The different luminescence of the three samples can be rationalized by considering their structural characteristics. The two materials, 1,3-PDA and 1,4-PDA, with larger values of   and  oct (Figure ) show a dominant role of the broadband emission, as expected in materials with significant deviations from ideal octahedral geometry. On the other hand, 1,4-XDA, which has relatively undistorted octahedra, but shows significant tilting of the Pb-Br-Pb angle ( < 150°) exhibits a mixture of narrow and broad band emission, with only the free exciton component persisting at room temperature. However, it is interesting to note that the respective degrees of inter-and intra-octahedral distortion are not sufficient to fully explain the luminescence properties we have observed. In particular, 1,3-PDA has a highly distorted geometry, very similar to 1,4-PDA in terms of the most commonly used short-hands for octahedral distortion: their values of  oct   and Dtilt are comparable. However, 1,3-PDA also shows a small narrowband component at 420 nm, which is quickly transferred (< 3 ps) to the broadband feature, but not before radiative free exciton recombination can occur. No such feature is observed for 1,4-PDA: this behavior may indicate a much more effective transfer to the broadband emissive states which completely overtakes radiative recombination.