Theoretical investigation of the absorption spectra and singlet-triplet energy gap of positively charged tetraphenylporphyrins as potential photodynamic therapy photosensitizers

DFT and TD-DFT calculations have been performed on a series of positively charged tetraphenylporphyrins with the aim to check whether these compounds can be used as photosensitizers in photodynamic therapy (PDT). Absorption spectra and singlet-triplet energy gaps have been computed by using the BP86, PBE0, and omega B97XD exchange-correlation functionals. Polarizable continuum model (PCM) has been used to take into account solvent effects. A careful analysis has been made on the Q-band, localized in the near-red visible region of the spectrum, since it plays a fundamental role in the drug design of new photodynamic therapy photosensitizers. Our results show that all the examined molecules have an adsorption band that falls in the so-called therapeutic window and possess a singlet-triplet energy gap able to promote the excitation of molecular oxygen from its ground triplet to the excited singlet state. The use of the omega B97XD exchange correlation functional, which accounts for dispersion interactions, allows calculating excitation energy values close to the experimental values.