Our strategy to investigate the impact of the conformations on the fluorescence of pyrene dimers consists of two steps. In the first step, we started by stochastically generating dimer conformations, emulating the result of a diffusive process. We then applied unsupervised methods and expert-guided analysis to cluster these geometries into a few independent species. This process is described in Section 3.1. Then, in the second step, we performed electronic structure and rate constant analyses to evaluate the competition between conformational rearrangements and radiative relaxation. This part is reported in Section 3.2.