Issue 12, 2003
From the journal:

Dalton Transactions

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

Kristian H. Sugiyarto,†a   Wendy-Anne McHale,a   Donald C. Craig,a   A. David Rae,b   Marcia L. Scuddera  and  Harold A. Goodwin*a  

* Corresponding authors

a School of Chemical Sciences, University of New South Wales, UNSW, Sydney 2052, Australia
E-mail: H.Goodwin@unsw.edu.au

b Research School of Chemistry, Australian National University, Canberra ACT 2601, Australia

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 1A1 ↔ 5T2 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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Article information

DOI
https://doi.org/10.1039/B301218B
Article type
Paper
Submitted
30 Jan 2003
Accepted
15 Apr 2003
First published
14 May 2003

Dalton Trans., 2003, 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, 2443 DOI: 10.1039/B301218B

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