Theoretical Chemistry Accounts

, Volume 127, Issue 5–6, pp 475–484 | Cite as

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

  • Ramón López
  • M. Isabel MenéndezEmail author
  • Mireya Santander-Nelli
  • Gloria I. Cárdenas-JirónEmail author
Regular Article


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.


Sapphyrin Heterosapphyrins Photosensitizers TD-DFT V/UV spectra Excited states 



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.

Supplementary material

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Supplementary material 1 (DOC 54 kb)
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Copyright information

© Springer-Verlag 2010

Authors and Affiliations

  1. 1.Departamento de Química Física y Analítica, Facultad de QuímicaUniversidad de OviedoOviedo, AsturiasSpain
  2. 2.Laboratorio de Química Teórica, Departamento de Ciencias del Ambiente, Facultad de Química y BiologíaUniversidad de Santiago de Chile (USACH)SantiagoCHILE

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