title: Can phthalocyanines and their substituted alpha-para-(methoxy)phenyl derivatives act as photosensitizers in photodynamic therapy? A TD-DFT study.
abstract: A time-dependent density functional theory study (TD-DFT) is presented regarding the substituent effects on the Q-bands of two classes of non-planar phthalocyanines: the alpha-octaphenyl and p-alpha-octamethoxyphenyl substituted compounds, in their free-base and zinc complex forms. Singlet vertical excitation energies, computed at the PBE0/SVP//BP86/SVP level of theory also including bulk solvent effects (COSMO model), resulted within 0.1 eV of experiment. The experimental red-shift for the Q-band, going from the phenylated to the methoxyphenylated case, was well-reproduced theoretically and in the latter case it was found to depend mainly on the nature of the substituents and partly on structure distortion effects. The energetic gap between the singlet ground and first triplet excited state was calculated in solvent to be 1.28 eV for the free-base phthalocyanine (H2Pc) and 1.45 eV for the unsubstituted zinc complex (ZnPc) and lower than 0.98 eV for all the other compounds, which is the energetic lower limit for a molecule to act as photosensitiser in photodynamic therapy according to a Type II reaction mechanism. As a consequence, since this property-requirement for drugs used in photodynamic therapy is not fulfilled by the investigated near-infrared photosensitizers, they cannot be proposed as candidates for their use in this medical treatment.
authors.affiliation: Dipartimento di Chimica and Centro di Calcolo ad Alte Prestazioni per Elaborazioni Parallele e Distribuite-Centro di Eccellenza MURST, Università della Calabria, I-87030, Arcavacata di Rende, Italy.
authors.forename: Angelo Domenico
authors.initials: AD
authors.lastname: Quartarolo
authors.forename: Ida
authors.initials: I
authors.lastname: Lanzo
authors.forename: Emilia
authors.initials: E
authors.lastname: Sicilia
authors.forename: Nino
authors.initials: N
authors.lastname: Russo
mesh_terms: D003198:Computer Simulation; D007211:Indoles / Q000737:chemistry*; D054833:Isoindoles; D008958:Models, Molecular; D015394:Molecular Structure; D011789:Quantum Theory; D011838:Radiation-Sensitizing Agents / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry; D013997:Time Factors
chemical_list: D007211:Indoles; D054833:Isoindoles; D011838:Radiation-Sensitizing Agents; D012997:Solvents; C013647:phthalocyanine