To further understand the absorption and emission behaviour of 1c and 1c .-, time-dependent DFT (TD-DFT) analysis have been performed at CAM-B3LYP/6-311g(d) level using the polar continuum model (PCM) model with DMF as solvent. The theoretical calculation corroborated well with the experimental observation (Figure ). The molecular orbital analysis of 1c predicted that the electronic transition from HOMO-2 to LUMO+2 (f = 1.16) contributed majorly to the shorter wavelength (370 nm) absorptions. In addition to that HOMO and HOMO-1 located in between the HOMO-2 and LUMO+2. Interestingly, an energetically favourable local electron transfer from HOMO/HOMO-1 to HOMO-2 was observed which prevented the reversal of the excited electron from the LUMO+2 to HOMO-2 state leading to a low emission of 1c (Figure ). On the other hand, TD-DFT investigation on 1c .-showed that the transitions from HOMO-3 to LUMO+3 (345 nm, f = 1.1) accounted for the absorptions in the shorter wavelength region. Molecular orbital analysis of 1c .-showed that degenerate HOMO-1/HOMO-2, HOMO and LUMO located in between the transitioning orbital LUMO+2 and HOMO-3. As a result, a possibility of local electronic excitation from HOMO-1/HOMO-2 to LUMO (507 nm, f = 0.21) and HOMO to LUMO+5 (432 nm, = 0.95) was found in the DFT simulation. These transitions reduced the possibility of local electron transfer (PET) from HOMO-1/HOMO-2 to HOMO-3 and HOMO to HOMO-3. which explains the subsequent enhancement of fluorescence intensity upon the formation of 1c .-(1c→1c .-) (Figure ).