Taking the idea from the previous literatures published on the photochemistry of the Bi(III)I6 ions, and halide photochemistry, we assume that the lower energy absorption band (450-550 nm in DMF and 440-525 nm in ACN) is purely the halide LMCT in nature. Additionally, when the complexes are excited at 440-525 nm in ACN, no emission was observed which further confirms that these bands lead to the population of LMCT states which are generally known to be non-emissive. Moreover, the reduction in the intensity and quenching of the ligand excited state These initial studies further confirm the stability of the complexes in the excited and thus provide the opportunity to explore the excited state dynamics of the bismuth based coordination complexes for the optoelectronics applications.