Designing UiO-66-Based Superprotonic Conductor with the Highest Metal–Organic Framework Based Proton Conductivity MukhopadhyaySubhabrata DebguptaJoyashish SinghChandani SarkarRudraditya BasuOlivia DasSamar K. 2019 Metal–organic framework (MOF) based proton conductors have received immense importance recently. The present study endeavors to design two post synthetically modified UiO-66-based MOFs and examines the effects of their structural differences on their proton conductivity. UiO-66-NH<sub>2</sub> is modified by reaction with sultones to prepare two homologous compounds, that is, <b>PSM 1</b> and <b>PSM 2</b>, with SO<sub>3</sub>H functionalization in comparable extent (Zr:S = 2:1) in both. However, the pendant alkyl chain holding the −SO<sub>3</sub>H group is of different length. <b>PSM 2</b> has longer alkyl chain attachment than <b>PSM 1</b>. This difference in the length of side arms results in a huge difference in proton conductivity of the two compounds. <b>PSM 1</b> is observed to have the highest MOF-based proton conductivity (1.64 × 10<sup>–1</sup> S cm<sup>–1</sup>) at 80 °C, which is comparable to commercially available Nafion, while <b>PSM 2</b> shows significantly lower conductivity (4.6 × 10<sup>–3</sup> S cm<sup>–1</sup>). Again, the activation energy for proton conduction is one of the lowest among all MOF-based proton conductors in the case of <b>PSM 1</b>, while <b>PSM 2</b> requires larger activation energy (almost 3 times). This profound effect of variation of the chain length of the side arm by one carbon atom in the case of <b>PSM 1</b> and <b>PSM 2</b> was rather surprising and never documented before. This effect of the length of the side arm can be very useful to understand the proton conduction mechanism of MOF-based compounds and also to design better proton conductors. Besides, <b>PSM 1</b> showed proton conductivity as high as 1.64 × 10<sup>–1</sup> S cm<sup>–1</sup> at 80 °C, which is the highest reported value to date among all MOF-based systems. The lability of the −SO<sub>3</sub>H proton of the post synthetically modified UiO-66 MOFs has theoretically been determined by molecular electrostatic potential analysis and theoretical p<i>K</i><sub>a</sub> calculation of models of functional sites along with relevant NBO analyses.