Solid-solid interactions in co-crystals lead to alternations of the physico-chemical properties of the mixture compared to its single components. Herein, we report a setup that makes use of mechanochemistry to promote these interactions and is coupled with the analytical power of nuclear magnetic resonance (NMR) to in operando monitor the resulting variation. The system is applied to the analysis of optically active species responding to cases of self-disproportionation of enantiomers (SDE) by sublimation. The fundamentals behind the observed phenomenon led to an advanced concept of enantiomers recognition based on selective sublimation.