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Research Article Open access CC BY 4.0

Absorption Spectra of Protonated Corroles: Two Distinct Patterns Due to Peripheral Substitution Architecture

Lev L. Gladkov, Dmitry V. Klenitsky, Mikalai M. Kruk

Organics · pp. 490–502 · Published 9 Oct 2023

10.3390/org4040034

Abstract

The origin of individual features in the ground state absorption spectra of two protonated corroles differing in the architecture of peripheral substitution (either Cm-aryl or Cb-alkyl) have been studied in detail with the ground state absorption spectroscopy and density functional theory calculations. The geometry optimization, molecular orbitals and absorption spectra calculation have been carried out. It was found that protonation leads to the saddle type macrocycle conformation in contrast with the wave type conformation known for the parent-free base corroles. The mean plane deviation parameter Δ23 for the macrocycle, pyrrole tilting angles and the degree of pyramidalization λ2 of all four pyrrole nitrogens was found to depend on the peripheral substitution architecture. Macrocycle conformation of the protonated forms has distinct asymmetrical features which are reflected by the sets of values of the tilting angles and values of pyramidalization degree. The pair of pyrroles B and C has smaller tilting angles and higher pyramidalization degree values, whereas the opposite trend was found for the pair of pyrroles A and D. Electronic effects and structural differences induced by substitution lead to the pronounced shifts of the molecular orbitals. In the Cb-alkylated corrole, almost-degenerated HOMO and HOMO-1 molecular orbitals lead to enhancement of the configuration interaction. As a result, the Qx transition oscillator strength goes down, becoming comparable to that of the Qy one. A large HOMO-HUMO-1gap in the Cm-aryl corrole minimizes the configuration interaction, giving rise to Qx band domination in the visible range spectrum.

Corrole Protonation Chemistry Absorption spectroscopy Density functional theory Crystallography Pyrrole Molecular orbital

References (34)

  1. 1 Senge, 1992, The conformational flexibility of tetrapyrroles—Current model studies and photobiological relevance [DOI]
  2. 2 Senge, 2015, Conformational control of cofactors in nature—The influence of protein-induced macrocycle distortion on the biological function of tetrapyrroles [DOI]
  3. 3 Kielmann, 2019, Molecular engineering of free-base porphyrins as ligands—The N-H…X binding motif in tetrapyrroles [DOI]
  4. 4 Stone, 1968, The molecular and crystal structure of porphyrin diacids [DOI]
  5. 5 Cheng, 1997, An analysis of porphyrin molecular flexibility—Use of porphyrin diacids [DOI]
  6. 6 Lavallee, D.K. (1987). The Chemistry and Biochemistry of N-Substituted Porphyrins, Wiley-VCH. [1st ed.].
  7. 7 Kadish, 2000, Highly substituted porphyrins
  8. 8 Roucan, 2018, Nonplanar porphyrins by N-substitution: A neglected pathway [DOI]
  9. 9 Fang, 2014, Planar and nonplanar free-base tetrarylporphyrins: β-pyrrole substituents and geometric effects on electrochemistry, spectroelectrochemistry, and protonation/deprotonation reactions in nonaqueous media [DOI]
  10. 10 Ballester, 2020, Protonation of planar and nonplanar porphyrins: A calorimetric and computational study [DOI]
  11. 11 Kruk, 2008, Highly sensitive halide ions recognition with diprotonated porphyrin [DOI]
  12. 12 Kruk, 2009, Tetrapyrrolic compounds as the hosts for binding of halides and alkali metal cations [DOI]
  13. 13 Novaritsa, 2019, Conformational Re-engineering of porphyrins as receptors with switchable N-H…X-type binding modes [DOI]
  14. 14 Roucan, 2018, Conformational control of nonplanar freebase porphyrins: Toward bifunctional catalysts of tunable basicity [DOI]
  15. 15 Ding, 2017, Development of ion chemosensors based on porphyrin analogues [DOI]
  16. 16 Paolesse, 2017, Porphyrinoids for chemical sensor applications [DOI]
  17. 17 Kruk, 2019, Molecular structure and conformation of free base corroles [DOI]
  18. 18 Ivanova, 2012, Corrole NH Tautomers: Spectral Features and Individual Protonation [DOI]
  19. 19 Kruk, 2012, Solvent-Dependent Deprotonation ofmeso-Pyrimidinylcorroles: Absorption and Fluorescence Studies [DOI]
  20. 20 Ngo, 2010, Synthetic, Structural, and Photophysical Exploration of meso-Pyrimidinyl-Substituted AB2-Corroles [DOI]
  21. 21 Petrova, 2019, Synthesis and Some Physical-Chemical Properties of meso-Aryl- and Alkyl Substituted Corroles and their Metal Complexes [DOI]
  22. 22 Laikov, 1997, Fast evaluation of density functional exchange-correlation terms using the expansion of the electron density in auxiliary basis sets [DOI]
  23. 23 Laikov, 2005, PRIRODA-04: A quantum-chemical program suite. New possibilities in the study of molecular systems with the application of parallel computing [DOI]
  24. 24 Alabugin, 2015, Orbital hybridization: A key electronic factor in control of structure and reactivity [DOI]
  25. 25 Beenken, 2014, Molecular Structures and Absorption Spectra Assignmentof Corrole NH Tautomers [DOI]
  26. 26 Ajeeb, 2020, Spectral and luminescent properties and NH-tautomerism of alkylated corrole free bases [DOI]
  27. 27 Kruk, 2011, Influence of macrocycle protonation on the photophysical properties of porphyrins [DOI]
  28. 28 Rosa, 2006, Synergism of porphyrin-core saddling and twisting of meso-aryl substituents [DOI]
  29. 29 Klenitsky, 2022, Inversion of aromaticity of NH-tautomers of the free base corroles in the lowest triplet T1 state [DOI]
  30. 30 Gao, 2012, Density Functional Theory Investigation of Structures and Electronic Spectra of N-protonated Corroles [DOI]
  31. 31 Kruk, 2023, Molecular conformation and aromaticity of N-substituted porphine derivatives
  32. 32 Dolphin, 1978, Optical spectra and electronic structure of porphyrins and related rings
  33. 33 Kruk, 2022, Solvatochromism of the free base corroles [DOI]
  34. 34 Gladkov, L.L., Klenitsky, D.V., and Kruk, M.M. (2023). Mechanisms of bathochromic band shifts in the absorption spectra of the N-substituted porphine derivatives. J. Appl. Spectr. [DOI]

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