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

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• 作者：Charles Lochenie ; Wolfgang Bauer ; Antoine P. Railliet ; Stephan Schlamp ; Yann Garcia ; Birgit Weber
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：November 3, 2014
• 年：2014
• 卷：53
• 期：21
• 页码：11563-11572
• 全文大小：539K
• ISSN：1520-510X

文摘

A new series of iron(II) 1D coordination polymers with the general formula [FeL1(pina)]路xsolvent with L1 being a tetradentate N₂O₂^{2鈥?/sup> coordinating Schiff-base-like ligand [([3,3鈥瞉-[1,2-phenylenebis(iminomethylidyne)]bis(2,4-pentanedionato)(2-)-N,N鈥?O2,O2鈥瞉, and pina being a bridging axial ligand N-(pyrid-4-yl)isonicotinamide, are discussed. The X-ray crystal structure of [FeL1(pina)]路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)]路xH₂O/MeOH. The 88 K wide thermal hysteresis loop (T_{1/2鈫?/sub> = 328 K and T1/2鈫?/sub> = 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)]路2MeOH, a 51 K wide hysteresis loop is observed (T1/2鈫?/sub> = 296 K and T1/2鈫?/sub> = 245 K) that is also stable for several cycles. For a powder sample of [FeL1(pina)]路0.5H2O路0.5MeOH a cooperative spin transition with a 46 K wide hysteresis loop around room temperature is observed (T1/2鈫?/sub> = 321 K and T1/2鈫?/sub> = 275 K). This compound was further investigated using M枚ssbauer 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.}}