Influence of HF2- geometry on magnetic interactions elucidated from polymorphs of the metal-organic framework [Ni(HF2)(pyz)2]PF6 (pyz = pyrazine)

Jamie L. Manson; Kimberly E. Carreiro; Saul H. Lapidus; Peter W. Stephens; Paul A. Goddard; Rico E. Del Sesto; Jesper Bendix; Saman Ghannadzadeh; Isabel Franke; John Singleton; Tom Lancaster; Johannes S. Möller; Peter J. Baker; Francis L. Pratt; Stephen J. Blundell; Jinhee Kang; Changhoon Lee; Myung-Hwan Whangbo

doi:10.1039/c2dt30113j

Influence of HF₂^- geometry on magnetic interactions elucidated from polymorphs of the metal-organic framework [Ni(HF₂)(pyz)₂]PF₆ (pyz = pyrazine)

Jamie L. Manson, Kimberly E. Carreiro, Saul H. Lapidus, Peter W. Stephens, Paul A. Goddard, Rico E. Del Sesto, Jesper Bendix, Saman Ghannadzadeh, Isabel Franke, John Singleton, Tom Lancaster, Johannes S. Möller, Peter J. Baker, Francis L. Pratt, Stephen J. Blundell, Jinhee Kang, Changhoon Lee, Myung-Hwan Whangbo

Department of Chemistry

14 Citations (Scopus)

Abstract

A tetragonal polymorph of [Ni(HF ₂)(pyz) ₂]PF ₆ (designated β) is isomorphic to its SbF ₆-congener at 295 K and features linear Ni-FHF-Ni pillars. Enhancements in the spin exchange (J _FHF = 7.7 K), Néel temperature (T _N = 7 K), and critical field (B _c = 24 T) were found relative to monoclinic α-PF ₆. DFT reveals that the HF ₂ ^- bridges are significantly better mediators of magnetic exchange than pyz (J _pyz), where J _FHF ≈ 3J _pyz, thus leading to quasi-1D behavior. Spin density resides on all atoms of the HF ₂ ^- bridge whereas N-donor atoms of the pyz ring bear most of the density.

Original language	English
Journal	Dalton Transactions (Print Edition)
Volume	41
Issue number	24
Pages (from-to)	7235-7243
Number of pages	9
ISSN	1477-9226
DOIs	https://doi.org/10.1039/c2dt30113j
Publication status	Published - 28 Jun 2012

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Manson, J. L., Carreiro, K. E., Lapidus, S. H., Stephens, P. W., Goddard, P. A., Sesto, R. E. D., Bendix, J., Ghannadzadeh, S., Franke, I., Singleton, J., Lancaster, T., Möller, J. S., Baker, P. J., Pratt, F. L., Blundell, S. J., Kang, J., Lee, C., & Whangbo, M-H. (2012). Influence of HF₂^- geometry on magnetic interactions elucidated from polymorphs of the metal-organic framework [Ni(HF₂)(pyz)₂]PF₆ (pyz = pyrazine). Dalton Transactions (Print Edition), 41(24), 7235-7243. https://doi.org/10.1039/c2dt30113j

Influence of HF₂^- geometry on magnetic interactions elucidated from polymorphs of the metal-organic framework [Ni(HF₂)(pyz)₂]PF₆ (pyz = pyrazine). / Manson, Jamie L.; Carreiro, Kimberly E.; Lapidus, Saul H. et al.

In: Dalton Transactions (Print Edition), Vol. 41, No. 24, 28.06.2012, p. 7235-7243.

Research output: Contribution to journal › Journal article › Research › peer-review

Manson, JL, Carreiro, KE, Lapidus, SH, Stephens, PW, Goddard, PA, Sesto, RED, Bendix, J, Ghannadzadeh, S, Franke, I, Singleton, J, Lancaster, T, Möller, JS, Baker, PJ, Pratt, FL, Blundell, SJ, Kang, J, Lee, C & Whangbo, M-H 2012, 'Influence of HF₂^- geometry on magnetic interactions elucidated from polymorphs of the metal-organic framework [Ni(HF₂)(pyz)₂]PF₆ (pyz = pyrazine)', Dalton Transactions (Print Edition), vol. 41, no. 24, pp. 7235-7243. https://doi.org/10.1039/c2dt30113j

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title = "Influence of HF2- geometry on magnetic interactions elucidated from polymorphs of the metal-organic framework [Ni(HF2)(pyz)2]PF6 (pyz = pyrazine)",

abstract = "A tetragonal polymorph of [Ni(HF 2)(pyz) 2]PF 6 (designated β) is isomorphic to its SbF 6-congener at 295 K and features linear Ni-FHF-Ni pillars. Enhancements in the spin exchange (J FHF = 7.7 K), N{\'e}el temperature (T N = 7 K), and critical field (B c = 24 T) were found relative to monoclinic α-PF 6. DFT reveals that the HF 2 - bridges are significantly better mediators of magnetic exchange than pyz (J pyz), where J FHF ≈ 3J pyz, thus leading to quasi-1D behavior. Spin density resides on all atoms of the HF 2 - bridge whereas N-donor atoms of the pyz ring bear most of the density.",

author = "Manson, {Jamie L.} and Carreiro, {Kimberly E.} and Lapidus, {Saul H.} and Stephens, {Peter W.} and Goddard, {Paul A.} and Sesto, {Rico E. Del} and Jesper Bendix and Saman Ghannadzadeh and Isabel Franke and John Singleton and Tom Lancaster and M{\"o}ller, {Johannes S.} and Baker, {Peter J.} and Pratt, {Francis L.} and Blundell, {Stephen J.} and Jinhee Kang and Changhoon Lee and Myung-Hwan Whangbo",

year = "2012",

month = jun,

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doi = "10.1039/c2dt30113j",

language = "English",

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T1 - Influence of HF2- geometry on magnetic interactions elucidated from polymorphs of the metal-organic framework [Ni(HF2)(pyz)2]PF6 (pyz = pyrazine)

AU - Manson, Jamie L.

AU - Carreiro, Kimberly E.

AU - Lapidus, Saul H.

AU - Stephens, Peter W.

AU - Goddard, Paul A.

AU - Sesto, Rico E. Del

AU - Bendix, Jesper

AU - Ghannadzadeh, Saman

AU - Franke, Isabel

AU - Singleton, John

AU - Lancaster, Tom

AU - Möller, Johannes S.

AU - Baker, Peter J.

AU - Pratt, Francis L.

AU - Blundell, Stephen J.

AU - Kang, Jinhee

AU - Lee, Changhoon

AU - Whangbo, Myung-Hwan

PY - 2012/6/28

Y1 - 2012/6/28

N2 - A tetragonal polymorph of [Ni(HF 2)(pyz) 2]PF 6 (designated β) is isomorphic to its SbF 6-congener at 295 K and features linear Ni-FHF-Ni pillars. Enhancements in the spin exchange (J FHF = 7.7 K), Néel temperature (T N = 7 K), and critical field (B c = 24 T) were found relative to monoclinic α-PF 6. DFT reveals that the HF 2 - bridges are significantly better mediators of magnetic exchange than pyz (J pyz), where J FHF ≈ 3J pyz, thus leading to quasi-1D behavior. Spin density resides on all atoms of the HF 2 - bridge whereas N-donor atoms of the pyz ring bear most of the density.

AB - A tetragonal polymorph of [Ni(HF 2)(pyz) 2]PF 6 (designated β) is isomorphic to its SbF 6-congener at 295 K and features linear Ni-FHF-Ni pillars. Enhancements in the spin exchange (J FHF = 7.7 K), Néel temperature (T N = 7 K), and critical field (B c = 24 T) were found relative to monoclinic α-PF 6. DFT reveals that the HF 2 - bridges are significantly better mediators of magnetic exchange than pyz (J pyz), where J FHF ≈ 3J pyz, thus leading to quasi-1D behavior. Spin density resides on all atoms of the HF 2 - bridge whereas N-donor atoms of the pyz ring bear most of the density.

U2 - 10.1039/c2dt30113j

DO - 10.1039/c2dt30113j

M3 - Journal article

SN - 1477-9226

VL - 41

SP - 7235

EP - 7243

JO - Acta chemica Scandinavica. Series A: Physical and inorganic chemistry

JF - Acta chemica Scandinavica. Series A: Physical and inorganic chemistry

IS - 24

ER -

Influence of HF2- geometry on magnetic interactions elucidated from polymorphs of the metal-organic framework [Ni(HF2)(pyz)2]PF6 (pyz = pyrazine)

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Influence of HF₂^- geometry on magnetic interactions elucidated from polymorphs of the metal-organic framework [Ni(HF₂)(pyz)₂]PF₆ (pyz = pyrazine)