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Thermally induced spin transition in Fe(pyrazine)[Fe(CN)5NO]
Journal of Physics and Chemistry of Solids ( IF 4 ) Pub Date : 2021-03-01 , DOI: 10.1016/j.jpcs.2020.109843
Y. Plasencia , Y. Avila , J. Rodríguez-Hernández , M. Ávila , E. Reguera

Abstract Transition metal nitroprussides form a family of coordination polymers with interesting physical properties. From their three-dimensional (3D) phases, by inducing rupture of the axial T–NC bond through organic molecules (L) with a high ability to form a T–L coordination bond, pillared transition metal nitroprussides can be obtained. For monodentate molecules, for example, pyridine and its derivatives, the pillars are formed in the interlayer region by pairs of molecules coupled through their dipole moments, and the resulting solid has a two-dimensional (2D) structure with T(L)2[Fe(CN)5NO] as the formula unit. In this contribution, we report the use of a bidentate molecule, pyrazine, to obtain pillared ferrous nitroprusside. According to the refined crystal structure, this solid has a 3D framework, which results from the pyrazine molecule (L) coordinating to two iron atoms to afford Fe(pyrazine)[Fe(CN)5NO]. This material shows spin-crossover (SCO) behavior with thermal hysteresis of about 40 K, which is associated with relatively large structural changes, for instance, a reversible variation of 12% in the unit cell volume. The thermally induced spin transition is accompanied by a notable color change of the material. The main features of this thermally activated spin transition in the material under study are discussed herein on the basis of its structural characterization at 100 and 300 K, magnetic and differential scanning calorimetry (DSC) measurements, and Raman and Mossbauer spectra for both the low- and high-spin phases. The reversibility of this thermally activated spin transition has been verified by magnetic, Mossbauer, X-ray powder diffraction (XRD), and infrared (IR) data. To the best of our knowledge, this is the first report on the preparation and characterization of Fe(pyrazine)[Fe(CN)5NO] and its thermally induced SCO behavior.

中文翻译:

Fe(吡嗪)[Fe(CN)5NO]中的热诱导自旋跃迁

摘要 过渡金属硝普盐是一类具有有趣物理性质的配位聚合物。从它们的三维 (3D) 相中,通过具有形成 T-L 配位键的高能力的有机分子 (L) 诱导轴向 T-NC 键断裂,可以获得柱撑过渡金属硝普盐。对于单齿分子,例如吡啶及其衍生物,柱子由通过偶极矩耦合的分子对在层间区域形成,所得固体具有二维 (2D) 结构,T(L)2[ Fe(CN)5NO]为分子式单位。在这篇文章中,我们报告了使用双齿分子吡嗪来获得柱撑硝普亚铁。根据精制的晶体结构,该固体具有3D骨架,这是由于吡嗪分子 (L) 与两个铁原子配位得到 Fe(pyrazine)[Fe(CN)5NO]。这种材料显示出自旋交叉 (SCO) 行为,热滞后约为 40 K,这与相对较大的结构变化有关,例如,晶胞体积的可逆变化为 12%。热诱导的自旋转变伴随着材料的显着颜色变化。本文根据材料在 100 和 300 K 下的结构表征、磁性和差示扫描量热法 (DSC) 测量以及拉曼和穆斯堡尔光谱对所研究材料中这种热激活自旋跃迁的主要特征进行了讨论。和高自旋阶段。这种热激活自旋跃迁的可逆性已被磁性、穆斯堡尔、X 射线粉末衍射 (XRD) 和红外 (IR) 数据。据我们所知,这是关于 Fe(pyrazine)[Fe(CN)5NO] 及其热诱导 SCO 行为的制备和表征的第一份报告。
更新日期:2021-03-01
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