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Title: Quantum chemical replica-exchange umbrella sampling molecular dynamics simulations reveal the formation mechanism of iron phthalocyanine from iron and phthalonitrile

Abstract

Phthalocyanine (Pc) and its metal complexes (MPcs) have been used industrially since their discovery in the early 20th century. The phthalonitrile (PN) method is a well-known synthesis method in which Pc or MPc can be afforded by heating a mixture of PN and metal powders over 280 °C with only moderate yield. However, the formation mechanism of the phthalocyanines and the intermediate stages of this seemingly simple reaction have yet to be fully understood. To study this mechanism computationally, we carried out quantum chemical molecular dynamics (MD) simulations based on the density-functional tight-binding (DFTB) method, applying the replica-exchange umbrella sampling (REUS) method, starting from four PN molecules and one iron atom. The DFTB-REUS-MD simulations successfully yielded FePc, and a metastable structure very similar to FePc but with a reactive nitrene unit was also identified that might explain the incomplete conversion of the reactants into FePc. Furthermore, analysis of the MD trajectories reveals a three-step FePc formation mechanism for the PN method.

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [4]
  1. Nagoya Univ., Nagoya (Japan)
  2. Nagoya Univ., Nagoya (Japan); Chinese Academy of Sciences, Changchun (People's Republic of China)
  3. Nagoya Univ., Nagoya (Japan); JST-CREST, Nagoya (Japan)
  4. Nagoya Univ., Nagoya (Japan); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1474873
Alternate Identifier(s):
OSTI ID: 1460501
Grant/Contract Number:  
[AC05-00OR22725]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
[ Journal Volume: 149; Journal Issue: 7]; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; phthalocyanine; phthalonitrile; density-functional tight-binding; replica-exchange umbrella sampling; formation mechanism

Citation Formats

Ito, Shingo, Wang, Ying, Okamoto, Yuko, and Irle, Stephan. Quantum chemical replica-exchange umbrella sampling molecular dynamics simulations reveal the formation mechanism of iron phthalocyanine from iron and phthalonitrile. United States: N. p., 2018. Web. doi:10.1063/1.5026956.
Ito, Shingo, Wang, Ying, Okamoto, Yuko, & Irle, Stephan. Quantum chemical replica-exchange umbrella sampling molecular dynamics simulations reveal the formation mechanism of iron phthalocyanine from iron and phthalonitrile. United States. doi:10.1063/1.5026956.
Ito, Shingo, Wang, Ying, Okamoto, Yuko, and Irle, Stephan. Mon . "Quantum chemical replica-exchange umbrella sampling molecular dynamics simulations reveal the formation mechanism of iron phthalocyanine from iron and phthalonitrile". United States. doi:10.1063/1.5026956. https://www.osti.gov/servlets/purl/1474873.
@article{osti_1474873,
title = {Quantum chemical replica-exchange umbrella sampling molecular dynamics simulations reveal the formation mechanism of iron phthalocyanine from iron and phthalonitrile},
author = {Ito, Shingo and Wang, Ying and Okamoto, Yuko and Irle, Stephan},
abstractNote = {Phthalocyanine (Pc) and its metal complexes (MPcs) have been used industrially since their discovery in the early 20th century. The phthalonitrile (PN) method is a well-known synthesis method in which Pc or MPc can be afforded by heating a mixture of PN and metal powders over 280 °C with only moderate yield. However, the formation mechanism of the phthalocyanines and the intermediate stages of this seemingly simple reaction have yet to be fully understood. To study this mechanism computationally, we carried out quantum chemical molecular dynamics (MD) simulations based on the density-functional tight-binding (DFTB) method, applying the replica-exchange umbrella sampling (REUS) method, starting from four PN molecules and one iron atom. The DFTB-REUS-MD simulations successfully yielded FePc, and a metastable structure very similar to FePc but with a reactive nitrene unit was also identified that might explain the incomplete conversion of the reactants into FePc. Furthermore, analysis of the MD trajectories reveals a three-step FePc formation mechanism for the PN method.},
doi = {10.1063/1.5026956},
journal = {Journal of Chemical Physics},
number = [7],
volume = [149],
place = {United States},
year = {2018},
month = {7}
}

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Works referenced in this record:

New Monte Carlo algorithms for protein folding
journal, April 1999


Fractional occupations and density-functional energies and forces
journal, June 1992


Nonphysical sampling distributions in Monte Carlo free-energy estimation: Umbrella sampling
journal, February 1977


Über die Produkte der Einwirkung von Acetanhydrid auf Phthalamid
journal, March 1907


Nosé–Hoover chains: The canonical ensemble via continuous dynamics
journal, August 1992

  • Martyna, Glenn J.; Klein, Michael L.; Tuckerman, Mark
  • The Journal of Chemical Physics, Vol. 97, Issue 4
  • DOI: 10.1063/1.463940

Constant-temperature free energy surfaces for physical and chemical processes
journal, April 1993

  • Boczko, Erik M.; Brooks, Charles L.
  • The Journal of Physical Chemistry, Vol. 97, Issue 17
  • DOI: 10.1021/j100119a043

An investigation into the mechanism of the phthalonitrile route to copper phthalocyanines using differential scanning calorimetry
journal, January 1989

  • Christie, Robert M.; Deans, Derek D.
  • Journal of the Chemical Society, Perkin Transactions 2, Issue 2
  • DOI: 10.1039/p29890000193

382. Phthalocyanines. Part VII. Phthalocyanine as a co-ordinating group. A general investigation of the metallic derivatives
journal, January 1936

  • Barrett, P. A.; Dent, C. E.; Linstead, R. P.
  • Journal of the Chemical Society (Resumed)
  • DOI: 10.1039/jr9360001719

DFTB+, a Sparse Matrix-Based Implementation of the DFTB Method
journal, July 2007

  • Aradi, B.; Hourahine, B.; Frauenheim, Th.
  • The Journal of Physical Chemistry A, Vol. 111, Issue 26
  • DOI: 10.1021/jp070186p

Quelques sels complexes des o-dinitriles avec le cuivre et la pyridine
journal, January 1927


Generalized-ensemble algorithms: enhanced sampling techniques for Monte Carlo and molecular dynamics simulations
journal, May 2004


Multidimensional replica-exchange method for free-energy calculations
journal, October 2000

  • Sugita, Yuji; Kitao, Akio; Okamoto, Yuko
  • The Journal of Chemical Physics, Vol. 113, Issue 15
  • DOI: 10.1063/1.1308516

THE weighted histogram analysis method for free-energy calculations on biomolecules. I. The method
journal, October 1992

  • Kumar, Shankar; Rosenberg, John M.; Bouzida, Djamal
  • Journal of Computational Chemistry, Vol. 13, Issue 8
  • DOI: 10.1002/jcc.540130812

Wave Functions for Impurity Levels
journal, September 1954


Parameter Calibration of Transition-Metal Elements for the Spin-Polarized Self-Consistent-Charge Density-Functional Tight-Binding (DFTB) Method:  Sc, Ti, Fe, Co, and Ni
journal, May 2007

  • Zheng, Guishan; Witek, Henryk A.; Bobadova-Parvanova, Petia
  • Journal of Chemical Theory and Computation, Vol. 3, Issue 4
  • DOI: 10.1021/ct600312f

Implementation of replica-exchange umbrella sampling in the DFTB + semiempirical quantum chemistry package
journal, July 2016


Oligomeric cyclization of dinitriles in the synthesis of phthalocyanines and related compounds: the role of the alkoxide anion
journal, January 1987

  • Oliver, Stuart W.; Smith, Thomas D.
  • Journal of the Chemical Society, Perkin Transactions 2, Issue 11
  • DOI: 10.1039/p29870001579

Simulation of the (H2O)8 cluster with the SCC-DFTB electronic structure method
journal, August 2012


Auxiliary basis sets for main row atoms and transition metals and their use to approximate Coulomb potentials
journal, October 1997

  • Eichkorn, Karin; Weigend, Florian; Treutler, Oliver
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 97, Issue 1-4
  • DOI: 10.1007/s002140050244

Replica-exchange molecular dynamics method for protein folding
journal, November 1999


Industrial Applications of Cyclodextrins
journal, July 1998


Ab initio replica-exchange Monte Carlo method for cluster studies
journal, January 2001


214. Phthalocyanines. Part III. Preliminary experiments on the preparation of phthalocyanines from phthalonitrile
journal, January 1934