A2PbBr4 2D perovskites (A= 1,3-phenylenediammonium (1,3-PDA), 1,3xylylenediamimonium (1,3-XDA), 1,4-phenylenediammonium (1,4-PDA), and 1,4xylylenediamimonium (1,4-XDA), cfr. Figure ) have been prepared by wet-chemistry route as reported in the Experimental Section. Single crystal XRD revealed that the compounds crystallize in triclinic and monoclinic space groups, as reported in Table . Not all the samples investigated crystallize as a layered perovskite structure, in particular this does not occur for the composition including the 1,3-XDA cation, giving the chemical formula (1,3-XDA)2PbBr6. A sketch of the crystal structures is reported in Figure . As mentioned, (1,3-XDA)2PbBr6 does not assume the perovskite structure, being constituted by slightly distorted isolated octahedra, corresponding to a so-called 0D perovskitoid. The crystal cohesion is then given by the aromatic cations whose NH3 + groups interact with both equatorial and axial Br atoms. To the best of our knowledge, this is one of the first 0D bromide perovskite derivative including a diammonium cation, while chloride containing 0D systems have been reported in the past. (1,3-PDA)PbBr4, (1,4-PDA)PbBr4, and