Structural Effects of meso-Halogenation on Porphyrins: meso-Xn-ABCD Macrocycles

  1. Keith J. Flanagan,
  2. Maximilian Paradiz DominguezORCID Logo,
  3. Zoi MelissariORCID Logo,
  4. Hans-Georg EckhardtORCID Logo,
  5. René M. Williams,
  6. Dáire Gibbons,
  7. Caroline Prior,
  8. Gemma M. Locke,
  9. Alina Meindl,
  10. Aoife A. Ryan and
  11. Mathias O SengeORCID Logo

Submitting author affiliation: Trinity College Dublin, The University of Dubin, Dublin, Ireland

Beilstein Arch. 2021, 202121.

Published 12 Mar 2021

  • Preprint


The use of halogens in the crystal engineering of porphyrin scaffolds has been a topic of strong interest over the past decades. Previously, this was focused on the introduction of a variety of halogens on the meso-phenyl groups of the porphyrin. However, investigations into the effects of direct halogenation of porphyrins at the meso-position on their crystalline architectures have not been conducted to date. Herein we have characterized a series of direct meso-halogenated porphyrins using single crystal X-ray crystallography. This is accompanied by a detailed conformational analysis of all deposited meso-halogenated porphyrins in the CCDC. In this study we have used the Hirshfeld fingerprint plots together with normal-coordinate structural decomposition and determined crystal structures to elucidate the conformation, present intermolecular interactions, and compare respective contacts within the crystalline architectures. Additionally, we have used density functional theory calculations to determine the structure of several halogenated porphyrins. This contrasts conformational analysis with existing X-ray structures and gives a method to characterize samples that are difficult to crystallize.

Keywords: porphyrins; conformational analysis; supramolecular chemsitry; crystallography

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Flanagan, K. J.; Paradiz Dominguez, M.; Melissari, Z.; Eckhardt, H.-G.; Williams, R. M.; Gibbons, D.; Prior, C.; Locke, G. M.; Meindl, A.; Ryan, A. A.; Senge, M. O. Beilstein Arch. 2021, 202121. doi:10.3762/bxiv.2021.21.v1

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