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Issue 12, 2003
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Spin transition centres linked by the nitroprusside ion. The cooperative transition in bis(2,6-bis(pyrazol-3-yl)pyridine)iron(II) nitroprusside

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Abstract

The complex [Fe(3-bpp)2][Fe(CN)5(NO)] (3-bpp = 2,6-bis(pyrazol-3-yl)pyridine) undergoes an abrupt, thermally-induced 1A15T2 spin transition associated with a narrow (∼3 K) hysteresis loop (T1/2↓ = 181 K; T1/2↑ = 184 K). The transition is accompanied by a change in crystallographic space group (P4/ncc at 294 K; Pnca at 100 K) along with a change in the average Fe–N distance of 0.21 Å. The complex cation and anion are linked by hydrogen bonding involving each of the four pyrazolyl-NH moieties of each complex cation and the four equatorial cyano groups of each anion, resulting in layers of 4,4-nets. The hydrogen bonding remains essentially the same in both phases but the relative orientations of the cations and anions change significantly to allow for the change in the dimensions of the complex cation, accounting for the cooperativity associated with the spin change.

Graphical abstract: Spin transition centres linked by the nitroprusside ion. The cooperative transition in bis(2,6-bis(pyrazol-3-yl)pyridine)iron(ii) nitroprusside

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Publication details

The article was received on 30 Jan 2003, accepted on 15 Apr 2003 and first published on 14 May 2003


Article type: Paper
DOI: 10.1039/B301218B
Citation: Dalton Trans., 2003,0, 2443-2448
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    Spin transition centres linked by the nitroprusside ion. The cooperative transition in bis(2,6-bis(pyrazol-3-yl)pyridine)iron(II) nitroprusside

    K. H. Sugiyarto, W. McHale, D. C. Craig, A. D. Rae, M. L. Scudder and H. A. Goodwin, Dalton Trans., 2003, 0, 2443
    DOI: 10.1039/B301218B

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