As the halide is changed from Cl to I, the halide p states follow the expected trend of rising in energy with respect to the organic levels -in the iodide compound, this is sufficient for them to equally dominate the valence band maximum. In all three compounds, the halide p bands are split into two sets: the lower-lying states that are purely halide-dominated, and the higher-lying bands that involve the antibonding contribution from mixing with Bi s. The lack of contribution of Bi p to the latter levels is consistent with the regular bioctahedral coordination, and lack of a stereochemically active lone pair. As bismuth is a heavy element, and additionally iodine in compound 3, it is necessary to also explore the effect of spin-orbit coupling on the DOS of the three compounds: the HSE06+SOC densities of states are included in Figure . While SOC has an appreciable effect on the Bi p states in the conduction band of all three compounds, splitting them by 1 eV, this is still insufficient for any to lie lower than the unoccupied states of the organic ligand, retaining the 1 LC character of the fundamental gap in compounds 1 and 2. In compound 3, the additional splitting of the iodine p states in the valence band is small, but sufficient to lead to their further dominating the valence band maximum.