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Poly[(2,2 ’-bipyridine)tetrakis(imidazolato)diiron(II)]: Structural and spin-state phase transitions and low-temperature magnetic ordering in a unique 2-dimensional material

TitlePoly[(2,2 ’-bipyridine)tetrakis(imidazolato)diiron(II)]: Structural and spin-state phase transitions and low-temperature magnetic ordering in a unique 2-dimensional material
Publication TypeJournal Article
Year of Publication2004
AuthorsPatrick, BO, Reiff, WM, Sanchez, V, Storr, A, Thompson, RC
JournalInorganic Chemistry
Volume43
Pagination2330-2339
Date PublishedApr
Type of ArticleArticle
ISBN Number0020-1669
KeywordsCHEMISTRY, COMPLEXES, CROSSOVER, CRYSTAL-STRUCTURE, ELECTRONIC-STRUCTURE, IRON(II), PYRAZOLATE
Abstract

Poly[(2,2’-bipyridine)tetrakis(imidazolato)diiron(II)] was synthesized by the reaction of ferrocene with imidazole in an excess of 2,2’- bipyridine in a Carius tube at 130degreesC. Dc magnetic susceptibility studies at an applied field of 1000 G reveal that on cooling from room temperature, the material undergoes two structural phase transitions designated alpha –> beta, and beta –> gamma at 151 and 133 K, respectively. On warming, the gamma –> beta and beta –> alpha transitions are observed at 137 and 151 K, respectively; a 4 K thermal hysteresis clearly detectable in the lower temperature beta <––> gamma transition. These structural phase transitions have also been studied by detailed, variable-temperature, ac susceptibility and Mossbauer spectroscopy techniques. Single-crystal X-ray diffraction studies done at 294, 143, and 113 K reveal 2, 12, and 6 unique iron centers in the alpha-, beta-, and gamma-forms, respectively. All three forms have the same basic structure involving 2D extended double layer sheets (bilayers) of alternating tetrahedral and octahedral irons singly bridged by imidazolate ligands, with the octahedral centers additionally coordinated by 2,2’-bipyridine ligands that occupy positions between the sheets. Magnetic susceptibility and bond length data reveal that in the gamma-phase one in three six-coordinate sites corresponds to spin singlet ground-state iron(II); i.e., the overall alpha –> gamma process involves a spin-crossover transition such that at least 1/6 of the iron sites in the gamma-phase correspond to S = 0. This is supported by the low-temperature Mossbauer spectra of the gamma-phase, which reveal the simultaneous presence of both S = 2 and S = 0 iron(II) centers. The compound magnetically orders, with a resultant small remnant magnetization, at low temperatures. The magnetic phase transition, studied by a combination of dc and ac susceptibility and Mossbauer techniques, occurs at T-c similar to 6.5 K.

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