Antiferroelectric Phase Transition in a Proton-Transfer Salt of Squaric Acid and 2,3-Dimethylpyrazine

Jeff Lengyel; Xiaoping Wang; Eun Sang Choi; Tiglet Besara; Rico Schönemann; Sanath Kumar Ramakrishna; Jade Holleman; Avery L. Blockmon; Kendall D. Hughey; Tianhan Liu; Jacob Hudis; Drake Beery; Luis Balicas; Stephen A. McGill; Kenneth Hanson; Janice L. Musfeldt; Theo Siegrist; Naresh S. Dalal; Michael Shatruk

doi:10.1021/jacs.9b04473

Antiferroelectric Phase Transition in a Proton-Transfer Salt of Squaric Acid and 2,3-Dimethylpyrazine

Jeff Lengyel, Xiaoping Wang, Eun Sang Choi, Tiglet Besara, Rico Schönemann, Sanath Kumar Ramakrishna, Jade Holleman, Avery L. Blockmon, Kendall D. Hughey, Tianhan Liu, Jacob Hudis, Drake Beery, Luis Balicas, Stephen A. McGill, Kenneth Hanson, Janice L. Musfeldt, Theo Siegrist, Naresh S. Dalal, Michael Shatruk

Single Crystal Diffraction

Research output: Contribution to journal › Article › peer-review

6 Scopus citations

Abstract

A proton-transfer reaction between squaric acid (H₂sq) and 2,3-dimethylpyrazine (2,3-Me₂pyz) results in crystallization of a new organic antiferroelectric (AFE), (2,3-Me₂pyzH⁺)(Hsq^-)·H₂O (1), which possesses a layered structure. The structure of each layer can be described as partitioned into strips lined with methyl groups of the Me₂pyzH⁺ cations and strips featuring extensive hydrogen bonding between the Hsq^- anions and water molecules. Variable-temperature dielectric measurements and crystal structures determined through a combination of single-crystal X-ray and neutron diffraction reveal an AFE ordering at 104 K. The phase transition is driven by ordering of protons within the hydrogen-bonded strips. Considering the extent of proton transfer, the paraelectric (PE) state can be formulated as (2,3-Me₂pyzH⁺)₂(Hsq₂ ^3-)(H₅O₂ ⁺), whereas the AFE phase can be described as (2,3-Me₂pyzH⁺)(Hsq^-)(H₂O). The structural transition caused by the localization of protons results in the change in color from yellow in the PE state to colorless in the AFE state. The occurrence and mechanism of the AFE phase transition have been also confirmed by heat capacity measurements and variable-temperature infrared and Raman spectroscopy. This work demonstrates a potentially promising approach to the design of new electrically ordered materials by engineering molecule-based crystal structures in which hydrogen-bonding interactions are intentionally partitioned into quasi-one-dimensional regions.

Original language	English
Pages (from-to)	16279-16287
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	141
Issue number	41
DOIs	https://doi.org/10.1021/jacs.9b04473
State	Published - Oct 16 2019

Funding

We gratefully acknowledge the support of this research project by the National Science Foundation (award CHE-1464955 to M.S. and N.D.) and the Florida State University Council on Research and Creativity (planning grant to M.S. and N.D.). Single-crystal neutron diffraction experiment performed on TOPAZ used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory, under contract no. DE-AC05-00OR22725 with UT-Battelle, LLC. The dielectric and Raman measurements were performed at the National High Magnetic Field Laboratory (NHMFL), which is supported by the NSF Cooperative Agreement (DMR-1644779) and the State of Florida. L.B. is supported by the Department of Energy Basic Energy Sciences (award DE-SC0002613), and T.S. is supported by the National Science Foundation (award DMR-1606952). Research at the University of Tennessee is supported by the National Science Foundation (DMR-1707846). A.L.B. thanks the PEER program funded by the National Institute of Health (R25GM086761).

Funders	Funder number
DOE Office of Science
Florida State University Council on Research and Creativity
National Institute of Health	R25GM086761
State of Florida
National Science Foundation	CHE-1464955, DMR-1644779, 1707846
Basic Energy Sciences	DE-SC0002613, DMR-1606952
Oak Ridge National Laboratory
University of Tennessee	DMR-1707846

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Lengyel, J., Wang, X., Choi, E. S., Besara, T., Schönemann, R., Ramakrishna, S. K., Holleman, J., Blockmon, A. L., Hughey, K. D., Liu, T., Hudis, J., Beery, D., Balicas, L., McGill, S. A., Hanson, K., Musfeldt, J. L., Siegrist, T., Dalal, N. S., & Shatruk, M. (2019). Antiferroelectric Phase Transition in a Proton-Transfer Salt of Squaric Acid and 2,3-Dimethylpyrazine. Journal of the American Chemical Society, 141(41), 16279-16287. https://doi.org/10.1021/jacs.9b04473

@article{5e1b94a382b94511b15cb8fb84695557,

title = "Antiferroelectric Phase Transition in a Proton-Transfer Salt of Squaric Acid and 2,3-Dimethylpyrazine",

abstract = "A proton-transfer reaction between squaric acid (H2sq) and 2,3-dimethylpyrazine (2,3-Me2pyz) results in crystallization of a new organic antiferroelectric (AFE), (2,3-Me2pyzH+)(Hsq-)·H2O (1), which possesses a layered structure. The structure of each layer can be described as partitioned into strips lined with methyl groups of the Me2pyzH+ cations and strips featuring extensive hydrogen bonding between the Hsq- anions and water molecules. Variable-temperature dielectric measurements and crystal structures determined through a combination of single-crystal X-ray and neutron diffraction reveal an AFE ordering at 104 K. The phase transition is driven by ordering of protons within the hydrogen-bonded strips. Considering the extent of proton transfer, the paraelectric (PE) state can be formulated as (2,3-Me2pyzH+)2(Hsq2 3-)(H5O2 +), whereas the AFE phase can be described as (2,3-Me2pyzH+)(Hsq-)(H2O). The structural transition caused by the localization of protons results in the change in color from yellow in the PE state to colorless in the AFE state. The occurrence and mechanism of the AFE phase transition have been also confirmed by heat capacity measurements and variable-temperature infrared and Raman spectroscopy. This work demonstrates a potentially promising approach to the design of new electrically ordered materials by engineering molecule-based crystal structures in which hydrogen-bonding interactions are intentionally partitioned into quasi-one-dimensional regions.",

author = "Jeff Lengyel and Xiaoping Wang and Choi, {Eun Sang} and Tiglet Besara and Rico Sch{\"o}nemann and Ramakrishna, {Sanath Kumar} and Jade Holleman and Blockmon, {Avery L.} and Hughey, {Kendall D.} and Tianhan Liu and Jacob Hudis and Drake Beery and Luis Balicas and McGill, {Stephen A.} and Kenneth Hanson and Musfeldt, {Janice L.} and Theo Siegrist and Dalal, {Naresh S.} and Michael Shatruk",

note = "Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = oct,

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doi = "10.1021/jacs.9b04473",

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volume = "141",

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Lengyel, J, Wang, X, Choi, ES, Besara, T, Schönemann, R, Ramakrishna, SK, Holleman, J, Blockmon, AL, Hughey, KD, Liu, T, Hudis, J, Beery, D, Balicas, L, McGill, SA, Hanson, K, Musfeldt, JL, Siegrist, T, Dalal, NS & Shatruk, M 2019, 'Antiferroelectric Phase Transition in a Proton-Transfer Salt of Squaric Acid and 2,3-Dimethylpyrazine', Journal of the American Chemical Society, vol. 141, no. 41, pp. 16279-16287. https://doi.org/10.1021/jacs.9b04473

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T1 - Antiferroelectric Phase Transition in a Proton-Transfer Salt of Squaric Acid and 2,3-Dimethylpyrazine

AU - Lengyel, Jeff

AU - Wang, Xiaoping

AU - Choi, Eun Sang

AU - Besara, Tiglet

AU - Schönemann, Rico

AU - Ramakrishna, Sanath Kumar

AU - Holleman, Jade

AU - Blockmon, Avery L.

AU - Hughey, Kendall D.

AU - Liu, Tianhan

AU - Hudis, Jacob

AU - Beery, Drake

AU - Balicas, Luis

AU - McGill, Stephen A.

AU - Hanson, Kenneth

AU - Musfeldt, Janice L.

AU - Siegrist, Theo

AU - Dalal, Naresh S.

AU - Shatruk, Michael

PY - 2019/10/16

Y1 - 2019/10/16

N2 - A proton-transfer reaction between squaric acid (H2sq) and 2,3-dimethylpyrazine (2,3-Me2pyz) results in crystallization of a new organic antiferroelectric (AFE), (2,3-Me2pyzH+)(Hsq-)·H2O (1), which possesses a layered structure. The structure of each layer can be described as partitioned into strips lined with methyl groups of the Me2pyzH+ cations and strips featuring extensive hydrogen bonding between the Hsq- anions and water molecules. Variable-temperature dielectric measurements and crystal structures determined through a combination of single-crystal X-ray and neutron diffraction reveal an AFE ordering at 104 K. The phase transition is driven by ordering of protons within the hydrogen-bonded strips. Considering the extent of proton transfer, the paraelectric (PE) state can be formulated as (2,3-Me2pyzH+)2(Hsq2 3-)(H5O2 +), whereas the AFE phase can be described as (2,3-Me2pyzH+)(Hsq-)(H2O). The structural transition caused by the localization of protons results in the change in color from yellow in the PE state to colorless in the AFE state. The occurrence and mechanism of the AFE phase transition have been also confirmed by heat capacity measurements and variable-temperature infrared and Raman spectroscopy. This work demonstrates a potentially promising approach to the design of new electrically ordered materials by engineering molecule-based crystal structures in which hydrogen-bonding interactions are intentionally partitioned into quasi-one-dimensional regions.

AB - A proton-transfer reaction between squaric acid (H2sq) and 2,3-dimethylpyrazine (2,3-Me2pyz) results in crystallization of a new organic antiferroelectric (AFE), (2,3-Me2pyzH+)(Hsq-)·H2O (1), which possesses a layered structure. The structure of each layer can be described as partitioned into strips lined with methyl groups of the Me2pyzH+ cations and strips featuring extensive hydrogen bonding between the Hsq- anions and water molecules. Variable-temperature dielectric measurements and crystal structures determined through a combination of single-crystal X-ray and neutron diffraction reveal an AFE ordering at 104 K. The phase transition is driven by ordering of protons within the hydrogen-bonded strips. Considering the extent of proton transfer, the paraelectric (PE) state can be formulated as (2,3-Me2pyzH+)2(Hsq2 3-)(H5O2 +), whereas the AFE phase can be described as (2,3-Me2pyzH+)(Hsq-)(H2O). The structural transition caused by the localization of protons results in the change in color from yellow in the PE state to colorless in the AFE state. The occurrence and mechanism of the AFE phase transition have been also confirmed by heat capacity measurements and variable-temperature infrared and Raman spectroscopy. This work demonstrates a potentially promising approach to the design of new electrically ordered materials by engineering molecule-based crystal structures in which hydrogen-bonding interactions are intentionally partitioned into quasi-one-dimensional regions.

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ER -

Antiferroelectric Phase Transition in a Proton-Transfer Salt of Squaric Acid and 2,3-Dimethylpyrazine

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