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A theoretical investigation on the spectroscopic properties and photosensitizing capability of 5, 10, 15, 20-tetraphenylsapphyrin and 5, 10, 15, 20-tetraphenyl-26,28-diheterosapphyrins with two O, S, or Se Atoms

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Abstract

A density functional theory (DFT) study of the V/UV spectrum and the adiabatic energy released from the triplet excited state of sapphyrin and three disubstituted derivatives (with O, S or Se atoms) is performed in order to obtain an accurate theoretical description of their capability as photosensitizers in photodynamic therapy (PDT). For the calculation of the V/UV spectra, we used two functionals already tested for porphyrin derivatives, B3LYP and PBE0, and two new ones recently proposed, MPWB1 K and M05, all of them with two different basis sets and two continuum solvent models. The best agreement with experimental data was obtained at the CPCM-M05/6-31 + G(d)//B3LYP/6-31 + G(d) level, at which errors lie in the range of 0.13–0.20 eV for the Q band in CH2Cl2 solution. A careful comparison between triplet and singlet geometries shows that the inner macrocycle enlarges, but planarity distortions lead to a volume contraction upon excitation to the triplet state for sapphyrin, and O and S heterosapphyrins, and to negligible volume changes for Se heterosapphyrin. Actually, the heterosapphyrins with S and Se atoms acquire a saddle shape in the triplet state. According to our results, the energy released from the triplet state for S- and Se- disubstituted sapphyrins could be adequate to generate activated oxygen both in the gas phase and in CH2Cl2 solution.

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Acknowledgments

The authors thank MEC (SPAIN, PCI2005-A7-0304), FONDECYT No 1060203, 1090700 and No 7080007 (CONICYT/CHILE) for financial support. GIC-J thanks to DICYT/USACH Apoyo Complementario for computational time provided.

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Authors and Affiliations

  1. Departamento de Química Física y Analítica, Facultad de Química, Universidad de Oviedo, C/Julián Clavería 8, 33006, Oviedo, Asturias, Spain

    Ramón López & M. Isabel Menéndez

  2. Laboratorio de Química Teórica, Departamento de Ciencias del Ambiente, Facultad de Química y Biología, Universidad de Santiago de Chile (USACH), Casilla 40, Correo 33, Santiago, CHILE

    Mireya Santander-Nelli & Gloria I. Cárdenas-Jirón

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  1. Ramón López
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  2. M. Isabel Menéndez
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  3. Mireya Santander-Nelli
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  4. Gloria I. Cárdenas-Jirón
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Correspondence to M. Isabel Menéndez or Gloria I. Cárdenas-Jirón.

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López, R., Menéndez, M.I., Santander-Nelli, M. et al. A theoretical investigation on the spectroscopic properties and photosensitizing capability of 5, 10, 15, 20-tetraphenylsapphyrin and 5, 10, 15, 20-tetraphenyl-26,28-diheterosapphyrins with two O, S, or Se Atoms. Theor Chem Acc 127, 475–484 (2010). https://doi.org/10.1007/s00214-010-0735-5

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