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Large Thermal Hysteresis for Iron(II) Spin Crossover Complexes with N-(Pyrid-4-yl)isonicotinamide

Title data

Lochenie, Charles ; Bauer, Wolfgang ; Railliet, Antoine P. ; Schlamp, Stephan ; Garcia, Yann ; Weber, Birgit:
Large Thermal Hysteresis for Iron(II) Spin Crossover Complexes with N-(Pyrid-4-yl)isonicotinamide.
In: Inorganic Chemistry. Vol. 53 (2014) Issue 21 . - pp. 11563-11572.
ISSN 1520-510X
DOI: https://doi.org/10.1021/ic501624b

Abstract in another language

A new series of iron(II) 1D coordination polymers with the general formula [FeL1(pina)]·xsolvent with L1 being a tetradentate N2O22– coordinating Schiff-base-like ligand [([3,3′]-[1,2-phenylenebis(iminomethylidyne)]bis(2,4-pentanedionato)(2-)-N,N′,O2,O2′], and pina being a bridging axial ligand N-(pyrid-4-yl)isonicotinamide, are discussed. The X-ray crystal structure of [FeL1(pina)]·2MeOH was solved for the low-spin state. The compound crystallizes in the monoclinic space group P21/c, and the analysis of the crystal packing reveals the formation of a hydrogen bond network where additional methanol molecules are included. Different magnetic properties are observed for the seven samples analyzed, depending on the nature of the included solvent molecules. The widest hysteresis loop is observed for a fine crystalline sample of composition [FeL1(pina)]·xH2O/MeOH. The 88 K wide thermal hysteresis loop (T1/2↑ = 328 K and T1/2↓ = 240 K) is centered around room temperature and can be repeated without of a loss of the spin transition properties. For the single crystals of [FeL1(pina)]·2MeOH, a 51 K wide hysteresis loop is observed (T1/2↑ = 296 K and T1/2↓ = 245 K) that is also stable for several cycles. For a powder sample of [FeL1(pina)]·0.5H2O·0.5MeOH a cooperative spin transition with a 46 K wide hysteresis loop around room temperature is observed (T1/2↑ = 321 K and T1/2↓ = 275 K). This compound was further investigated using Mössbauer spectroscopy and DSC. Both methods reveal that, in the cooling mode, the spin transition is accompanied by a phase transition while in the heating mode a loss of the included methanol is observed that leads to a loss of the spin transition properties. These results show that the pina ligand was used successfully in a crystal-engineering-like approach to generate 1D coordination polymers and improve their spin crossover properties.

Further data

Item Type: Article in a journal
Refereed: Yes
Institutions of the University: Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Anorganic Chemistry IV > Chair Anorganic Chemistry IV - Univ.-Prof. Dr. Birgit Weber
Faculties
Faculties > Faculty of Biology, Chemistry and Earth Sciences
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Anorganic Chemistry IV
Result of work at the UBT: Yes
DDC Subjects: 500 Science > 540 Chemistry
Date Deposited: 25 Jul 2017 12:46
Last Modified: 25 Jul 2017 12:46
URI: https://eref.uni-bayreuth.de/id/eprint/38809