Development of water-soluble phenazine-2,3-diol-based photosensitizers for singlet oxygen generation

Abstract

Phenazine-2,3-diol-based dyes, KY-1Na and KY-2Na bearing one and two carboxylic acid sodium salts, respectively, have been newly developed as water-soluble photosensitizers (PSs) possessing the ability to generate singlet oxygen (¹O₂). In order to evaluate the solubility of KY-1Na and KY-2Na in water, the hydrophobicity/hydrophilicity of the two PSs was investigated by experimental measurement of the logarithms (log P_o/w) of the 1-octanol/water partition coefficient (P_o/w) for the PS. The log P_o/w values of both KY-1Na and KY-2Na were determined to be −0.9, indicating that both the PSs are more hydrophilic than Rose Bengal (−0.6) and have hydrophilicity equivalent to methylene blue (−0.9). Both the PSs in water show a broad photoabsorption band in the range of 500 to 600 nm. Thus, we estimated the ¹O₂ quantum yields (Φ_Δ) of KY-1Na and KY-2Na in water by using 9,10-anthracenediyl-bis(methylene)dimalonic acid (ABDA) as a water-soluble ¹O₂ scavenger. It was found that in water the Φ_Δ value (0.19) of KY-2Na is higher than that of KY-1Na (0.06). Density functional theory (DFT) calculations suggested that the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) distributions for the molecular structure of KY-2Na are adequately separated, leading to a decrease in the energy gap (ΔE_ST) between the singlet state (S₁) and the triplet state (T₁) that causes efficient intersystem crossing (ISC), compared to that for the molecular structure of KY-1Na. Indeed, time-dependent DFT (TD-DFT) calculations demonstrated that the ΔE_ST(S₁–T₁) value (0.82 eV) of KY-2Na is smaller than that (0.98 eV) of KY-1Na, resulting in a relatively high Φ_Δ value of KY-2Na. Consequently, we demonstrate that phenazine-2,3-diol-based PSs bearing carboxylic acid salts possess high solubility and moderate ¹O₂ generation ability in water.