skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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, H 2[(CF 3) 7T pFPP], 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 H 2[(CF 3) 7T pFPP]∙ 2H 2O 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]
+ Show Author Affiliations
  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) (SC-22)
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.
Copy to clipboard
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:10.1002/anie.201701965.
Copy to clipboard
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:10.1002/anie.201701965. https://www.osti.gov/servlets/purl/1436613.
Copy to clipboard
@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}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI:  10.1002/anie.201701965
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science

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).
All figures and tables (5 total)
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

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

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

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

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

Circular hydrogen bonds
journal, May 1979

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

Octaiodoporphyrin
journal, November 2015

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

The Hydrogen Bond in the Solid State
journal, January 2002

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

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

“Strong” Hydrogen Bonds in Chemistry and Biology
journal, October 1997

Redetermination of the structure of porphine
journal, June 1972

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

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

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

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

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

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

Primary kinetic HH/HD/DH/DD isotope effects and proton tunnelling in double proton-transfer reactions
journal, January 1982

  • Limbach, Hans-Heinrich; Hennig, J�rgen; Gerritzen, Detlef
  • Faraday Discussions of the Chemical Society, Vol. 74
  • DOI: 10.1039/dc9827400229

The crystal and molecular structure of triclinic tetraphenylporphyrin
journal, June 1967

  • 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
journal, October 1990

  • Butenhoff, Thomas J.; Chuck, Roy S.; Limbach, Hans Heinrich.
  • The Journal of Physical Chemistry, Vol. 94, Issue 20
  • DOI: 10.1021/j100383a021

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

Nonplanar distortion modes for highly substituted porphyrins
journal, December 1992

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

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

Die Wasserstoffbrücke im Festkörper
journal, January 2002

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

NMR Study of the Tautomerism of Porphyrin Including the Kinetic HH/HD/DD Isotope Effects in the Liquid and the Solid State
journal, July 1994

  • Braun, Juergen; Koecher, Martin; Schlabach, Martin
  • Journal of the American Chemical Society, Vol. 116, Issue 15
  • DOI: 10.1021/ja00094a014

Ab initio calculations on porphin
journal, November 1974

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

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

SHELXT – Integrated space-group and crystal-structure determination
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053273314026370

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

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

Electron correlation in tetrapyrroles: ab initio calculations on porphyrin and the tautomers of chlorin
journal, October 1993

  • Almlof, Jan; Fischer, Thomas H.; Gassman, Paul G.
  • The Journal of Physical Chemistry, Vol. 97, Issue 42
  • DOI: 10.1021/j100144a012

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

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

A Metallocorrole with Orthogonal Pyrrole Rings
journal, March 2011

  • Thomas, Kolle E.; Conradie, Jeanet; Hansen, Lars K.
  • European Journal of Inorganic Chemistry, Vol. 2011, Issue 12
  • DOI: 10.1002/ejic.201100170
    [ × clear filter / sort ]

    Works referencing / citing this record:

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

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

    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

    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

    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

    A Metallocorrole with Orthogonal Pyrrole Rings
    journal, March 2011

    • Thomas, Kolle E.; Conradie, Jeanet; Hansen, Lars K.
    • European Journal of Inorganic Chemistry, Vol. 2011, Issue 12
    • DOI: 10.1002/ejic.201100170

    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

    Ab initio calculations on porphin
    journal, November 1974

    Octaiodoporphyrin
    journal, November 2015

    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

    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

    Electron correlation in tetrapyrroles: ab initio calculations on porphyrin and the tautomers of chlorin
    journal, October 1993

    • Almlof, Jan; Fischer, Thomas H.; Gassman, Paul G.
    • The Journal of Physical Chemistry, Vol. 97, Issue 42
    • DOI: 10.1021/j100144a012

    Vibrational photochemistry of porphine imbedded in a hexane-d14 Shpol'skii matrix
    journal, October 1990

    • Butenhoff, Thomas J.; Chuck, Roy S.; Limbach, Hans Heinrich.
    • The Journal of Physical Chemistry, Vol. 94, Issue 20
    • DOI: 10.1021/j100383a021

    Nonplanar distortion modes for highly substituted porphyrins
    journal, December 1992

    • 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
    journal, July 1994

    • Braun, Juergen; Koecher, Martin; Schlabach, Martin
    • Journal of the American Chemical Society, Vol. 116, Issue 15
    • DOI: 10.1021/ja00094a014

    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

    Redetermination of the structure of porphine
    journal, June 1972

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

    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

    The crystal and molecular structure of triclinic tetraphenylporphyrin
    journal, June 1967

    • Silvers, Stuart J.; Tulinsky, Alexander.
    • Journal of the American Chemical Society, Vol. 89, Issue 13
    • DOI: 10.1021/ja00989a036

    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

    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

    Circular hydrogen bonds
    journal, May 1979

    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

    Primary kinetic HH/HD/DH/DD isotope effects and proton tunnelling in double proton-transfer reactions
    journal, January 1982

    • Limbach, Hans-Heinrich; Hennig, J�rgen; Gerritzen, Detlef
    • Faraday Discussions of the Chemical Society, Vol. 74
    • DOI: 10.1039/dc9827400229

    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

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

    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

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

    “Strong” Hydrogen Bonds in Chemistry and Biology
    journal, October 1997

      [ × clear filter / sort ]

      Figures / Tables found in this record:

      Figure 1(p. 3)figure
      Table 2(p. 3)table
      Table 3(p. 4)table
      Figure 2(p. 5)figure
      Figure 3(p. 5)figure
        [ × clear filter / sort ]
        Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

        Similar records in OSTI.GOV collections:

        Other research related to this record: