In this study we present a new series of phenantridine-based substituted difluoroboranyls. The effects of substitution and double benzannulation on their photophysical properties were examined with experimental techniques and compared with the results obtained for previously reported quinoline and isoquinoline derivatives. The experimental characterizations are supported by state-of-the-art quantum-chemical calculations. In particular, the theoretical calculations were performed to gain insights into the complex nature of the relevant excited-states. These calculations reveal that both the nature of the substituent and its position on the phenyl ring significantly impact the magnitude of the electronic charge transferred upon excitation. Additionally, vibrationally resolved spectra were determined allowing for the analysis of the key vibrations playing a role in the band shapes.