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We examine the diffusion of methane in the metal–organic frameworks M₂(dobdc) (M = Mg, Ni, Zn; dobdc^4– = 2,5-dioxido-1,4-benzenedicarboxylate) as a function of methane loading through a combination of nuclear magnetic resonance and molecular dynamics simulations. At low gas densities, our results suggest that favorable CH₄–CH₄ interactions lower the free energy barrier for methane hopping between coordinatively unsaturated metal sites and thus enhance the translational motion of methane down the c-axis. At higher gas densities, CH₄–CH₄ interactions become more significant, CH₄–CH₄ collisions become more frequent, and the gas self-diffusion begins to decrease. Finally, we observe that the self-diffusion coefficient of methane is inversely related to the binding energy at the coordinatively unsaturated metal sites, such that diffusion is most rapid in the Zn₂(dobdc) framework.