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The halogen bond in weakly bonded complexes and the consequences for aromaticity and spin-orbit coupling

Ana V. Cunha, Remco Havenith (UGent) , Jari van Gog, Freija De Vleeschouwer, Frank De Proft and Wouter Herrebout
(2023) MOLECULES. 28(2).
Author
Organization
Abstract
The halogen bond complexes CF(3)Xmiddot middot middot Y and C(2)F(3)Xmiddot middot middot Y, with Y = furan, thiophene, selenophene and X = Cl, Br, I, have been studied by using DFT and CCSD(T) in order to understand which factors govern the interaction between the halogen atom X and the aromatic ring. We found that PBE0-dDsC/QZ4P gives an adequate description of the interaction energies in these complexes, compared to CCSD(T) and experimental results. The interaction between the halogen atom X and the pi-bonds in perpendicular orientation is stronger than the interaction with the in-plane lone pairs of the heteroatom of the aromatic cycle. The strength of the interaction follows the trend Cl < Br < I; the chalcogenide in the aromatic ring nor the hybridization of the C-X bond play a decisive role. The energy decomposition analysis shows that the interaction energy is dominated by all three contributions, viz., the electrostatic, orbital, and dispersion interactions: not one factor dominates the interaction energy. The aromaticity of the ring is undisturbed upon halogen bond formation: the pi-ring current remains equally strong and diatropic in the complex as it is for the free aromatic ring. However, the spin-orbit coupling between the singlet and triplet pi -> pi(*) states is increased upon halogen bond formation and a faster intersystem crossing between these states is therefore expected.
Keywords
Chemistry (miscellaneous), Analytical Chemistry, Organic Chemistry, Physical and Theoretical Chemistry, Molecular Medicine, Drug Discovery, Pharmaceutical Science, halogen bonds, density functional theory, energy decomposition analysis, ring current analysis, spin-orbit coupling, ROOM-TEMPERATURE PHOSPHORESCENCE, DENSITY-FUNCTIONAL THEORY, RING CURRENTS, CRYSTAL-STRUCTURE, ORGANIC MATERIALS, PI INTERACTIONS, C-13 NMR, DISPERSION, 1,4-DIIODOTETRAFLUOROBENZENE, COMPETITION

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Citation

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MLA
Cunha, Ana V., et al. “The Halogen Bond in Weakly Bonded Complexes and the Consequences for Aromaticity and Spin-Orbit Coupling.” MOLECULES, vol. 28, no. 2, 2023, p. 772, doi:10.3390/molecules28020772.
APA
Cunha, A. V., Havenith, R., van Gog, J., De Vleeschouwer, F., De Proft, F., & Herrebout, W. (2023). The halogen bond in weakly bonded complexes and the consequences for aromaticity and spin-orbit coupling. MOLECULES, 28(2), 772. https://doi.org/10.3390/molecules28020772
Chicago author-date
Cunha, Ana V., Remco Havenith, Jari van Gog, Freija De Vleeschouwer, Frank De Proft, and Wouter Herrebout. 2023. “The Halogen Bond in Weakly Bonded Complexes and the Consequences for Aromaticity and Spin-Orbit Coupling.” MOLECULES 28 (2): 772. https://doi.org/10.3390/molecules28020772.
Chicago author-date (all authors)
Cunha, Ana V., Remco Havenith, Jari van Gog, Freija De Vleeschouwer, Frank De Proft, and Wouter Herrebout. 2023. “The Halogen Bond in Weakly Bonded Complexes and the Consequences for Aromaticity and Spin-Orbit Coupling.” MOLECULES 28 (2): 772. doi:10.3390/molecules28020772.
Vancouver
1.
Cunha AV, Havenith R, van Gog J, De Vleeschouwer F, De Proft F, Herrebout W. The halogen bond in weakly bonded complexes and the consequences for aromaticity and spin-orbit coupling. MOLECULES. 2023;28(2):772.
IEEE
[1]
A. V. Cunha, R. Havenith, J. van Gog, F. De Vleeschouwer, F. De Proft, and W. Herrebout, “The halogen bond in weakly bonded complexes and the consequences for aromaticity and spin-orbit coupling,” MOLECULES, vol. 28, no. 2, p. 772, 2023.
@article{01H3XXYYRZ47DYG85H6J2Y6Q0W,
  abstract     = {{The halogen bond complexes CF(3)Xmiddot middot middot Y and C(2)F(3)Xmiddot middot middot Y, with Y = furan, thiophene, selenophene and X = Cl, Br, I, have been studied by using DFT and CCSD(T) in order to understand which factors govern the interaction between the halogen atom X and the aromatic ring. We found that PBE0-dDsC/QZ4P gives an adequate description of the interaction energies in these complexes, compared to CCSD(T) and experimental results. The interaction between the halogen atom X and the pi-bonds in perpendicular orientation is stronger than the interaction with the in-plane lone pairs of the heteroatom of the aromatic cycle. The strength of the interaction follows the trend Cl < Br < I; the chalcogenide in the aromatic ring nor the hybridization of the C-X bond play a decisive role. The energy decomposition analysis shows that the interaction energy is dominated by all three contributions, viz., the electrostatic, orbital, and dispersion interactions: not one factor dominates the interaction energy. The aromaticity of the ring is undisturbed upon halogen bond formation: the pi-ring current remains equally strong and diatropic in the complex as it is for the free aromatic ring. However, the spin-orbit coupling between the singlet and triplet pi -> pi(*) states is increased upon halogen bond formation and a faster intersystem crossing between these states is therefore expected.}},
  author       = {{Cunha, Ana V. and Havenith, Remco and van Gog, Jari and De Vleeschouwer, Freija and De Proft, Frank and Herrebout, Wouter}},
  issn         = {{1420-3049}},
  journal      = {{MOLECULES}},
  keywords     = {{Chemistry (miscellaneous),Analytical Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Molecular Medicine,Drug Discovery,Pharmaceutical Science,halogen bonds,density functional theory,energy decomposition analysis,ring current analysis,spin-orbit coupling,ROOM-TEMPERATURE PHOSPHORESCENCE,DENSITY-FUNCTIONAL THEORY,RING CURRENTS,CRYSTAL-STRUCTURE,ORGANIC MATERIALS,PI INTERACTIONS,C-13 NMR,DISPERSION,1,4-DIIODOTETRAFLUOROBENZENE,COMPETITION}},
  language     = {{eng}},
  number       = {{2}},
  title        = {{The halogen bond in weakly bonded complexes and the consequences for aromaticity and spin-orbit coupling}},
  url          = {{http://doi.org/10.3390/molecules28020772}},
  volume       = {{28}},
  year         = {{2023}},
}
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