The phase purity of powder samples of [A]Ni(C2N3)3 was verified using laboratory PXRD and Pawley analysis (Fig. ). Furthermore, thermal analysis (TGA/DSC) showed decomposition temperatures (Td) between 570 and 600 K (Fig. ). These are at the upper end of previously reported Td of dicyanamide-based molecular perovskites. In parts, we rationalise this by the stability of the here employed A + , which has previously been suggested as an important factor determining Td; 46 however, Td is a generally complex quantity, which depends upon many parameters, including crystal chemistry factors and analytic concerns. In the DSC curves, several heat events related to 1 st and 2 nd order phase transitions were observed (Fig. ), while no evidence of melting before Td was found; 11 however, the nature of these phase transitions is beyond the focus of this study. Here, we employ our new [A]Ni(C2N3)3 family as model compounds to study the relation between A + and B.