Slip/Stick Viscosity Models of Nanoconfined Liquids: Solvent-Dependent Rotation in Metal-Organic Frameworks

Artificial molecular machines are expected to operate in environments where viscous forces impact molecules significantly. With that, it is well-known that solvent behaviors dramatically change upon confinement into limited spaces as compared to bulk solvents. In this study, we demonstrate the utility of an amphidynamic metal-organic framework with pillars consisting of ²H-labeled dialkynyltriptycene and dialkynylphenylene barrierless rotators that operate as NMR sensors for solvent viscosity. Using line-shape analysis of quadrupolar spin echo spectra we showed that solvents such as dimethylformamide, diethylformamide, 2-octanone, bromobenzene, o-dichlorobenzene, and benzonitrile slow down their Brownian rotational motion (10³-10⁶ s^-1) to values consistent with confined viscosity values (ca. 10⁰-10³ pa s) that are up to 10000 greater than those in the bulk. Magic angle spinning assisted ¹H T₂ measurements of included solvents revealed relaxation times of approximately 100-1000 ms over the explored temperature ranges, and MAS-assisted ¹H T₁ measurements of included solvents suggested a much lower activation energy for rotational dynamics as compared to those measured by the rotating pillars using ²H measurements. Finally, translational diffusion measurements of DMF using pulsed-field gradient methods revealed intermediate dynamics for the translational motion of the solvent molecules in MOFs.