A new molecular donoracceptordonor (DAD) triad, comprised of an electron deficient 1,4,5,8-naphthalene tetracarboxylic diimide (NDI) unit covalently connected to two flanking photosensitizers, i.e., a bis-heteroleptic Ru(II) complex of 1,10-phenanthroline and pyridine triazole hybrid ligand, is described. The single crystal X-ray structure of the perchlorate salt of the triad demonstrates that the electron deficient NDI unit can act as a host for anions via anion-p interaction. Detailed solution-state studies indicate that fluoride selectively interacts with the DAD triad to form a dianionic NDI, NDI2, via a radical anion, NDI. On the contrary, cyanide reduces the NDI moiety to NDI, as confirmed by UVvis, NMR, and EPR spectroscopy. Further, femtosecond transient absorption spectroscopic studies reveal a low luminescence quantum yield of the DAD triad attributable to the photoinduced electron transfer (PET) process from the photoactive Ru(II) center to the NDI unit. Interestingly, the triad displays OFFON luminescence behavior in the presence of fluoride by restoring the Ru(II) to phenanthroline/pyridine-triazole-based MLCT emission, whereas cyanide fails to show a similar property due to a different redox process operational in the latter. The reduction of NDI in the presence of fluoride and cyanide in different polar solvents indicates that involvement of such deprotonated solvents in the electron transfer mechanism may not be operative in our present system. Low-temperature kinetic studies support the formation of a charge transfer associative transient species, which likely allows overcoming the thermodynamically uphill barrier for the direct electron transfer mechanism.