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Characterization of the UV-Visible absorption spectra of manganese(III) porphyrins with time-dependent density functional theory calculations

  • Melinda A. Fodor , Péter Szabó EMAIL logo , György Lendvay EMAIL logo and Ottó Horváth
Published/Copyright: June 24, 2021
Zeitschrift für Physikalische Chemie
From the journal Zeitschrift für Physikalische Chemie Volume 236 Issue 1

Abstract

Mn(III) porphyrins display a unique UV–Vis spectrum: compared to the free-base and other metalloporphyrins, a strong red shift of the Soret-band and several extra bands can be observed in their spectra. To understand this behavior, we have recorded the UV–Vis spectra of differently substituted water-soluble Mn(III) porphyrins and conducted extensive theoretical investigations using time-dependent density functional theory. The calculated optical transitions, using the O3LYP functional, agree well with the measured absorption bands. According to the spectral interpretation, the Soret-band involves a mixture of L–L and ligand-to-metal charge transfer excitations, while the Q-bands and the higher-energy bands in the UV region correspond to pure LMCT as well as to ligand to metal-ligand mixed orbital excitations. The impact of the explicit and implicit water solvent on the spectral features is also discussed.

Keywords: DFT; manganese; optical spectrum; porphyrin; TD-DFT
Corresponding authors: Péter Szabó, Department of Physics and Material Science, University of Luxembourg, L-1511, Luxembourg City, Luxembourg; and György Lendvay, Center for Natural Sciences, Department of General and Inorganic Chemistry, University of Pannonia, Egyetem u. 10, H-8200, Veszprém, Hungary; and Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Magyar tudósok körútja 2, H-1117, Budapest, Hungary, E-mail: (P. Szabó), (G. Lendvay)

Funding source: Széchenyi 2020

Award Identifier / Grant number: GINOP-2.3.2-15-2016-00016 and VEKOP-2.3.1-16-2017-00013

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: This work was supported by the Széchenyi 2020 under the GINOP-2.3.2-15-2016-00016 and VEKOP-2.3.1-16-2017-00013.

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Supplementary Material

The online version of this article offers supplementary material (https://doi.org/10.1515/zpch-2020-1787).

Received: 2020-11-24
Accepted: 2021-05-27
Published Online: 2021-06-24
Published in Print: 2022-01-27

© 2021 Walter de Gruyter GmbH, Berlin/Boston

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https://doi.org/10.1515/zpch-2020-1787
Keywords for this article
DFT; manganese; optical spectrum; porphyrin; TD-DFT

Articles in the same Issue

  1. Frontmatter
  2. Original Papers
  3. Efficient adsorption of chlorpyrifos onto modified activated carbon by gamma irradiation; a plausible adsorption mechanism
  4. Characterization of the UV-Visible absorption spectra of manganese(III) porphyrins with time-dependent density functional theory calculations
  5. Extended visible light driven photocatalytic hydrogen generation by electron induction from g-C3N4 nanosheets to ZnO through the proper heterojunction
  6. The use of FCNT/PANI nanocomposites to extend the life of lithium-ion batteries
  7. Jellyfish-like few-layer graphene nanoflakes: high paramagnetic response alongside increased interlayer interaction
  8. Multi-functional organic–inorganic hydrogel microspheres as efficient catalytic system for reduction of toxic dyes in aqueous medium
  9. Aggregation behavior and thermodynamic properties of the mixture of sodium carboxymethyl cellulose and cetyltrimethylammonium bromide in numerous temperatures and mixed solvents
  10. A comparative study on the performance of photo/sono/peroxone processes for the removal and mineralization of reactive dye red 198 from aquatic environments
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