Tuning the Electronic Excitation of Meta Nitrophenolate Anions to the Biological Transparency Window by Amino Substitution.

Nitrophenolate anions are molecules that release nitric oxide (NO) after electronic excitation. This class of molecules is particularly interesting for potential applications in skin cancer treatment, which requires the use of wavelengths in the biological transparency window. Among the various isomers, meta NP- (mNP-) has the lowest excitation energy with a band origin at 625 nm. Here, using cryogenic photodissociation spectroscopy, we studied the effect on the electronic spectroscopy of mNP- of methyl and amino electron-donating groups at the ortho position relative to NO2. Unlike the bare mNP- anion, all compounds exhibit broad photodissociation spectra, revealing significant geometric changes between the S0 and S1 (ππNO2*) states. While methyl substitution causes a blue shift of the absorption band maximum, amino-substituted mNP- anions show large red shifts, with the absorption band starting below 800 nm for 4NH2mNP-, i.e., in the biological transparency window, while still leading to NO photorelease. The spectral shifts induced by the substituents are interpreted by comparison with coupled-cluster calculations performed in the ground state and the first excited state. These electron-donating groups in the ortho position relative to NO2 perturb the electronic properties of mNP- through opposing steric and electrostatic effects.