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. https://doi.org/10.3762/bxiv.2021.21.v1

Published 12 Mar 2021

  • Preprint

Abstract

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

Supporting Information

Format: CIF Size: 1.1 MB   Download
Format: CIF Size: 447.4 KB   Download
Format: CIF Size: 417.0 KB   Download
Format: DOCX Size: 3.8 MB   Download
Format: CIF Size: 759.8 KB   Download
Format: CIF Size: 303.1 KB   Download
Format: CIF Size: 489.9 KB   Download
Format: CIF Size: 855.4 KB   Download
Format: CIF Size: 386.3 KB   Download
Format: CIF Size: 657.6 KB   Download
Format: CIF Size: 581.5 KB   Download
Format: CIF Size: 777.9 KB   Download
Format: CIF Size: 411.3 KB   Download
Format: DOC Size: 42.4 MB   Download
Format: CIF Size: 558.7 KB   Download

How to Cite

When a peer-reviewed version of this preprint is available, this information will be updated in the information box above. If no peer-reviewed version is available, please cite this preprint using the following information:

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

Download Citation
Download RIS (Reference Manager) Download BIB (BIBTEX)

© 2021 Flanagan et al.; licensee Beilstein-Institut.
This is an open access work under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/4.0). Please note that the reuse, redistribution and reproduction in particular requires that the author(s) and source are credited and that individual graphics may be subject to special legal provisions.
The license is subject to the Beilstein Archives terms and conditions: (https://www.beilstein-archives.org/xiv/terms)

Other Beilstein-Institut Open Science Activities

Logo
Logo
Logo
Symposia