In summary, we synthesized and investigated the photophysical properties of the series of bismuth-halide based coordination complexes. The results demonstrate that both the conventional and solvothermal synthesis can be utilized to synthesize the bismuth based bioctahedral complexes however, conventional synthetic conditions provide more control over the reaction products, hence lead to the formation of single phase product. Also, the kinetic NMR studies provides the stability of complexes in the solution and shows that the complexes are stable in solution to study their fundamental properties. The detailed photophysical studies of the complexes in the solution phase