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

Dalton Transactions : an International Journal of Inorganic Chemistry
Jamie L MansonMyung-Hwan Whangbo

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.

References

Sep 1, 1990·Physical Review. B, Condensed Matter·T Sakai, M Takahashi
Apr 15, 2005·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Sebastian SinneckerWolfgang Lubitz
Nov 23, 2006·The Journal of Chemical Physics·A Martín PendásE Francisco
Feb 1, 2008·Physical Review Letters·T LancasterJ A Schlueter
Sep 14, 2010·Angewandte Chemie·Gregory J HalderJamie L Manson
Jun 8, 2011·Inorganic Chemistry·J L MusfeldtM-H Whangbo

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