A Time-Dependent Density Functional Study of a Non-Aromatic [1.1.1.1.1]-Pentaphyrin and Its Lutetium Complex

作者：Sousa Flavio Fortes Ramos; Quartarolo Angelo Domenico; Sicilia Emilia; Russo Nino^*

来源：Journal of Physical Chemistry B, 2012, 116(35): 10816-10823.

DOI：10.1021/jp3068359

The molecular structures and absorption electronic spectra of two novel phototoxic pentapyrrolic expanded porphyrins (a isopentaphyrin derivative and its lutetium complex) have been studied at the density functional level and its time-dependent extension (TDDFT). The geometries were optimized with three different exchange-correlation functionals (PBE0, B3LYP, and omega B97XD) and the SV(P) basis set plus the pseudopotential method for the complex. With respect to the porphyrin, the structure of [1.1.1.1.1]-pentaphyrin and its lutetium complex are predicted much distorted due to the lack of conjugation. The lowest excitation energy band (experimental at 814 nm) for the free-base isopentaphyrin is well predicted by the omega B97XD at 772 nm. The possible photodynamic reaction mechanisms (types I and II) were studied through the calculation of the electron affinity and ionization potentials in solvent, using the COSMO model.

• 出版日期2012-9-6