Formation of the layered conductive magnet CrCl2(pyrazine)2 through redox-active coordination chemistry [A non-innocent coordination chemistry approach to 2D conductive magnets]
Abstract
The unique properties of graphene, transition-metal dichalcogenides and other two-dimensional (2D) materials have boosted interest in layered coordination solids. In particular, 2D materials that behave as both conductors and magnets could find applications in quantum magnetoelectronics and spintronics. Here, we report the synthesis of CrCl2(pyrazine)2, an air-stable layered solid, by reaction of CrCl2 with pyrazine (pyz). This compound displays a ferrimagnetic order below ~55 K, reflecting the presence of strong magnetic interactions. Electrical conductivity measurements demonstrate that CrCl2(pyz)2 reaches a conductivity of 32 mS cm-1 at room temperature, which operates through a 2D hopping-based transport mechanism. These properties are induced by the redox-activity of the pyrazine ligand, which leads to a smearing of the Cr 3d and pyrazine π states. We suggest that the combination of redox-active ligands and reducing paramagnetic metal ions represents a general approach towards tuneable 2D materials that consist of charge-neutral layers and exhibit both long-range magnetic order and high electronic conductivity.
- Authors:
-
- CNRS, Pessac (France); Univ. Bordeaux, Pessac (France); Technical Univ. of Denmark, Lyngby (Denmark)
- CNRS, Pessac (France); Univ. Bordeaux, Pessac (France)
- Univ. of California, Berkeley, CA (United States)
- Univ. of Oxford, Oxford (United Kingdom)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Univ.Andres Bello, Santiago (Chile)
- Univ. of Copenhagen, Copenhagen (Denmark)
- Technical Univ. of Denmark, Lyngby (Denmark)
- Aarhus Univ., Aarhus (Denmark)
- CNRS, Pessac (France); Univ. Bordeaux, Pessac (France); Sara Pharm Solutions, Bucharest (Romania)
- ESRF – The European Synchrotron, Grenoble (France)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Kavli Energy Nanosciences Inst. at Berkeley, Berkeley, CA (United States)
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
- OSTI Identifier:
- 1560564
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Chemistry
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 10; Journal ID: ISSN 1755-4330
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Pedersen, Kasper S., Perlepe, Panagiota, Aubrey, Michael L., Woodruff, Daniel N., Reyes-Lillo, Sebastian E., Reinholdt, Anders, Voigt, Laura, Li, Zheshen, Borup, Kasper, Rouzières, Mathieu, Samohvalov, Dumitru, Wilhelm, Fabrice, Rogalev, Andrei, Neaton, Jeffrey B., Long, Jeffrey R., and Clérac, Rodolphe. Formation of the layered conductive magnet CrCl2(pyrazine)2 through redox-active coordination chemistry [A non-innocent coordination chemistry approach to 2D conductive magnets]. United States: N. p., 2018.
Web. doi:10.1038/s41557-018-0107-7.
Pedersen, Kasper S., Perlepe, Panagiota, Aubrey, Michael L., Woodruff, Daniel N., Reyes-Lillo, Sebastian E., Reinholdt, Anders, Voigt, Laura, Li, Zheshen, Borup, Kasper, Rouzières, Mathieu, Samohvalov, Dumitru, Wilhelm, Fabrice, Rogalev, Andrei, Neaton, Jeffrey B., Long, Jeffrey R., & Clérac, Rodolphe. Formation of the layered conductive magnet CrCl2(pyrazine)2 through redox-active coordination chemistry [A non-innocent coordination chemistry approach to 2D conductive magnets]. United States. https://doi.org/10.1038/s41557-018-0107-7
Pedersen, Kasper S., Perlepe, Panagiota, Aubrey, Michael L., Woodruff, Daniel N., Reyes-Lillo, Sebastian E., Reinholdt, Anders, Voigt, Laura, Li, Zheshen, Borup, Kasper, Rouzières, Mathieu, Samohvalov, Dumitru, Wilhelm, Fabrice, Rogalev, Andrei, Neaton, Jeffrey B., Long, Jeffrey R., and Clérac, Rodolphe. Mon .
"Formation of the layered conductive magnet CrCl2(pyrazine)2 through redox-active coordination chemistry [A non-innocent coordination chemistry approach to 2D conductive magnets]". United States. https://doi.org/10.1038/s41557-018-0107-7. https://www.osti.gov/servlets/purl/1560564.
@article{osti_1560564,
title = {Formation of the layered conductive magnet CrCl2(pyrazine)2 through redox-active coordination chemistry [A non-innocent coordination chemistry approach to 2D conductive magnets]},
author = {Pedersen, Kasper S. and Perlepe, Panagiota and Aubrey, Michael L. and Woodruff, Daniel N. and Reyes-Lillo, Sebastian E. and Reinholdt, Anders and Voigt, Laura and Li, Zheshen and Borup, Kasper and Rouzières, Mathieu and Samohvalov, Dumitru and Wilhelm, Fabrice and Rogalev, Andrei and Neaton, Jeffrey B. and Long, Jeffrey R. and Clérac, Rodolphe},
abstractNote = {The unique properties of graphene, transition-metal dichalcogenides and other two-dimensional (2D) materials have boosted interest in layered coordination solids. In particular, 2D materials that behave as both conductors and magnets could find applications in quantum magnetoelectronics and spintronics. Here, we report the synthesis of CrCl2(pyrazine)2, an air-stable layered solid, by reaction of CrCl2 with pyrazine (pyz). This compound displays a ferrimagnetic order below ~55 K, reflecting the presence of strong magnetic interactions. Electrical conductivity measurements demonstrate that CrCl2(pyz)2 reaches a conductivity of 32 mS cm-1 at room temperature, which operates through a 2D hopping-based transport mechanism. These properties are induced by the redox-activity of the pyrazine ligand, which leads to a smearing of the Cr 3d and pyrazine π states. We suggest that the combination of redox-active ligands and reducing paramagnetic metal ions represents a general approach towards tuneable 2D materials that consist of charge-neutral layers and exhibit both long-range magnetic order and high electronic conductivity.},
doi = {10.1038/s41557-018-0107-7},
journal = {Nature Chemistry},
number = 10,
volume = 10,
place = {United States},
year = {Mon Sep 10 00:00:00 EDT 2018},
month = {Mon Sep 10 00:00:00 EDT 2018}
}
Web of Science
Works referenced in this record:
Stabilizing and color tuning pyrazine radicals by coordination for photochromism
journal, January 2016
- Zhang, Xian; Wang, Ming-Sheng; Sun, Cai
- Chemical Communications, Vol. 52, Issue 51
Graphene spintronics
journal, October 2014
- Han, Wei; Kawakami, Roland K.; Gmitra, Martin
- Nature Nanotechnology, Vol. 9, Issue 10
Rhenium-Based Molecular Rectangles as Frameworks for Ligand-Centered Mixed Valency and Optical Electron Transfer
journal, October 2004
- Dinolfo, Peter H.; Williams, Mary Elizabeth; Stern, Charlotte L.
- Journal of the American Chemical Society, Vol. 126, Issue 40
Experimental and theoretical study of a paradigm Jahn-Teller molecule, all-trans-CrCl2(H2O)2(pyridine)2, and the related trans-CrCl2(pyridine)4·acetone
journal, July 1995
- Cotton, F. Albert; Daniels, Lee M.; Feng, Xuejun
- Inorganica Chimica Acta, Vol. 235, Issue 1-2
Giant Zeeman splitting in nucleation-controlled doped CdSe:Mn2+ quantum nanoribbons
journal, November 2009
- Yu, Jung Ho; Liu, Xinyu; Kweon, Kyoung Eun
- Nature Materials, Vol. 9, Issue 1
Infrared transmission of heavily doped polyacetylene
journal, January 1983
- Benoit, C.; Bernard, O.; Palpacuer, M.
- Journal de Physique, Vol. 44, Issue 11
High Electrical Conductivity in Ni 3 (2,3,6,7,10,11-hexaiminotriphenylene) 2 , a Semiconducting Metal–Organic Graphene Analogue
journal, April 2014
- Sheberla, Dennis; Sun, Lei; Blood-Forsythe, Martin A.
- Journal of the American Chemical Society, Vol. 136, Issue 25
Scrutinizing Low-Spin Cr(II) Complexes
journal, June 2012
- Scarborough, Christopher C.; Sproules, Stephen; Doonan, Christian J.
- Inorganic Chemistry, Vol. 51, Issue 12
2D materials and van der Waals heterostructures
journal, July 2016
- Novoselov, K. S.; Mishchenko, A.; Carvalho, A.
- Science, Vol. 353, Issue 6298
2D Conductive Iron-Quinoid Magnets Ordering up to T c = 105 K via Heterogenous Redox Chemistry
journal, March 2017
- DeGayner, Jordan A.; Jeon, Ie-Rang; Sun, Lei
- Journal of the American Chemical Society, Vol. 139, Issue 11
Effect of covalent bonding on magnetism and the missing neutron intensity in copper oxide compounds
journal, October 2009
- Walters, Andrew C.; Perring, Toby G.; Caux, Jean-Sébastien
- Nature Physics, Vol. 5, Issue 12
Superexchange Coupling and Spin Susceptibility Spectral Weight in Undoped Monolayer Cuprates
journal, December 1997
- Bourges, P.; Casalta, H.; Ivanov, A. S.
- Physical Review Letters, Vol. 79, Issue 24
Coexistence of ferromagnetism and metallic conductivity in a molecule-based layered compound
journal, November 2000
- Coronado, Eugenio; Galán-Mascarós, José R.; Gómez-García, Carlos J.
- Nature, Vol. 408, Issue 6811
Organic Conductors: From Charge Density Wave TTF−TCNQ to Superconducting (TMTSF) 2 PF 6
journal, November 2004
- Jérome, Denis
- Chemical Reviews, Vol. 104, Issue 11
Introduction: Molecular Conductors
journal, November 2004
- Batail, Patrick
- Chemical Reviews, Vol. 104, Issue 11
Electric Field Effect in Atomically Thin Carbon Films
journal, October 2004
- Novoselov, K. S.
- Science, Vol. 306, Issue 5696, p. 666-669
A completely suppressed jahn-teller effect in the structure of hexaaquachromium(II) hexafluorosilicate
journal, January 1992
- Cotton, F. Albert; Falvello, Larry R.; Murillo, Carlos A.
- Journal of Solid State Chemistry, Vol. 96, Issue 1
Layer-dependent ferromagnetism in a van der Waals crystal down to the monolayer limit
journal, June 2017
- Huang, Bevin; Clark, Genevieve; Navarro-Moratalla, Efrén
- Nature, Vol. 546, Issue 7657
Magnetic Molecular Conductors
journal, November 2004
- Coronado, Eugenio; Day, Peter
- Chemical Reviews, Vol. 104, Issue 11
Electronic Conductivity, Ferrimagnetic Ordering, and Reductive Insertion Mediated by Organic Mixed-Valence in a Ferric Semiquinoid Metal–Organic Framework
journal, December 2015
- Darago, Lucy E.; Aubrey, Michael L.; Yu, Chung Jui
- Journal of the American Chemical Society, Vol. 137, Issue 50
A two-dimensional π–d conjugated coordination polymer with extremely high electrical conductivity and ambipolar transport behaviour
journal, June 2015
- Huang, Xing; Sheng, Peng; Tu, Zeyi
- Nature Communications, Vol. 6, Issue 1
Crystal Structure and Physical Properties of Conducting Molecular Antiferromagnets with a Halogen-Substituted Donor: (EDO-TTFBr 2 ) 2 FeX 4 (X = Cl, Br)
journal, April 2007
- Miyazaki, A.; Yamazaki, H.; Aimatsu, M.
- Inorganic Chemistry, Vol. 46, Issue 8
Magnetically ordered molecule-based materials
journal, January 2011
- Miller, Joel S.
- Chemical Society Reviews, Vol. 40, Issue 6
The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets
journal, April 2013
- Chhowalla, Manish; Shin, Hyeon Suk; Eda, Goki
- Nature Chemistry, Vol. 5, Issue 4, p. 263-275
Signature of Metallic Behavior in the Metal–Organic Frameworks M 3 (hexaiminobenzene) 2 (M = Ni, Cu)
journal, September 2017
- Dou, Jin-Hu; Sun, Lei; Ge, Yicong
- Journal of the American Chemical Society, Vol. 139, Issue 39
Kinetic and thermodynamic properties of chromium(III) complexes containing pyrazine radical ligands
journal, May 1980
- Dunne, Thomas G.; Hurst, James K.
- Inorganic Chemistry, Vol. 19, Issue 5
Electrochemistry of the intensely green complexes formed by the reaction of chromium(2+) with pyrazine ("pyrazine green"), pyrazinecarboxamide, and pyrazinecarboxylic acid
journal, July 1981
- Swartz, James.; Anson, Fred C.
- Inorganic Chemistry, Vol. 20, Issue 7
Origin of orbital magnetization and magnetocrystalline anisotropy in TX ordered alloys (where T =Fe,Co and X =Pd,Pt)
journal, November 1995
- Solovyev, I. V.; Dederichs, P. H.; Mertig, I.
- Physical Review B, Vol. 52, Issue 18
Radical Ligands Confer Nobility on Base-Metal Catalysts
journal, February 2010
- Chirik, P. J.; Wieghardt, K.
- Science, Vol. 327, Issue 5967
Unraveling the Semiconducting/Metallic Discrepancy in Ni 3 (HITP) 2
journal, January 2018
- Foster, Michael E.; Sohlberg, Karl; Allendorf, Mark D.
- The Journal of Physical Chemistry Letters, Vol. 9, Issue 3
MasterChem: cooking 2D-polymers
journal, January 2016
- Rodríguez-San-Miguel, D.; Amo-Ochoa, P.; Zamora, F.
- Chemical Communications, Vol. 52, Issue 22
Reticular synthesis and the design of new materials
journal, June 2003
- Yaghi, Omar M.; O'Keeffe, Michael; Ockwig, Nathan W.
- Nature, Vol. 423, Issue 6941, p. 705-714
Ligand K-Edge X-ray Absorption Spectroscopy: A Direct Probe of Ligand−Metal Covalency
journal, December 2000
- Glaser, Thorsten; Hedman, Britt; Hodgson, Keith O.
- Accounts of Chemical Research, Vol. 33, Issue 12
Zener Model Description of Ferromagnetism in Zinc-Blende Magnetic Semiconductors
journal, February 2000
- Dietl, T.
- Science, Vol. 287, Issue 5455
Mixed Valency in a 3D Semiconducting Iron–Fluoranilate Coordination Polymer
journal, July 2017
- Murase, Ryuichi; Abrahams, Brendan F.; D’Alessandro, Deanna M.
- Inorganic Chemistry, Vol. 56, Issue 15
π-Conjugated Nickel Bis(dithiolene) Complex Nanosheet
journal, February 2013
- Kambe, Tetsuya; Sakamoto, Ryota; Hoshiko, Ken
- Journal of the American Chemical Society, Vol. 135, Issue 7
Mechanical and optical properties of ultralarge flakes of a metal–organic framework with molecular thickness
journal, January 2015
- Hermosa, Cristina; Horrocks, Benjamin R.; Martínez, José I.
- Chemical Science, Vol. 6, Issue 4
Polarons, bipolarons, and solitons in conducting polymers
journal, October 1985
- Bredas, Jean Luc; Street, G. Bryan
- Accounts of Chemical Research, Vol. 18, Issue 10
Magnetic Ordering-Induced Multiferroic Behavior in [CH 3 NH 3 ][Co(HCOO) 3 ] Metal–Organic Framework
journal, January 2016
- Gómez-Aguirre, L. Claudia; Pato-Doldán, Breogán; Mira, J.
- Journal of the American Chemical Society, Vol. 138, Issue 4
Non-innocent ligands in bioinorganic chemistry—An overview
journal, July 2010
- Kaim, Wolfgang; Schwederski, Brigitte
- Coordination Chemistry Reviews, Vol. 254, Issue 13-14
Observation of Resonant Quantum Magnetoelectric Effect in a Multiferroic Metal–Organic Framework
journal, January 2016
- Tian, Ying; Shen, Shipeng; Cong, Junzhuang
- Journal of the American Chemical Society, Vol. 138, Issue 3
Coordination Programming of Two-Dimensional Metal Complex Frameworks
journal, March 2016
- Maeda, Hiroaki; Sakamoto, Ryota; Nishihara, Hiroshi
- Langmuir, Vol. 32, Issue 11
Multielectron excitations probed by helicity-modulation XMCD at K -edge in 3 d transition metal compounds
journal, March 2001
- Kawamura, Naomi; Yamamoto, Tatsuya; Maruyama, Hiroshi
- Journal of Synchrotron Radiation, Vol. 8, Issue 2
Electrically Conductive Porous Metal-Organic Frameworks
journal, January 2016
- Sun, Lei; Campbell, Michael G.; Dincă, Mircea
- Angewandte Chemie International Edition, Vol. 55, Issue 11
Organic Conductors: From Charge Density Wave TTF?TCNQ to Superconducting (TMTSF)2PF6
journal, February 2005
- Jerome, Denis
- ChemInform, Vol. 36, Issue 7
Graphene spintronics
conference, August 2010
- Shiraishi, Masashi
- SPIE NanoScience + Engineering, SPIE Proceedings
Magnetically Ordered Molecule-Based Materials
journal, July 2007
- Miller, Joel S.
- MRS Bulletin, Vol. 32, Issue 7
Magnetic Molecular Conductors
journal, February 2005
- Coronado, Eugenio; Day, Peter
- ChemInform, Vol. 36, Issue 7
2D materials and van der Waals heterostructures
text, January 2016
- Novoselov, K. S.; Mishchenko, A.; Carvalho, A.
- arXiv
Layer-dependent Ferromagnetism in a van der Waals Crystal down to the Monolayer Limit
text, January 2017
- Huang, Bevin; Clark, Genevieve; Navarro-Moratalla, Efren
- arXiv
Electric Field Effect in Atomically Thin Carbon Films
text, January 2004
- Novoselov, K. S.; Geim, A. K.; Morozov, S. V.
- arXiv
Superexchange coupling and spin susceptibility spectral weight in undoped monolayer cuprates
text, January 1997
- Bourges, P.; Casalta, H.; Ivanov, A. S.
- arXiv
Works referencing / citing this record:
A Phthalocyanine‐Based Layered Two‐Dimensional Conjugated Metal–Organic Framework as a Highly Efficient Electrocatalyst for the Oxygen Reduction Reaction
journal, July 2019
- Zhong, Haixia; Ly, Khoa Hoang; Wang, Mingchao
- Angewandte Chemie, Vol. 131, Issue 31
A Phthalocyanine-Based Layered Two-Dimensional Conjugated Metal-Organic Framework as a Highly Efficient Electrocatalyst for the Oxygen Reduction Reaction
journal, July 2019
- Zhong, Haixia; Ly, Khoa Hoang; Wang, Mingchao
- Angewandte Chemie International Edition, Vol. 58, Issue 31
Evidence for Non‐Innocence of a β‐Diketonate Ligand
journal, January 2020
- Vinum, Morten Gotthold; Voigt, Laura; Bell, Colby
- Chemistry – A European Journal, Vol. 26, Issue 10
A semiconducting layered metal-organic framework magnet
journal, July 2019
- Yang, Chongqing; Dong, Renhao; Wang, Mao
- Nature Communications, Vol. 10, Issue 1
Coordination assembly of 2D ordered organic metal chalcogenides with widely tunable electronic band gaps
journal, January 2020
- Li, Yanzhou; Jiang, Xiaoming; Fu, Zhihua
- Nature Communications, Vol. 11, Issue 1
Molecular magnetism: from chemical design to spin control in molecules, materials and devices
journal, October 2019
- Coronado, Eugenio
- Nature Reviews Materials
Interdigitated conducting tetrathiafulvalene-based coordination networks
journal, January 2020
- Bechu, Damien; Xie, Lilia S.; Le Breton, Nolwenn
- Chemical Communications, Vol. 56, Issue 16
Two-dimensional magnetic materials of cobalt( ii ) triangular lattices constructed by a mixed benzimidazole–dicarboxylate strategy
journal, January 2019
- Kong, Jiao-Jiao; Jiang, Yu-Xuan; Zhang, Jia-Chen
- CrystEngComm, Vol. 21, Issue 15
Syntheses, structures, magnetism and electrocatalytic oxygen evolution for four cobalt, manganese and copper complexes with dinuclear, 1D and 3D structures
journal, January 2019
- Zhong, Li; Xie, Shang-Fang; He, Jian-Qiang
- Dalton Transactions, Vol. 48, Issue 10
Slow magnetization dynamics in a six-coordinate Fe( ii )–radical complex
journal, January 2019
- Michalowicz, Carolyn A.; Mills, Michelle B.; Song, Ellen
- Dalton Transactions, Vol. 48, Issue 14
Reversible redox switching of magnetic order and electrical conductivity in a 2D manganese benzoquinoid framework
journal, January 2019
- Liu, Lujia; DeGayner, Jordan A.; Sun, Lei
- Chemical Science, Vol. 10, Issue 17
Zirconium metal–organic frameworks incorporating tetrathiafulvalene linkers: robust and redox-active matrices for in situ confinement of metal nanoparticles
journal, January 2020
- Su, Jian; Yuan, Shuai; Wang, Tao
- Chemical Science, Vol. 11, Issue 7
From 2D to 3D solids: stacking of transition metal nitroprusside layers through intermolecular physical interactions
journal, February 2020
- Avila, Y.; Osiry, H.; Torres, A. E.
- Journal of Coordination Chemistry, Vol. 73, Issue 3
2D CrCl 2 (pyrazine) 2 monolayer: high-temperature ferromagnetism and half-metallicity
journal, December 2019
- Xie, Huanhuan; Qie, Yu; Muhammad, Imran
- Journal of Physics: Condensed Matter, Vol. 32, Issue 13
Graphene and Other 2D Layered Hybrid Nanomaterial-Based Films: Synthesis, Properties, and Applications
journal, November 2018
- Cesano, Federico; Scarano, Domenica
- Coatings, Vol. 8, Issue 12
Substituted N-(Pyrazin-2-yl)benzenesulfonamides; Synthesis, Anti-Infective Evaluation, Cytotoxicity, and In Silico Studies
journal, December 2019
- Bouz, Ghada; Juhás, Martin; Pausas Otero, Lluis
- Molecules, Vol. 25, Issue 1
First principles methods using CASTEP
journal, January 2005
- Clark, Stewart J.; Segall, Matthew D.; Pickard, Chris J.
- Zeitschrift für Kristallographie - Crystalline Materials, Vol. 220, Issue 5/6
From 2D to 3D solids: stacking of transition metal nitroprusside layers through intermolecular physical interactions
text, January 2020
- Avila, Y.; Osiry, H.; Torres, A. E.
- Taylor & Francis
From 2D to 3D solids: stacking of transition metal nitroprusside layers through intermolecular physical interactions
text, January 2020
- Avila, Y.; Osiry, H.; Torres, A. E.
- Taylor & Francis
A semiconducting layered metal-organic framework magnet
journal, July 2019
- Yang, Chongqing; Dong, Renhao; Wang, Mao
- Nature Communications, Vol. 10, Issue 1