2026-07-072026-07-07http://salesiana.dossiersoluciones.com/handle/123456789/156172From 59Co and 23Na NMR, we demonstrate the impact of the Na+ vacancy ordering on the cobalt electronic states in Na0.75CoO2: at long time scales, there is neither a disproportionation into 75 % Co3+ and 25 % Co4+ states, nor a mixed-valence metal with a uniform Co3.25+ state. Instead, the system adopts an intermediate configuration in which 30 % of the lattice sites form an ordered pattern of localized Co3+ states. Above 180 K, an anomalous mobility of specific Na+ sites is found to coexist with this electronic texture, suggesting that the formation of the latter may contribute to stabilizing the Na+ ordering. Control of the ion doping in these materials thus appears to be crucial for fine-tuning of their thermoelectric properties.4 pages, to appear in Phys. Rev. LettStrongly Correlated Electronstext