The ultrafast dynamics of the photochromic reaction of dithizonatophenylmercury(II) was recently reported. For purpose of investigating the effect of electronically different substituents (X = o-F, m-F, p-F, p-Cl, o-CH3, m-CH3, p-CH3, m,p-diCH(3), p-OCH3, o-SCH3, and p-SCH3) on this reaction, a series of phenyl-substituted dithizones were synthesized and complexed with phenylmercury(II). A variation of more than 3 ps in ground state repopulation times was observed, with the o-methyl derivative absorbing both at shortest wavelength and having the fastest repopulation time, while the p-S-methyl derivative lies at the opposite extremity. An increase in both decay times and lambda(max) values is generally reflected by an increase in electron density in the chromophore. Ultrafast rates also proved to be dependent on solvent polarity, while a profound solvatochromic effect was observed in the transition state absorbance. Density functional theory realistically simulated isomer stabilities, electronic spectra and molecular orbitals. Increased electron density enhances stability in the photoexcited blue isomer relative to the orange resting state, as seen from a comparison between orange and blue isomer total bonding energies. A linear trend between computed HOMO energies and experimental lambda(max) of related aliphatic substituted derivatives was found.