Theoretical UV-Vis spectra of tetracationic porphyrin: effects of environment on electronic spectral properties
- 80 Downloads
Electronic and spectroscopic properties of tetracationic 5,10,15,20-tetrakis(1-methyl-4-pyridyl)-21H,23H-porphyrin (TMPyP) were investigated in the framework of the density functional theory (DFT). Modeling of implicit solvent, charge effects, and medium acidity were performed and compared with experimental results. Various hybrid exchange correlation functionals in the Kohn-Sham Scheme of the DFT were employed and various porphyrin models were constructed, simulating different environmental conditions. Since porphyrins present several technological applications with a plethora of interacting systems and the optical spectra profiles are often used to characterize these macrocyclic compounds, the study performed here aims to stablish a correct description of the UV-Vis spectrum. These results allowed to reproduce, both qualitatively as well as quantitatively, the Soret band of the TMPyP.
KeywordsDFT Porphyrin UV-Vis spectroscopy CAM-B3YLP
The calculations used the computational resources provided by the HPC-USP/Rice agreement and the cluster funded by FAPESP. The authors also acknowledge the computational time provided by the CENAPAD/SP.
The authors thank the financial support provided by the INCT-INEO, CNPq and FAPESP.
- 3.Takagi S, Eguchi M, Tryk D, Inoue H (2006) Porphyrin photochemistry in inorganic/organic hybrid materials: clays, layered semiconductors, nanotubes, and mesoporous materials. J Photochem Photobiol C: Photochem Rev 7:104–126. https://doi.org/10.1016/j.jphotochemrev.2006.04.002 CrossRefGoogle Scholar
- 4.Alberti G, Constantino U (1996) Solid-state supramolecular chemistry: two- and three-dimensional inorganic networks1st edn. Pergamon, New YorkGoogle Scholar
- 9.Tuffy B (2011) Porphyrin materials for organic light emitting diodes1st edn. LAP LAMBERT Academic Publishing, SaarbrückenGoogle Scholar
- 15.Díaz C, Catalán-Toledo J, Flores ME et al (2017) Dispersion of the photosensitizer 5,10,15,20-tetrakis(4-sulfonatophenyl)-porphyrin by the amphiphilic polymer poly(vinylpirrolidone) in highly porous solid materials designed for photodynamic therapy. J Phys Chem B 121:7373–7381. https://doi.org/10.1021/acs.jpcb.7b04727 CrossRefPubMedGoogle Scholar
- 40.De Simone BC, Mazzone G, Russo N et al (2018) Excitation energies, singlet–triplet energy gaps, spin–orbit matrix elements and heavy atom effects in BOIMPYs as possible photosensitizers for photodynamic therapy: a computational investigation. Phys Chem Chem Phys 20:2656–2661. https://doi.org/10.1039/C7CP06763A CrossRefPubMedGoogle Scholar
- 47.Ishida Y, Masui D, Shimada T et al (2012) The mechanism of the porphyrin spectral shift on inorganic nanosheets: the molecular flattening induced by the strong host–guest interaction due to the “size-matching rule”. J Phys Chem C 116:7879–7885. https://doi.org/10.1021/jp300842f CrossRefGoogle Scholar
- 49.Frisch MJ, Trucks GW, Schlegel HB et al (2009) Gaussian 09, Rev A.1. Gaussian, Inc, WallingfordGoogle Scholar
- 62.Véras LMC, Cunha VRR, Lima FCDA et al (2013) Industrial scale isolation, structural and spectroscopic characterization of epiisopiloturine from Pilocarpus microphyllus Stapf leaves: a promising alkaloid against schistosomiasis. PLoS One 8:e66702. https://doi.org/10.1371/journal.pone.0066702 CrossRefPubMedPubMedCentralGoogle Scholar