The rational design of photoacids requires accessible predictive models of the electronic effect of functional groups on chemical templates of interest. Here, the effect of substituents on the photoacidity and excited-state proton transfer (PT) pathways of prototype 2-naphthol (2OH) at the symmetric C7 position was investigated through photochemical and computational studies of 7-amino-2-naphthol (7N2OH) and 7-methoxy-2-naphthol (7OMe2OH). Time-resolved emission experiments of 7N2OH revealed that the presence of an electron-withdrawing versus electron-donating group (EWG vs EDG, NH3+ vs NH2) led to a drastic decline in photoacidity: pK(a)* = 1.1 +/- 0.2 vs 9.6 +/- 0.2. Time-dependent density functional theory calculations with explicit water molecules confirmed that the excited neutral state (x = NH2) is greatly stabilized by water, with equation-of-motion coupled cluster singles and doubles calculations supporting potential mixing between the La and Lb states. Similar suppression of photoacidity, however, was not observed for 7OMe(2)OH with EDG OCH3, pK(a)* = 2.7 +/- 0.1. Hammett plots of the ground- and excited-state PT reactions of substituted 7-x-2OH compounds (x = CN, NH3+, H, CH3, OCH3, OH, and NH2) vs Hammett parameters sigma(p) showed breaks in the linearity between the EDG and EWG regions: rho similar to 0 vs 1.14 and rho* similar to 0 vs 3.86. The divergent acidic behavior most likely arises from different mixing mechanisms of the lowest L-b state with the L-a and possible B-b states upon substitution of naphthalene in water.
