores of UiO-66 with PEDOT and occupancy up to 29.6% has brought up conformational changes, vibrational responses as well as altered carrier transport phenomena characterized through different techniques. X-ray diffraction (XRD) and Brunner-Emmett-Teller (BET) surface area analysis have revealed the structural stability of the MOF after the inclusion of PEDOT while microporous nature was maintained with a primary filling of octahedral micropores. Interestingly, the PEDOT polymerization is believed to draw a conformational change from benzoid to quinoid structure as substantiated through the Raman studies. Moreover, a noticeable improvement in electrical conductivity has been realized (typically, ≈10${}^{-3}$ to 10${}^{-2}$ S cm${}^{-1}$) for the composite while its temperature dependency followed a semiconducting feature. Controlled insertion, limited space-filling, and occupancy can strengthen the insights on soft matter models and reptation theory and would find scope in applications where porosity, stability, and conductivity are desired. (© 2022 Wiley‐VCH GmbH)