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Molecular structure of a free-base β-Octaiodo -meso-tetraarylporphyrin. A rational route to cis porphyrin tautomers?

Molecular structure of a free-base β-Octaiodo -meso-tetraarylporphyrin. A rational route to cis porphyrin tautomers?
Molecular structure of a free-base β-Octaiodo -meso-tetraarylporphyrin. A rational route to cis porphyrin tautomers?

Although a cis tautomer has long been invoked as an intermediate in porphyrin tautomerism, the first such species was only recently isolated and structurally characterized in the form of a β-heptakis(trifluoromethyl)-meso-tetraarylporphyrin. Reported herein is the molecular structure of a β-octaiodo-meso-tetraarylporphyrin solvate, which also exhibits a cis tautomeric structure. Both structures implicate two factors as critical to the stabilization of the cis tautomeric form - a free-base porphyrin that is naturally strongly saddled on steric grounds and a hydroxylic or amphiprotic solvent that can provide hydrogen-bonded N-H···X-H···N (X = O in both the above examples) straps connecting the central NH groups with the antipodal unprotonated nitrogens. The results raise the prospect that a rational strategy affording cis porphyrin tautomers in a predictable manner may be within reach.

1528-7483
4257-4259
Thomassen, Ivar K.
c2d0503b-d24b-4eb6-ba83-5204ec3d7c78
McCormick, Laura J.
f1c2f8cd-adcc-4bbf-9289-0b33a006d2bb
Ghosh, Abhik
01a311da-a139-43f0-ae29-0efa0e8788f7
Thomassen, Ivar K.
c2d0503b-d24b-4eb6-ba83-5204ec3d7c78
McCormick, Laura J.
f1c2f8cd-adcc-4bbf-9289-0b33a006d2bb
Ghosh, Abhik
01a311da-a139-43f0-ae29-0efa0e8788f7

Thomassen, Ivar K., McCormick, Laura J. and Ghosh, Abhik (2018) Molecular structure of a free-base β-Octaiodo -meso-tetraarylporphyrin. A rational route to cis porphyrin tautomers? Crystal Growth and Design, 18 (8), 4257-4259. (doi:10.1021/acs.cgd.8b00629).

Record type: Article

Abstract

Although a cis tautomer has long been invoked as an intermediate in porphyrin tautomerism, the first such species was only recently isolated and structurally characterized in the form of a β-heptakis(trifluoromethyl)-meso-tetraarylporphyrin. Reported herein is the molecular structure of a β-octaiodo-meso-tetraarylporphyrin solvate, which also exhibits a cis tautomeric structure. Both structures implicate two factors as critical to the stabilization of the cis tautomeric form - a free-base porphyrin that is naturally strongly saddled on steric grounds and a hydroxylic or amphiprotic solvent that can provide hydrogen-bonded N-H···X-H···N (X = O in both the above examples) straps connecting the central NH groups with the antipodal unprotonated nitrogens. The results raise the prospect that a rational strategy affording cis porphyrin tautomers in a predictable manner may be within reach.

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Published date: 1 August 2018

Identifiers

Local EPrints ID: 438916
URI: http://eprints.soton.ac.uk/id/eprint/438916
ISSN: 1528-7483
PURE UUID: 99d53c41-74cc-49c4-89e6-755853a1f644
ORCID for Laura J. McCormick: ORCID iD orcid.org/0000-0002-6634-4717

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Date deposited: 26 Mar 2020 17:35
Last modified: 26 Nov 2021 03:21

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Contributors

Author: Ivar K. Thomassen
Author: Abhik Ghosh

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