Table : Lattice parameters of compounds 1-3, with percentage differences from 150K experiment (Table ) given in parentheses. Compound 3 is given as the corresponding primitive cell due to The PBE+D3-optimized structures were used as the basis for electronic structure calculations with the HSE06 and HSE06+SOC methods, which have been suitable at determining band gaps in extended complexes with reasonable accuracy. Due to the structurally localized nature of the complexes, there is minimal band dispersion in these systems, with only some in the Bi p dominated states in the conduction band (and to a lesser extent the Bi s/I p states in the valence band of compound 3). As such, the electronic band structure, plotted across the Brillouin zone, is not informative in these systems. The densities of states of the three compounds, however, still help to show the distribution of organic and inorganic states in the solid state, and those calculated with the HSE06 functional are shown in Figure . The HSE06 densities of states show strong similarity across all three compounds in the position and contributions of the organic (C p/N p dominant) and Bi p states, consistent with the identical composition with the exception of the halide, but indicating that there is also minimal hybridization between the electronic state on the inorganic and organic sections of the complexes. In compounds 1 and 2, the frontier states around the gap are dominated by the organic ligand, strongly in-line with the dominance of the 1 LC transition in the absorption spectra in Figure ). The partial charge density plots of the valence band maximum (VBM) and conduction band minimum (CBM) of compound 1 in Figure further demonstrates the earlier assignment that the transition specifically arises from the charge transfer from the thiophene rings to the phenanthroline section involved in binding to the bismuth.