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Title: Stabilization and Structure of the cis Tautomer of a Free-Base Porphyrin

Abstract

Single-crystal X-ray analysis of the β-heptakis(trifluoromethyl)-meso-tetrakis(p-fluorophenyl)porphyrin, H2[(CF3)7TpFPP], has revealed the first example of a stable cis tautomer of a free-base porphyrin, the long-postulated intermediate of porphyrin tautomerism. The stability of the unique molecule appears to reflect a dual origin: a strongly saddled porphyrin skeleton, which alleviates electrostatic repulsion between the two NH protons, and two polarization-enhanced, transannular N-H∙∙∙O-H∙∙∙N hydrogen bond chains, each involving a molecule of water. DFT calculations suggest that the observed tautomer has a lower energy than the alternative, doubly hydrated trans tautomer by some 8.3 kcal mol-1 . A fascinating prospect thus exists that H2[(CF3)7TpFPP]∙2H2O and cognate structures may act as supramolecular synthons, which, given their chirality, may even be amenable to resolution into optically pure enantiomers.

Authors:
 [1];  [2];  [1]; ORCiD logo [1]
  1. The Arctic University of Norway, Tromso (Norway)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1436613
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 34; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Thomas, Kolle E., McCormick, Laura J., Vazquez-Lima, Hugo, and Ghosh, Abhik. Stabilization and Structure of the cis Tautomer of a Free-Base Porphyrin. United States: N. p., 2017. Web. doi:10.1002/anie.201701965.
Thomas, Kolle E., McCormick, Laura J., Vazquez-Lima, Hugo, & Ghosh, Abhik. Stabilization and Structure of the cis Tautomer of a Free-Base Porphyrin. United States. doi:https://doi.org/10.1002/anie.201701965
Thomas, Kolle E., McCormick, Laura J., Vazquez-Lima, Hugo, and Ghosh, Abhik. Wed . "Stabilization and Structure of the cis Tautomer of a Free-Base Porphyrin". United States. doi:https://doi.org/10.1002/anie.201701965. https://www.osti.gov/servlets/purl/1436613.
@article{osti_1436613,
title = {Stabilization and Structure of the cis Tautomer of a Free-Base Porphyrin},
author = {Thomas, Kolle E. and McCormick, Laura J. and Vazquez-Lima, Hugo and Ghosh, Abhik},
abstractNote = {Single-crystal X-ray analysis of the β-heptakis(trifluoromethyl)-meso-tetrakis(p-fluorophenyl)porphyrin, H2[(CF3)7TpFPP], has revealed the first example of a stable cis tautomer of a free-base porphyrin, the long-postulated intermediate of porphyrin tautomerism. The stability of the unique molecule appears to reflect a dual origin: a strongly saddled porphyrin skeleton, which alleviates electrostatic repulsion between the two NH protons, and two polarization-enhanced, transannular N-H∙∙∙O-H∙∙∙N hydrogen bond chains, each involving a molecule of water. DFT calculations suggest that the observed tautomer has a lower energy than the alternative, doubly hydrated trans tautomer by some 8.3 kcal mol-1 . A fascinating prospect thus exists that H2[(CF3)7TpFPP]∙2H2O and cognate structures may act as supramolecular synthons, which, given their chirality, may even be amenable to resolution into optically pure enantiomers.},
doi = {10.1002/anie.201701965},
journal = {Angewandte Chemie (International Edition)},
number = 34,
volume = 56,
place = {United States},
year = {2017},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 8 works
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Figures / Tables:

Figure 1 Figure 1: Thermal ellipsoid plots (33%) of H2[(CF3)7TpFPP]·2H2O: (a) top view and (b) close-up of the porphyrin core with hydrogen bond distances (Å).

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Works referenced in this record:

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Molecular structure of a gold β-octakis(trifluoromethyl)- meso -triarylcorrole: an 85° difference in saddling dihedral relative to copper
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Electron correlation in tetrapyrroles: ab initio calculations on porphyrin and the tautomers of chlorin
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    Works referencing / citing this record:

    Crystal structure refinement with SHELXL
    journal, January 2015

    • Sheldrick, George M.
    • Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8
    • DOI: 10.1107/s2053229614024218

    Structure and Stability of cis-Porphyrin
    journal, January 1995

    • Ghosh, Abhik; Almloef, Jan
    • The Journal of Physical Chemistry, Vol. 99, Issue 4
    • DOI: 10.1021/j100004a003

    Mechanism and Quantum Mechanical Tunneling Effects on Inner Hydrogen Atom Transfer in Free Base Porphyrin:  A Direct ab Initio Dynamics Study
    journal, February 2000

    • Maity, Dilip K.; Bell, Robert L.; Truong, Thanh N.
    • Journal of the American Chemical Society, Vol. 122, Issue 5
    • DOI: 10.1021/ja9925094

    The role of porphyrin chemistry in tumor imaging and photodynamic therapy
    journal, January 2011

    • Ethirajan, Manivannan; Chen, Yihui; Joshi, Penny
    • Chem. Soc. Rev., Vol. 40, Issue 1
    • DOI: 10.1039/b915149b

    Ab initio SCF studies of basis set effects in free base porphin
    journal, November 1991


    Nonplanar porphyrins and their significance in proteins
    journal, January 1998

    • A. Shelnutt, John; Song, Xing-Zhi; Ma, Jian-Guo
    • Chemical Society Reviews, Vol. 27, Issue 1
    • DOI: 10.1039/a827031z

    Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
    journal, January 2005

    • Weigend, Florian; Ahlrichs, Reinhart
    • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
    • DOI: 10.1039/b508541a

    Ab initio calculations on porphin
    journal, November 1974


    Supramolekulare Synthone für das Kristall-Engineering - eine neue organische Synthese
    journal, November 1995


    Chemistry with ADF
    journal, January 2001

    • te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.
    • Journal of Computational Chemistry, Vol. 22, Issue 9, p. 931-967
    • DOI: 10.1002/jcc.1056

    ShelXle : a Qt graphical user interface for SHELXL
    journal, November 2011

    • Hübschle, Christian B.; Sheldrick, George M.; Dittrich, Birger
    • Journal of Applied Crystallography, Vol. 44, Issue 6
    • DOI: 10.1107/s0021889811043202

    Rationale for mixing exact exchange with density functional approximations
    journal, December 1996

    • Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron
    • The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985
    • DOI: 10.1063/1.472933

    Generalized Gradient Approximation Made Simple
    journal, October 1996

    • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
    • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
    • DOI: 10.1103/physrevlett.77.3865

    Nonplanar distortion modes for highly substituted porphyrins
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    • Medforth, Craig J.; Senge, Mathias O.; Smith, Kevin M.
    • Journal of the American Chemical Society, Vol. 114, Issue 25
    • DOI: 10.1021/ja00051a019

    NMR Study of the Tautomerism of Porphyrin Including the Kinetic HH/HD/DD Isotope Effects in the Liquid and the Solid State
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    • Braun, Juergen; Koecher, Martin; Schlabach, Martin
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    • DOI: 10.1021/ja00094a014

    “Strong” Hydrogen Bonds in Chemistry and Biology
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    • Silvers, Stuart J.; Tulinsky, Alexander.
    • Journal of the American Chemical Society, Vol. 89, Issue 13
    • DOI: 10.1021/ja00989a036

    Vibrational photochemistry of porphine imbedded in a hexane-d14 Shpol'skii matrix
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    • Butenhoff, Thomas J.; Chuck, Roy S.; Limbach, Hans Heinrich.
    • The Journal of Physical Chemistry, Vol. 94, Issue 20
    • DOI: 10.1021/j100383a021

    Primary kinetic HH/HD/DH/DD isotope effects and proton tunnelling in double proton-transfer reactions
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    • Limbach, Hans-Heinrich; Hennig, J�rgen; Gerritzen, Detlef
    • Faraday Discussions of the Chemical Society, Vol. 74
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    A Metallocorrole with Orthogonal Pyrrole Rings
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    • Thomas, Kolle E.; Conradie, Jeanet; Hansen, Lars K.
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    SHELXT – Integrated space-group and crystal-structure determination
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    • Sheldrick, George M.
    • Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8
    • DOI: 10.1107/s2053273314026370

    Electron correlation in tetrapyrroles: ab initio calculations on porphyrin and the tautomers of chlorin
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    • Almlof, Jan; Fischer, Thomas H.; Gassman, Paul G.
    • The Journal of Physical Chemistry, Vol. 97, Issue 42
    • DOI: 10.1021/j100144a012

    Octaiodoporphyrin
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    Supramolecular Synthons in Crystal Engineering—A New Organic Synthesis
    journal, November 1995

    • Desiraju, Gautam R.
    • Angewandte Chemie International Edition in English, Vol. 34, Issue 21
    • DOI: 10.1002/anie.199523111

    OH-Cluster mit circular angeordneten, homodromen Wasserstoffbrückenbindungen
    journal, May 1980


    Circular hydrogen bonds
    journal, May 1979


    Hydrogen atom tunneling in the thermal tautomerism of porphine imbedded in a n-hexane matrix
    journal, December 1988

    • Butenhoff, Thomas J.; Moore, C. Bradley.
    • Journal of the American Chemical Society, Vol. 110, Issue 25
    • DOI: 10.1021/ja00233a009

    The Structure of free base Porphine: an Average of Three Independent Structures
    journal, October 1973


    Arrhenius curves of hydrogen transfers: tunnel effects, isotope effects and effects of pre-equilibria
    journal, July 2006

    • Limbach, Hans-Heinrich; Miguel Lopez, Juan; Kohen, Amnon
    • Philosophical Transactions of the Royal Society B: Biological Sciences, Vol. 361, Issue 1472
    • DOI: 10.1098/rstb.2006.1872

    Die Wasserstoffbrücke im Festkörper
    journal, January 2002


    OH Clusters with Homodromic Circular Arrangement of Hydrogen Bonds
    journal, May 1980

    • Saenger, Wolfram; Lindner, Klaus
    • Angewandte Chemie International Edition in English, Vol. 19, Issue 5
    • DOI: 10.1002/anie.198003981

    Copper β-Octakis(trifluoromethyl)corroles: New Paradigms for Ligand Substituent Effects in Transition Metal Complexes
    journal, November 2008

    • Thomas, Kolle Ekaney; Wasbotten, Ingar H.; Ghosh, Abhik
    • Inorganic Chemistry, Vol. 47, Issue 22
    • DOI: 10.1021/ic801101k

    Two Macrocycles in One Shot: Synthesis, Spectroscopy, Photophysics, and Tautomerism of 23-Oxahemiporphycene and 21-Oxacorrole-5-carbaldehyde
    journal, June 2018

    • Ostapko, Jakub; Kelm, Anna; Kijak, Michał
    • Chemistry - A European Journal, Vol. 24, Issue 39
    • DOI: 10.1002/chem.201801293

    Molecular structure of a gold β-octakis(trifluoromethyl)- meso -triarylcorrole: an 85° difference in saddling dihedral relative to copper
    journal, April 2012


    The Hydrogen Bond in the Solid State
    journal, January 2002


    Structure of tetra-n-propylporphine. Average structure for the free base macrocycle from three independent determinations
    journal, June 1972

    • Codding, Penelope W.; Tulinsky, A.
    • Journal of the American Chemical Society, Vol. 94, Issue 12
    • DOI: 10.1021/ja00767a016

    Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)]
    journal, February 1997


    Photophysical and Structural Properties of Saddle-Shaped Free Base Porphyrins:  Evidence for an “Orthogonal” Dipole Moment
    journal, August 2001

    • Sazanovich, Igor V.; Galievsky, Victor A.; van Hoek, Arie
    • The Journal of Physical Chemistry B, Vol. 105, Issue 32
    • DOI: 10.1021/jp010274o

    Redetermination of the structure of porphine
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    • Chen, Betty M. L.; Tulinsky, A.
    • Journal of the American Chemical Society, Vol. 94, Issue 12
    • DOI: 10.1021/ja00767a015

    Two Macrocycles in One Shot: Synthesis, Spectroscopy, Photophysics, and Tautomerism of 23-Oxahemiporphycene and 21-Oxacorrole-5-carbaldehyde
    journal, June 2018

    • Ostapko, Jakub; Kelm, Anna; Kijak, Michał
    • Chemistry - A European Journal, Vol. 24, Issue 39
    • DOI: 10.1002/chem.201801293

    Molekulares Engineering freier Porphyrinbasen als Liganden - das N-H⋅⋅⋅X-Bindungsmotiv in Tetrapyrrolen
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    Free-base porphyrins with localized NH protons. Can substituents alone stabilize the elusive cis tautomer?
    journal, January 2020

    • Thomas, Kolle E.; Conradie, Jeanet; Beavers, Christine M.
    • Organic & Biomolecular Chemistry, Vol. 18, Issue 15
    • DOI: 10.1039/d0ob00452a

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