We obtain an excellent agreement between the theoretical values of PL emission energies from STE and the experimental ones for a large set of perovskites, in particular (1,3-PDA)PbBr4, (1,4-PDA)PbBr4, (1,3-PDA)PbCl4, (1,4-PDA)Pb2Cl6, (1,3-XDA)2PbCl6 and (1,4-XDA)PbCl4, see Table . Emission from halide vacancies show comparable energy values, Table , likely contributing to the broad emission of all investigated perovskites. Note that for (1,3-XDA)2PbCl6 STE localizes within the organic cations, as the electronic states of the carbon moieties dominate the conduction band edge of the given 0-D perovskitoid, see Figure in the electronic structure in the electronic ground state is observed, see Figure . We consequently assign the sharp PL peak at 420 nm to band-to-band emission of delocalized excitons. Furthermore, the presence (absence) of STE may be attributed to a large (low) octahedral tilting, providing an indicator for a rapid screening of potential material candidates for broad emitters. Our results further suggest that the strong red-shift is dominated by differences in the singlet energies between the ground state and the STE geometry, causing a substantial relaxation upon emission, see Table .