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Title: Magnetic Transitions in Iron Porphyrin Halides by Inelastic Neutron Scattering and Ab-initio Studies of Zero-Field Splittings

Abstract

Zero-field splitting (ZFS) parameters of nondeuterated metalloporphyrins [Fe(TPP)X] (X = F, Br, I; H2TPP = tetraphenylporphyrin) are determined by inelastic neutron scattering (INS). The ZFS values are D = 4.49(9) cm–1 for tetragonal polycrystalline [Fe(TPP)F], and D = 8.8(2) cm–1, E = 0.1(2) cm–1 and D = 13.4(6) cm–1, E = 0.3(6) cm–1 for monoclinic polycrystalline [Fe(TPP)Br] and [Fe(TPP)I], respectively. Along with our recent report of the ZFS value of D = 6.33(8) cm–1 for tetragonal polycrystalline [Fe(TPP)Cl], these data provide a rare, complete determination of ZFS parameters in a metalloporphyrin halide series. The electronic structure of [Fe(TPP)X] (X = F, Cl, Br, I) has been studied by multireference ab initio methods: the complete active space self-consistent field (CASSCF) and the N-electron valence perturbation theory (NEVPT2) with the aim of exploring the origin of the large and positive zero-field splitting D of the 6A1 ground state. D was calculated from wave functions of the electronic multiplets spanned by the d5 configuration of Fe(III) along with spin–orbit coupling accounted for by quasi degenerate perturbation theory. Results reproduce trends of D from inelastic neutron scattering data increasing in the order from F, Cl, Br, to I. A mapping of energy eigenvalues andmore » eigenfunctions of the S = 3/2 excited states on ligand field theory was used to characterize the σ- and π-antibonding effects decreasing from F to I. This is in agreement with similar results deduced from ab initio calculations on CrX63- complexes and also with the spectrochemical series showing a decrease of the ligand field in the same directions. A correlation is found between the increase of D and decrease of the π- and σ-antibonding energies eλX (λ = σ, π) in the series from X = F to I. Analysis of this correlation using second-order perturbation theory expressions in terms of angular overlap parameters rationalizes the experimentally deduced trend. Furthermore, D parameters from CASSCF and NEVPT2 results have been calibrated against those from the INS data, yielding a predictive power of these approaches. Methods to improve the quantitative agreement between ab initio calculated and experimental D and spectroscopic transitions for high-spin Fe(III) complexes are proposed.« less

Authors:
 [1];  [2];  [3];  [1];  [2];  [1]
  1. Univ. of Tennessee, Knoxville, TN (United States)
  2. Max Planck Institute for Chemical Energy Conversion, Stiftstrase (Germany); Bulgaria Academy of Science (Bulgaria)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1224166
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 54; Journal Issue: 20; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Stavretis, Shelby E., Atanasov, Mihail, Podlesnyak, Andrey A., Hunter, Seth C., Neese, Frank, and Xue, Zi-Ling. Magnetic Transitions in Iron Porphyrin Halides by Inelastic Neutron Scattering and Ab-initio Studies of Zero-Field Splittings. United States: N. p., 2015. Web. https://doi.org/10.1021/acs.inorgchem.5b01505.
Stavretis, Shelby E., Atanasov, Mihail, Podlesnyak, Andrey A., Hunter, Seth C., Neese, Frank, & Xue, Zi-Ling. Magnetic Transitions in Iron Porphyrin Halides by Inelastic Neutron Scattering and Ab-initio Studies of Zero-Field Splittings. United States. https://doi.org/10.1021/acs.inorgchem.5b01505
Stavretis, Shelby E., Atanasov, Mihail, Podlesnyak, Andrey A., Hunter, Seth C., Neese, Frank, and Xue, Zi-Ling. Fri . "Magnetic Transitions in Iron Porphyrin Halides by Inelastic Neutron Scattering and Ab-initio Studies of Zero-Field Splittings". United States. https://doi.org/10.1021/acs.inorgchem.5b01505. https://www.osti.gov/servlets/purl/1224166.
@article{osti_1224166,
title = {Magnetic Transitions in Iron Porphyrin Halides by Inelastic Neutron Scattering and Ab-initio Studies of Zero-Field Splittings},
author = {Stavretis, Shelby E. and Atanasov, Mihail and Podlesnyak, Andrey A. and Hunter, Seth C. and Neese, Frank and Xue, Zi-Ling},
abstractNote = {Zero-field splitting (ZFS) parameters of nondeuterated metalloporphyrins [Fe(TPP)X] (X = F, Br, I; H2TPP = tetraphenylporphyrin) are determined by inelastic neutron scattering (INS). The ZFS values are D = 4.49(9) cm–1 for tetragonal polycrystalline [Fe(TPP)F], and D = 8.8(2) cm–1, E = 0.1(2) cm–1 and D = 13.4(6) cm–1, E = 0.3(6) cm–1 for monoclinic polycrystalline [Fe(TPP)Br] and [Fe(TPP)I], respectively. Along with our recent report of the ZFS value of D = 6.33(8) cm–1 for tetragonal polycrystalline [Fe(TPP)Cl], these data provide a rare, complete determination of ZFS parameters in a metalloporphyrin halide series. The electronic structure of [Fe(TPP)X] (X = F, Cl, Br, I) has been studied by multireference ab initio methods: the complete active space self-consistent field (CASSCF) and the N-electron valence perturbation theory (NEVPT2) with the aim of exploring the origin of the large and positive zero-field splitting D of the 6A1 ground state. D was calculated from wave functions of the electronic multiplets spanned by the d5 configuration of Fe(III) along with spin–orbit coupling accounted for by quasi degenerate perturbation theory. Results reproduce trends of D from inelastic neutron scattering data increasing in the order from F, Cl, Br, to I. A mapping of energy eigenvalues and eigenfunctions of the S = 3/2 excited states on ligand field theory was used to characterize the σ- and π-antibonding effects decreasing from F to I. This is in agreement with similar results deduced from ab initio calculations on CrX63- complexes and also with the spectrochemical series showing a decrease of the ligand field in the same directions. A correlation is found between the increase of D and decrease of the π- and σ-antibonding energies eλX (λ = σ, π) in the series from X = F to I. Analysis of this correlation using second-order perturbation theory expressions in terms of angular overlap parameters rationalizes the experimentally deduced trend. Furthermore, D parameters from CASSCF and NEVPT2 results have been calibrated against those from the INS data, yielding a predictive power of these approaches. Methods to improve the quantitative agreement between ab initio calculated and experimental D and spectroscopic transitions for high-spin Fe(III) complexes are proposed.},
doi = {10.1021/acs.inorgchem.5b01505},
journal = {Inorganic Chemistry},
number = 20,
volume = 54,
place = {United States},
year = {2015},
month = {10}
}

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Works referenced in this record:

Electron-nuclear double resonance spectroscopy (and electron spin-echo envelope modulation spectroscopy) in bioinorganic chemistry
journal, March 2003


Linear Correlation between 1 H and 13 C Chemical Shifts of Ferriheme Proteins and Model Ferrihemes
journal, February 2011

  • Yang, Fei; Shokhireva, Tatiana K.; Walker, F. Ann
  • Inorganic Chemistry, Vol. 50, Issue 4
  • DOI: 10.1021/ic1020274

Electronic Structure and Dynamics of Nitrosyl Porphyrins
journal, July 2010

  • Scheidt, W. Robert; Barabanschikov, Alexander; Pavlik, Jeffrey W.
  • Inorganic Chemistry, Vol. 49, Issue 14
  • DOI: 10.1021/ic100261b

Copperdioxygen complexes: Functional models for proteins
journal, January 1998

  • Karlin, K. D.; Lee, D. -H.; Obias, H. V.
  • Pure and Applied Chemistry, Vol. 70, Issue 4
  • DOI: 10.1351/pac199870040855

Photochemical hydrogen production with molecular devices comprising a zinc porphyrin and a cobaloxime catalyst
journal, March 2012


Zero-field splitting in metal complexes
journal, May 2004


Magnetic circular dichroism determination of zero-field splitting in chloro(meso-tetraphenylporphinato)iron(III)
journal, April 1983

  • Browett, W. R.; Fucaloro, A. F.; Morgan, T. V.
  • Journal of the American Chemical Society, Vol. 105, Issue 7
  • DOI: 10.1021/ja00345a032

Quantum Tunneling of Magnetization and Related Phenomena in Molecular Materials
journal, January 2003

  • Gatteschi, Dante; Sessoli, Roberta
  • Angewandte Chemie International Edition, Vol. 42, Issue 3
  • DOI: 10.1002/anie.200390099

Physical Techniques for the Investigation of Molecular Magnetic Clusters
journal, October 2000

  • Gatteschi, Dante
  • The Journal of Physical Chemistry B, Vol. 104, Issue 42
  • DOI: 10.1021/jp001644w

Multi-frequency, high-field EPR as a powerful tool to accurately determine zero-field splitting in high-spin transition metal coordination complexes
journal, September 2006

  • Krzystek, J.; Ozarowski, A.; Telser, J.
  • Coordination Chemistry Reviews, Vol. 250, Issue 17-18
  • DOI: 10.1016/j.ccr.2006.03.016

Magnetic Excitations in Metalloporphyrins by Inelastic Neutron Scattering: Determination of Zero-Field Splittings in Iron, Manganese, and Chromium Complexes
journal, December 2013

  • Hunter, Seth C.; Podlesnyak, Andrey A.; Xue, Zi-Ling
  • Inorganic Chemistry, Vol. 53, Issue 4
  • DOI: 10.1021/ic4028354

Far‐Infrared Magnetic Resonance in Fe(III) and Mn(III) Porphyrins, Myoglobin, Hemoglobin, Ferrichrome A, and Fe(III) Dithiocarbamates
journal, May 1971

  • Brackett, G. C.; Richards, P. L.; Caughey, W. S.
  • The Journal of Chemical Physics, Vol. 54, Issue 10
  • DOI: 10.1063/1.1674688

Correlations of axial ligand field strength and zero-field splittings in the carbon-13 NMR spectra of five- and six-coordinate high-spin iron(III) porphyrin complexes
journal, January 1983

  • Goff, Harold M.; Shimomura, Eric T.; Phillippi, Martin A.
  • Inorganic Chemistry, Vol. 22, Issue 1
  • DOI: 10.1021/ic00143a017

Magnetic susceptibility, anisotropy, low temperature magnetisation and zero field splitting in tetraphenylporphynato iron(III) bromide
journal, December 1979


Thermomagnetic analysis of hemin and related compounds
journal, September 1969

  • Maricondi, Chris; Swift, Wayne; Straub, Darel K.
  • Journal of the American Chemical Society, Vol. 91, Issue 19
  • DOI: 10.1021/ja01047a003

Far-infrared studies on hemin and hemin-like complexes
journal, March 1971


Magnetic Cluster Excitations
journal, July 2010


Inelastic Neutron Scattering and Magnetic Susceptibilities of the Single-Molecule Magnets [Mn 4 O 3 X(OAc) 3 (dbm) 3 ] (X = Br, Cl, OAc, and F):  Variation of the Anisotropy along the Series
journal, December 2000

  • Andres, Hanspeter; Basler, Reto; Güdel, Hans-Ulrich
  • Journal of the American Chemical Society, Vol. 122, Issue 50
  • DOI: 10.1021/ja0009424

Inelastic Neutron Scattering Study of Electron Reduction in Mn 12 Derivatives
journal, February 2005

  • Basler, Reto; Sieber, Andreas; Chaboussant, Grégory
  • Inorganic Chemistry, Vol. 44, Issue 3
  • DOI: 10.1021/ic048931p

Ground-State Electronic Structure of Vanadium(III) Trisoxalate in Hydrated Compounds
journal, July 2009

  • Kittilstved, Kevin R.; Sorgho, Lilit Aboshyan; Amstutz, Nahid
  • Inorganic Chemistry, Vol. 48, Issue 16
  • DOI: 10.1021/ic900613p

Spectroscopic and Structural Characterization of the [Fe(imidazole) 6 ] 2+ Cation
journal, September 2003

  • Carver, Graham; Tregenna-Piggott, Philip L. W.; Barra, Anne-Laure
  • Inorganic Chemistry, Vol. 42, Issue 18
  • DOI: 10.1021/ic034110t

Quantized antiferromagnetic spin waves in the molecular Heisenberg ring CsFe 8
journal, January 2010


The new cold neutron chopper spectrometer at the Spallation Neutron Source: Design and performance
journal, August 2011

  • Ehlers, G.; Podlesnyak, A. A.; Niedziela, J. L.
  • Review of Scientific Instruments, Vol. 82, Issue 8
  • DOI: 10.1063/1.3626935

On the preparation of metalloporphyrins
journal, July 1970

  • Adler, Alan D.; Longo, Frederick R.; Kampas, Frank
  • Journal of Inorganic and Nuclear Chemistry, Vol. 32, Issue 7
  • DOI: 10.1016/0022-1902(70)80535-8

Intermolecular Interactions in Solid-State Metalloporphyrins and Their Impacts on Crystal and Molecular Structures
journal, October 2014

  • Hunter, Seth C.; Smith, Brenda A.; Hoffmann, Christina M.
  • Inorganic Chemistry, Vol. 53, Issue 21
  • DOI: 10.1021/ic5015835

Preparation and molecular stereochemistry of fluoro(meso-tetraphenylporphinato)iron(III)
journal, July 1981

  • Anzai, Kazunori; Hatano, Keiichiro; Lee, Young Ja
  • Inorganic Chemistry, Vol. 20, Issue 7
  • DOI: 10.1021/ic50221a079

Monte Carlo indexing with McMaille
journal, September 2004


Crystal structure of Bromo(tetraphenylporphyrin)iron(III)
journal, January 1977

  • Skelton, Bw; White, Ah
  • Australian Journal of Chemistry, Vol. 30, Issue 12
  • DOI: 10.1071/CH9772655

An unusual methylene aziridine refined in P 2 1 / c and the nonstandard setting P 2 1 / n
journal, November 2009

  • Feast, George C.; Haestier, James; Page, Lee W.
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 65, Issue 12
  • DOI: 10.1107/S0108270109046952

Molecular stereochemistry of iodo(meso-tetraphenylporphinato)iron(III)
journal, March 1979

  • Hatano, K.; Scheidt, W. Robert
  • Inorganic Chemistry, Vol. 18, Issue 3
  • DOI: 10.1021/ic50193a073

Molecular Spin Clusters: New Synthetic Approaches and Neutron Scattering Studies
journal, September 2003

  • Basler, Reto; Boskovic, Colette; Chaboussant, Grégory
  • ChemPhysChem, Vol. 4, Issue 9
  • DOI: 10.1002/cphc.200300689

DAVE: A Comprehensive Software Suite for the Reduction, Visualization, and Analysis of Low Energy Neutron Spectroscopic Data
journal, November 2009

  • Azuah, Richard Tumanjong; Kneller, Larry R.; Qiu, Yiming
  • Journal of Research of the National Institute of Standards and Technology, Vol. 114, Issue 6
  • DOI: 10.6028/jres.114.025

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Effect of the damping function in dispersion corrected density functional theory
journal, March 2011

  • Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars
  • Journal of Computational Chemistry, Vol. 32, Issue 7
  • DOI: 10.1002/jcc.21759

All-Electron Scalar Relativistic Basis Sets for Third-Row Transition Metal Atoms
journal, May 2008

  • Pantazis, Dimitrios A.; Chen, Xian-Yang; Landis, Clark R.
  • Journal of Chemical Theory and Computation, Vol. 4, Issue 6
  • DOI: 10.1021/ct800047t

The CASSCF state interaction method
journal, February 1989


N-electron valence state perturbation theory: a fast implementation of the strongly contracted variant
journal, December 2001


Introduction of n -electron valence states for multireference perturbation theory
journal, June 2001

  • Angeli, C.; Cimiraglia, R.; Evangelisti, S.
  • The Journal of Chemical Physics, Vol. 114, Issue 23
  • DOI: 10.1063/1.1361246

n -electron valence state perturbation theory: A spinless formulation and an efficient implementation of the strongly contracted and of the partially contracted variants
journal, November 2002

  • Angeli, Celestino; Cimiraglia, Renzo; Malrieu, Jean-Paul
  • The Journal of Chemical Physics, Vol. 117, Issue 20
  • DOI: 10.1063/1.1515317

A quasidegenerate formulation of the second order n-electron valence state perturbation theory approach
journal, September 2004

  • Angeli, Celestino; Borini, Stefano; Cestari, Mirko
  • The Journal of Chemical Physics, Vol. 121, Issue 9
  • DOI: 10.1063/1.1778711

Third-order multireference perturbation theory: The n-electron valence state perturbation-theory approach
journal, February 2006

  • Angeli, Celestino; Bories, Benoît; Cavallini, Alex
  • The Journal of Chemical Physics, Vol. 124, Issue 5
  • DOI: 10.1063/1.2148946

The ORCA program system: The ORCA program system
journal, June 2011

  • Neese, Frank
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1
  • DOI: 10.1002/wcms.81

Detailed Ab Initio First-Principles Study of the Magnetic Anisotropy in a Family of Trigonal Pyramidal Iron(II) Pyrrolide Complexes
journal, August 2011

  • Atanasov, Mihail; Ganyushin, Dmitry; Pantazis, Dimitrios A.
  • Inorganic Chemistry, Vol. 50, Issue 16
  • DOI: 10.1021/ic200196k

First-principles calculations of zero-field splitting parameters
journal, July 2006

  • Ganyushin, Dmitry; Neese, Frank
  • The Journal of Chemical Physics, Vol. 125, Issue 2
  • DOI: 10.1063/1.2213976

Fully optimized contracted Gaussian basis sets for atoms Li to Kr
journal, August 1992

  • Schäfer, Ansgar; Horn, Hans; Ahlrichs, Reinhart
  • The Journal of Chemical Physics, Vol. 97, Issue 4
  • DOI: 10.1063/1.463096

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

Do the ``Ligand Field'' Parameters in Lanthanides Represent Weak Covalent Bonding?
journal, September 1963

  • Jo/rgensen, Chr. Klixbüll; Pappalardo, Romano; Schmidtke, Hans‐Herbert
  • The Journal of Chemical Physics, Vol. 39, Issue 6
  • DOI: 10.1063/1.1734458

The angular overlap model, an attempt to revive the ligand field approaches
journal, January 1965


A theoretical analysis of chemical bonding, vibronic coupling, and magnetic anisotropy in linear iron( ii ) complexes with single-molecule magnet behavior
journal, January 2013

  • Atanasov, Mihail; Zadrozny, Joseph M.; Long, Jeffrey R.
  • Chem. Sci., Vol. 4, Issue 1
  • DOI: 10.1039/C2SC21394J

Hints for the Control of Magnetic Anisotropy in Molecular Materials
journal, July 2001


Calculation of spin-orbit coupling within the LFDFT: Applications to [NiX4]2? (X?F?, Cl?, Br?, I?)
journal, January 2005

  • Atanasov, Mihail; Rauzy, C�drick; Baettig, Pio
  • International Journal of Quantum Chemistry, Vol. 102, Issue 2
  • DOI: 10.1002/qua.20376

Synthesis, Characterization and Spectral Properties of Substituted Tetraphenylporphyrin Iron Chloride Complexes
journal, April 2011


    Works referencing / citing this record:

    Impact of Substituent Variation on the Presence of Thermal Spin Crossover in a Series of Mononuclear Iron(III) Schiff Base Complexes with Terminal Pseudohalido Co-ligands
    journal, December 2017

    • Pogány, Lukáš; Brachňaková, Barbora; Moncol, Ján
    • Chemistry - A European Journal, Vol. 24, Issue 20
    • DOI: 10.1002/chem.201704546

    Probing Magnetic Excitations in Co II Single-Molecule Magnets by Inelastic Neutron Scattering: Probing Magnetic Excitations in Co II Single-Molecule Magnets by Inelastic Neutron Scattering
    journal, December 2018

    • Stavretis, Shelby E.; Cheng, Yongqiang; Daemen, Luke L.
    • European Journal of Inorganic Chemistry, Vol. 2019, Issue 8
    • DOI: 10.1002/ejic.201801088

    Neutron Instruments for Research in Coordination Chemistry: Neutron Instruments for Research in Coordination Chemistry
    journal, January 2019

    • Xue, Zi-Ling; Ramirez-Cuesta, Anibal J.; Brown, Craig M.
    • European Journal of Inorganic Chemistry, Vol. 2019, Issue 8
    • DOI: 10.1002/ejic.201801076

    Spin–phonon couplings in transition metal complexes with slow magnetic relaxation
    journal, July 2018

    • Moseley, Duncan H.; Stavretis, Shelby E.; Thirunavukkuarasu, Komalavalli
    • Nature Communications, Vol. 9, Issue 1
    • DOI: 10.1038/s41467-018-04896-0

    Iron doped gold cluster nanomagnets: ab initio determination of barriers for demagnetization
    journal, January 2019

    • Ehlert, Christopher; Hamilton, Ian P.
    • Nanoscale Advances, Vol. 1, Issue 4
    • DOI: 10.1039/c8na00359a

    Sandwich double-decker Er( iii ) and Yb( iii ) complexes containing naphthalocyanine moiety: synthesis and investigation of the effect of a paramagnetic metal center
    journal, January 2019

    • Dubinina, Tatiana V.; Kosov, Anton D.; Petrusevich, Elizaveta F.
    • Dalton Transactions, Vol. 48, Issue 35
    • DOI: 10.1039/c9dt03226f

    Structural and magnetic properties of heptacoordinated Mn II complexes containing a 15-membered pyridine-based macrocycle and halido/pseudohalido axial coligands
    journal, January 2016

    • Drahoš, Bohuslav; Herchel, Radovan; Trávníček, Zdeněk
    • RSC Advances, Vol. 6, Issue 41
    • DOI: 10.1039/c6ra03754b

    Spectroscopic Studies of the Magnetic Excitation and Spin‐Phonon Couplings in a Single‐Molecule Magnet
    journal, November 2019

    • Stavretis, Shelby E.; Moseley, Duncan H.; Fei, Fan
    • Chemistry – A European Journal, Vol. 25, Issue 69
    • DOI: 10.1002/chem.201903635

    Force detection of high-frequency electron paramagnetic resonance spectroscopy of microliter solution sample
    journal, November 2018

    • Okamoto, Tsubasa; Takahashi, Hideyuki; Ohmichi, Eiji
    • Applied Physics Letters, Vol. 113, Issue 22
    • DOI: 10.1063/1.5055743

    Rationalization of single-molecule magnet behavior in a three-coordinate Fe( iii ) complex with a high-spin state ( S = 5/2)
    journal, January 2018

    • Ge, Ning; Zhai, Yuan-Qi; Deng, Yi-Fei
    • Inorganic Chemistry Frontiers, Vol. 5, Issue 10
    • DOI: 10.1039/c8qi00701b

    Probing Magnetic Excitations in Co II Single-Molecule Magnets by Inelastic Neutron Scattering
    journal, February 2019

    • Stavretis, Shelby E.; Cheng, Yongqiang; Daemen, Luke L.
    • European Journal of Inorganic Chemistry, Vol. 2019, Issue 8
    • DOI: 10.1002/ejic.201900142