Near‐Room‐Temperature Magnetoelectric Coupling via Spin Crossover in an Iron(II) Complex

Owczarek, Magdalena; Lee, Minseong; Liu, Shuanglong; Blake, Ella R.; Taylor, Chloe S.; Newman, Georgia A.; Eckert, James C.; Leal, Juan H.; Semelsberger, Troy A.; Cheng, Hai‐Ping; Nie, Wanyi; Zapf, Vivien S.

doi:10.1002/anie.202214335

Title: Near‐Room‐Temperature Magnetoelectric Coupling via Spin Crossover in an Iron(II) Complex

Journal Article · 22 November 2022 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202214335 · OSTI ID:1899735

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Center for Integrated Nanotechnologies Los Alamos National Laboratory Los Alamos NM 87545 USA
National High Magnetic Field Laboratory Los Alamos National Laboratory Los Alamos NM 87545 USA
Department of Physics Quantum Theory Project Center for Molecular Magnetic Quantum Materials University of Florida Gainesville FL 32611 USA
Harvey Mudd College Claremont CA 91711 USA
Materials Physics and Applications Division Los Alamos National Laboratory Los Alamos NM 87545 USA

Abstract Magnetoelectric coupling is achieved near room temperature in a spin crossover Fe ^II molecule‐based compound, [Fe(1bpp) ₂ ](BF ₄ ) ₂ . Large atomic displacements resulting from Jahn–Teller distortions induce a change in the molecule dipole moment when switching between high‐spin and low‐spin states leading to a step‐wise change in the electric polarization and dielectric constant. For temperatures in the region of bistability, the changes in magnetic and electrical properties are induced with a remarkably low magnetic field of 3 T. This result represents a successful expansion of magnetoelectric spin crossovers towards ambient conditions. Moreover, the observed 0.3–0.4 mC m ⁻² changes in the H ‐induced electric polarization suggest that the high strength of the coupling obtained via this route is accessible not just at cryogenic temperatures but also near room temperature, a feature that is especially appealing in the light of practical applications.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC)

Grant/Contract Number:: 89233218CNA000001; SC0019330

OSTI ID:: 1899735

Report Number(s):: LA-UR-22-31219; LA-UR-23-32830; e202214335

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 52 Vol. 61; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (41)

Spin‐Crossover Materials Halcrow, Malcolm A. https://doi.org/10.1002/9781118519301	book	January 2013
Giant Barocaloric Effect at the Spin Crossover Transition of a Molecular Crystal Vallone, Steven P.; Tantillo, Anthony N.; dos Santos, António M. Advanced Materials, Vol. 31, Issue 23 https://doi.org/10.1002/adma.201807334	journal	March 2019
Stress‐Induced Domain Wall Motion in a Ferroelastic Mn ³⁺ Spin Crossover Complex Jakobsen, Vibe B.; Trzop, Elzbieta; Gavin, Laurence C. Angewandte Chemie, Vol. 132, Issue 32 https://doi.org/10.1002/ange.202003041	journal	June 2020
Thermal and Magnetic Field Switching in a Two‐Step Hysteretic Mn^III Spin Crossover Compound Coupled to Symmetry Breakings Dobbelaar, Emiel; Jakobsen, Vibe B.; Trzop, Elzbieta Angewandte Chemie, Vol. 134, Issue 4 https://doi.org/10.1002/ange.202114021	journal	December 2021
Photoinduced Persistent Polarization Change in a Spin Transition Crystal Su, Sheng‐Qun; Wu, Shu‐Qi; Huang, Yu‐Bo Angewandte Chemie, Vol. 134, Issue 39 https://doi.org/10.1002/ange.202208771	journal	August 2022
Stress‐Induced Domain Wall Motion in a Ferroelastic Mn ³⁺ Spin Crossover Complex Jakobsen, Vibe B.; Trzop, Elzbieta; Gavin, Laurence C. Angewandte Chemie International Edition, Vol. 59, Issue 32 https://doi.org/10.1002/anie.202003041	journal	June 2020
Thermal and Magnetic Field Switching in a Two‐Step Hysteretic Mn ^III Spin Crossover Compound Coupled to Symmetry Breakings Dobbelaar, Emiel; Jakobsen, Vibe B.; Trzop, Elzbieta Angewandte Chemie International Edition, Vol. 61, Issue 4 https://doi.org/10.1002/anie.202114021	journal	December 2021
Photoinduced Persistent Polarization Change in a Spin Transition Crystal Su, Sheng‐Qun; Wu, Shu‐Qi; Huang, Yu‐Bo Angewandte Chemie International Edition, Vol. 61, Issue 39 https://doi.org/10.1002/anie.202208771	journal	August 2022
Molecular Switchable Solids: towards photo-controlled magnetism Varret, François; Boukheddaden, Kamel; Codjovi, Epiphane ICAME 2005 https://doi.org/10.1007/978-3-540-49850-6_5	book	October 2006
Spin Crossover in Transition Metal Compounds III Gütlich, P.; Goodwin, H. A. Topics in Current Chemistry https://doi.org/10.1007/b96439	book	January 2004
The effect of a magnetic field on the high-spin α low-spin transition in [Fe(phen)2(NCS)2] Qi, Y.; Müller, E. W.; Spiering, H. Chemical Physics Letters, Vol. 101, Issue 4-5 https://doi.org/10.1016/0009-2614(83)87521-6	journal	October 1983
A photomagnetic study of three iron(II) compounds containing ligands from the 2,6-di(pyrazol-1-yl)pyridine series Money, Victoria A.; Costa, José Sánchez; Marcén, Sylvia Chemical Physics Letters, Vol. 391, Issue 4-6 https://doi.org/10.1016/j.cplett.2004.05.020	journal	June 2004
Unidirectional electric field-induced spin-state switching in spin crossover based microelectronic devices Lefter, Constantin; Tan, Reasmey; Dugay, Julien Chemical Physics Letters, Vol. 644 https://doi.org/10.1016/j.cplett.2015.11.036	journal	January 2016
Magnetoelectrics for magnetic sensor applications: status, challenges and perspectives Wang, Yaojin; Li, Jiefang; Viehland, D. Materials Today, Vol. 17, Issue 6 https://doi.org/10.1016/j.mattod.2014.05.004	journal	July 2014
Characteristics of organic light-emitting devices consisting of dye-doped spin crossover complex films Matsuda, Masaki; Kiyoshima, Keita; Uchida, Ryoma Thin Solid Films, Vol. 531 https://doi.org/10.1016/j.tsf.2013.01.094	journal	March 2013
Giant Magnetoelectric Coupling and Magnetic-Field-Induced Permanent Switching in a Spin Crossover Mn(III) Complex Jakobsen, Vibe B.; Chikara, Shalinee; Yu, Jie-Xiang Inorganic Chemistry, Vol. 60, Issue 9 https://doi.org/10.1021/acs.inorgchem.0c02789	journal	December 2020
First manganese(III) spin crossover, first d4 crossover. Comment on cytochrome oxidase Sim, P. Greig; Sinn, Ekk Journal of the American Chemical Society, Vol. 103, Issue 1 https://doi.org/10.1021/ja00391a067	journal	January 1981
Precise Control and Consecutive Modulation of Spin Transition Temperature Using Chemical Migration in Porous Coordination Polymers Ohtani, Ryo; Yoneda, Ko; Furukawa, Shuhei Journal of the American Chemical Society, Vol. 133, Issue 22 https://doi.org/10.1021/ja111674c	journal	June 2011
Dynamic Interplay between Spin-Crossover and Host−Guest Function in a Nanoporous Metal−Organic Framework Material Southon, Peter D.; Liu, Lang; Fellows, Elizabeth A. Journal of the American Chemical Society, Vol. 131, Issue 31 https://doi.org/10.1021/ja902187d	journal	August 2009
Domain Wall Dynamics in a Ferroelastic Spin Crossover Complex with Giant Magnetoelectric Coupling Jakobsen, Vibe Boel; Trzop, Elzbieta; Dobbelaar, Emiel Journal of the American Chemical Society, Vol. 144, Issue 1 https://doi.org/10.1021/jacs.1c08214	journal	December 2021
Tracking excited-state charge and spin dynamics in iron coordination complexes Zhang, Wenkai; Alonso-Mori, Roberto; Bergmann, Uwe Nature, Vol. 509, Issue 7500 https://doi.org/10.1038/nature13252	journal	May 2014
Towards a magnetoelectric memory Bibes, Manuel; Barthélémy, Agnès Nature Materials, Vol. 7, Issue 6 https://doi.org/10.1038/nmat2189	journal	June 2008
Magnetoelectric behavior via a spin state transition Chikara, Shalinee; Gu, Jie; Zhang, X. -G. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-11967-3	journal	September 2019
Synergetic effect between spin crossover and luminescence in the [Fe(bpp)2][BF4]2 (bpp = 2,6-bis(pyrazol-1-yl)pyridine) complex Jiao, Yang; Zhu, Jianping; Guo, Yan J. Mater. Chem. C, Vol. 5, Issue 21 https://doi.org/10.1039/C7TC00507E	journal	January 2017
An unusual abrupt thermal spin-state transition in [FeL2][BF4]2 [L = 2,6-di(pyrazol-1-yl)pyridine] Holland, Joanne M.; Kilner, Colin A.; Thornton-Pett, Mark Chemical Communications, Issue 6 https://doi.org/10.1039/b100995h	journal	January 2001
Light induced excited high spin-state trapping in [FeL2](BF4)2 (L = 2,6-di(pyrazol-1-yl)pyridine) Money, Victoria A.; Radosavljevic Evans, Ivana; Halcrow, Malcolm A. Chemical Communications, Issue 1 https://doi.org/10.1039/b210146g	journal	December 2002
Thermal, pressure and light switchable spin-crossover materials Real, José Antonio; Gaspar, Ana Belén; Muñoz, M. Carmen Dalton Transactions, Issue 12 https://doi.org/10.1039/b501491c	journal	January 2005
Applications of magnetoelectrics Scott, J. F. Journal of Materials Chemistry, Vol. 22, Issue 11 https://doi.org/10.1039/c2jm16137k	journal	January 2012
The spin state of a molecular adsorbate driven by the ferroelectric substrate polarization Zhang, Xin; Palamarciuc, Tatiana; Létard, Jean-François Chemical Communications, Vol. 50, Issue 18 https://doi.org/10.1039/c3cc46892e	journal	January 2014
Electric field control of magnetism using BiFeO ₃ -based heterostructures Heron, J. T.; Schlom, D. G.; Ramesh, R. Applied Physics Reviews, Vol. 1, Issue 2 https://doi.org/10.1063/1.4870957	journal	June 2014
Magnetocapacitance effect and magnetostriction by the field-induced spin-crossover in [Mn ^III (taa)] Otsuki, Y.; Kimura, S.; Awaji, S. AIP Advances, Vol. 9, Issue 8 https://doi.org/10.1063/1.5097891	journal	August 2019
Opportunities and challenges for magnetoelectric devices Hu, Jia-Mian; Nan, Ce-Wen APL Materials, Vol. 7, Issue 8 https://doi.org/10.1063/1.5112089	journal	August 2019
Magnetoelectronics with magnetoelectrics Binek, Ch; Doudin, B. Journal of Physics: Condensed Matter, Vol. 17, Issue 2 https://doi.org/10.1088/0953-8984/17/2/L06	journal	January 2005
Evolving magneto-electric device technologies Sharma, N.; Bird, J. P.; Binek, Ch Semiconductor Science and Technology, Vol. 35, Issue 7 https://doi.org/10.1088/1361-6641/ab8438	journal	June 2020
Dielectric behavior of manganese(III) spin-crossover complex [Mn(taa)] Nakano, Motohiro; Matsubayashi, Gen-etsu; Matsuo, Takasuke Physical Review B, Vol. 66, Issue 21 https://doi.org/10.1103/PhysRevB.66.212412	journal	December 2002
An Expanded Benchmarking of Beyond-CMOS Devices Based on Boolean and Neuromorphic Representative Circuits Pan, Chenyun; Naeemi, Azad IEEE Journal on Exploratory Solid-State Computational Devices and Circuits, Vol. 3 https://doi.org/10.1109/JXCDC.2018.2793536	journal	December 2017
Guest-Dependent Spin Crossover in a Nanoporous Molecular Framework Material Halder, G. J. Science, Vol. 298, Issue 5599 https://doi.org/10.1126/science.1075948	journal	November 2002
Voltage Control of Magnetism in Multiferroic Heterostructures and Devices Sun, Nian X.; Srinivasan, Gopalan SPIN, Vol. 02, Issue 03 https://doi.org/10.1142/S2010324712400048	journal	September 2012
Investigation of nucleation and growth phenomena during the thermal and light induced spin transition in the [Fe(1-bpp)₂][BF₄]₂ complex Rat, Sylvain; Sánchez Costa, José; Bedoui, Salma Pure and Applied Chemistry, Vol. 87, Issue 3 https://doi.org/10.1515/pac-2014-1002	journal	January 2015
Strain-mediated magnetoelectrics: Turning science fiction into reality Carman, Greg P.; Sun, Nian MRS Bulletin, Vol. 43, Issue 11 https://doi.org/10.1557/mrs.2018.236	journal	November 2018
Spin state switching in iron coordination compounds Gütlich, Philipp; Gaspar, Ana B.; Garcia, Yann Beilstein Journal of Organic Chemistry, Vol. 9 https://doi.org/10.3762/bjoc.9.39	journal	January 2013

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