The 4-functionalized 6,6'-dimethyl-3,3'-dihydroxy-2,2'-bipyridine dyes (BP(OH)2-Rs) have exhibited dienol and diketo emissions. The optimum geometrical structures for ground, singlet and triplet excited states are computed by DFT/B3LYP/6-31++G that showed the planarity of BP(OH)2-Rs structure. The emission spectra of the molecules are determined in the gas-phase at singlet and triplet excited states using CIS/6-31++G. The theoretical calculations are carried out for BP(OH)2-Rs to understand the impact of different substituents (R = -H (I), -Br (II), -TMS (III), -C2H (IV), -terpyridine (V) and -bodipy (diazaboraindacene) (VI)) on excited-state intramolecular proton transfer (ESIPT) in singlet and triplet excited states. Based on the calculations, the concerted diproton transfer proceeds in the triplet excited state, in which nπ* state has a significant participation in ESIPT. The spectral variation at ESIPT emission of BP(OH)2-Rs is influenced by the electron-acceptor ability of the substituents. The compound V revealed a higher spectral intensity compared to the others. From the comparison with the experimental data, the molecule V is almost planar agreed with the X-ray structure and trend variation of wavelengths. The molecule VI contains bodipy chromophore that excitation energy transfers completely from BP(OH)2 core to a bodipy substituent, leading to emission from the lowest-lying bodipy substituent, and consequently, ESIPT does not occur for this dye.
Keywords: ESIPT process; Excited state; Functionalized bipyridine dyes; Luminescence; Simulation.
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