Abstract

Synthesis and exploration of intriguing physical properties of alkali-metal-doped aromatic hydrocarbons have been the important research topics in the fields of physics, chemistry and materials science. In this work, a powder sample of potassium-doped tris(diphenacyl) iron molecular crystal is prepared by the high-vacuum annealing method. The X-ray diffraction results show that the crystal structure of the synthesized sample is different from that of pristine tris(diphenacyl)iron. The direct current (DC) magnetic susceptibilitiy shows a pronounced hump structure near 8.0 K, which is distinct from the paramagnetism of pristine material in the whole temperature range of 1.8–300 K. The alternating current (AC) magnetic susceptibility shows that the hump has a significant frequency dependence, which can safely rule out the possibility of antiferromagnetism. The combination of the Vogel-Fulcher law, the Néel-Brown model and the critical slowing down model reveals that the hump originates from superparamagnetism with a blocking temperature (<i>T</i><sub>B</sub>) of about 8.0 K. According to the results of Raman spectroscopy, it can be confirmed that the 4s electrons of potassium in the doped material are transferred to the benzene ring of tris(diphenacyl)iron, causing the characteristic Raman modes to be red-shifted and the local magnetic moment to form. Our work is of great significance in exploring alkali-metal-doped aromatic hydrocarbons, and provides a new route for searching organic magnetic materials.

Highlights

  • 图 7. 弛豫时间τ与温度Tf的依赖关系,红色曲线是Vogel-Fulcher law的拟合结果,绿色曲线是 Néel-Brown law的拟合结果,黑色实线是critical slowing down model 的拟合结果

  • Sin. 65 077402 (in Chinese) [高云,王仁树,邬小林,程佳,邓天郭,闫循 旺,黄忠兵 2016 物理学报 65 077402]

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Summary

Introduction

摘要 本研究通过高真空退火法制备了钾掺杂三(二苯甲酰甲基)铁分子晶体的 粉末样品。 X -射线衍射测试结果表明合成样品与纯三(二苯甲酰甲基)铁的 晶体结构明显不同,平均晶粒尺寸约为 20.5 nm。直流磁化率和交流磁化率 的测试结果表明合成的样品具有阻塞温度(TB)约为 8.0 K 的超顺磁性,这 与纯有机物在 1.8-300 K 整个测试温区的顺磁性存在本质的差异。根据拉曼光 谱测试结果可以确认,掺杂材料中钾的 4s 电子转移到了三(二苯甲酰甲基) 铁的苯环上,引起了拉曼模式的红移,同时电荷转移也导致苯环上局域磁矩 的形成。我们的研究工作对碱金属掺杂芳香烃分子晶体的合成和物性研究具 有重要的意义,并为寻找新型的有机铁磁体提供了一条新的途径。 具体制备工艺如下: 1) 混合:在水和氧含量均低于 0.1 ppm 的手套箱中将三(二苯甲酰甲基)铁 (TCI,>99.5%)和钾(Sinopharm Chemical Reagent,99%)按照钾原子: 三(二苯甲 酰甲基)铁=3 : 1 的化学计量比例混合, 其中纯有机物约为 0.1 g,钾被切成了直径 约 1.5 mm 的小块。将混合后的样品装入洗净烘干直径为 10 mm 的石英玻璃管中, 并做好临时密封处理。 2) 样品的高真空密封:将样品从手套箱移出,迅速连接到高真空设备中抽 气,当管内气压稳定在 10−4 Pa 时,利用氢氧焰进行高温熔断密封,使样品封存 在高真空的环境中。 3) 退火:将密封好的石英管放置高真空退火炉中退火。退火温度为 275°C, 退火时间为 1 天。然后自然降温,得到深黑色样品。 图 2 显示纯三(二苯甲酰甲基)铁和钾按照 1: 3 混合以及经过真空热烧结后的 照片。可以看到钾与三(二苯甲酰甲基)铁经过高真空烧结后得到黑色产物, 仅有 少许紫色有机物残留, 这说明钾与三(二苯甲酰甲基)铁已经发生了充分反应。 图 3 为纯三(二苯甲酰甲基)铁的磁性测试结果。从中我们可以观察到,纯 三(二苯甲酰甲基)铁在 1.8-300 K 温度范围内表现出典型的居里-外斯行为,这表 明材料在整个测量温区处于顺磁状态。

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