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Licensed Unlicensed Requires Authentication Published by De Gruyter August 10, 2020

Influence of meso-linker attachment on the formation of core···π interactions in urea-functionalized porphyrins

  • Keith J. Flanagan , Aoife A. Ryan , Brendan Twamley and Mathias O. Senge EMAIL logo


The ability to cover the face of a porphyrin macrocycle selectively is an attractive feature for concepts such as catalysis and anion binding that is reliant on porphyrin core interactions. Herein, we have synthesized a family of mono-urea functionalized porphyrin complexes with intent to investigate their potential to form core···π interactions selectively to one face of the porphyrin macrocycle. By altering the distance between the urea moiety and the porphyrin through direct linkage or introducing a linker group we can control the formation of the core interactions. This is clearly seen in the crystal structure of 1-phenyl-3-(2-([10,15,20-triphenylporphyrinato]zinc(II)-5-yl)phenyl)urea where a unique face capping effect is demonstrated. In the crystal of this complex, there is a hydrogen-bonding network between the urea group and the axial methanol ligand forming head-to-tail aggregates with the Zn–O axis all molecules pointing in one direction.

Corresponding author: Prof. Dr. Mathias O. Senge, School of Chemistry, Trinity Biomedical Sciences Institute, Trinity College Dublin, The University of Dublin, 152–160 Pearse Street, Dublin 2, Dublin, Ireland, E-mail:

Funding source: Science Foundation Ireland

Award Identifier / Grant number: IvP 13/IA/1894

Funding source: FET

Award Identifier / Grant number: 828779

  1. Author contribution: 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 a grant from Science Foundation Ireland (SFI, IvP 13/IA/1894) and through funding from the European Union’s Horizon 2020 research and innovation program under the FET Open grant agreement no. 828779.

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


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Received: 2020-06-05
Accepted: 2020-07-10
Published Online: 2020-08-10
Published in Print: 2020-09-25

© 2020 Walter de Gruyter GmbH, Berlin/Boston

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