CN107674212B - 一种一维自旋交叉分子磁性材料及其制备方法 - Google Patents

一种一维自旋交叉分子磁性材料及其制备方法 Download PDF

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CN107674212B
CN107674212B CN201710877924.3A CN201710877924A CN107674212B CN 107674212 B CN107674212 B CN 107674212B CN 201710877924 A CN201710877924 A CN 201710877924A CN 107674212 B CN107674212 B CN 107674212B
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张道鹏
薛冲冲
石景文
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Shandong University of Technology
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Abstract

一种基于吡啶酰胺配体的二价铁一维自旋交叉配位聚合物磁性材料，是由FeL2(SeCN)2中性一维链、结晶DMF(N,N‑二甲酰胺)、结晶甲醇分子构成。本发明的优点是：该配位聚合物呈现明显骤变的温控高低自旋转换现象，磁滞温度区间大约20K，在分子热磁开关材料和信息存储材料方面具有潜在的应用价值。

Description

一种一维自旋交叉分子磁性材料及其制备方法
技术领域
本发明属于分子基自旋交叉磁性材料的合成技术领域，具体涉及一种基于吡啶酰胺配体的二价铁一维自旋交叉配位聚合物磁性材料及其制备方法。
背景技术
近十几年来，分子基磁性材料得到了迅速发展。作为高度有序的分子体系，它具有结构多样性，易于用化学方法对分子进行修饰和剪裁而改变其磁性；磁性能的多样性，可以将磁性和其他如机械、光、电等特性相结合；可以用常温或低温的方法进行合成；易于加工成形，可以制成许多传统磁体难以实现的器件；低密度等特点，正是这些特点使它成了分钟材料领域科研工作者研究的焦点。目前，分子基磁性材料的研究热点主要集中在设计和合成纳米分子磁体（包括单分子和单链磁体）、高相变温度（Tc）磁材料、自旋交叉材料和光-磁、电-磁、磁-电、手性-磁、微孔-磁等多功能复合材料。
随着微电子的迅速发展，分子水平的电子器件材料的研究越来越受到人们的关注。(A. Cornia,; M. Mannini, P. Sainctavit, R. Sessoli, Chem. Soc. Rev. 2011,40, 3076; Spin-crossover materials (Ed.: M. Halcrow), Wiley, Chichester,2013, ISBN 9781119998679; P. Chakraborty, C. Enachescu, A. Humair, L. Egger,T. Delgado, A. Tissot, L. Gu|n|e, C. Besnard, R. Bronisz, A. Hauser, DaltonTrans. 2014, 43, 17786; E. Collet, L. Henry, L. Píro-Lypez, L. Toupet, J. A.Real, Curr. Inorg. Chem. 2016, 6, 61; M. G. Cowan, J. Olgün, S.Narayanaswamy, J. L. Tallon, S. Brooker, J. Am. Chem. Soc. 2012, 134, 2892)。分子双稳性与分子水平上的新型信息存储、光磁开关、热开关等分子电子器件材料密切相关，因而使得双稳性分子磁性材料成为当前化学、物理和材料科学的研究热点之一。著名的磁化学家Kahn曾对分子双稳性给出如下定义：分子双稳性是指在一定的外界条件下，分子存在两种稳定或介稳的电子状态。具有分子双稳性的化合物是实现分子集合体作为新的光磁开关和信息存储元件的理想分子体系。过渡金属配合物的自旋交叉现象是目前研究最为广泛而深入的分子双稳现象之一。然而，设计和构筑这类具有特殊结构和性能的双稳性自旋交叉分子磁性材料仍然具有很大的挑战性。因此，对它的研究和探索，对于分子基磁性材料领域有着非常重要的意义，对开发新型双稳态分子磁性材料也会产生很大的影响。
发明内容
本发明提供了一种一维自旋交叉分子磁性材料及其制备方法。
为实现上述目的，本发明采取的技术方案为：
一种一维自旋交叉分子磁性材料，所述材料的分子式C51H56FeN14O9Se2；化学式为：[FeL2(SeCN)2]n·4nDMF·nCH3OH (L 代表间苯二甲双-4-吡啶基酰胺)。
所述磁性材料的晶体结构为：晶体属于单斜晶系，空间群为C2/c，晶胞参数为a =25.1307(14) Å，b = 14.3256(8) Å ， c = 17.0759(11) Å, α ＝ 90°，β ＝118.119(8)°，γ＝ 90°。
所述磁性材料的制备方法为：
S1、材料制备是在常温常压下进行的。将配体L的DMF溶液置于双臂H型管的一侧，水合水合高氯酸亚铁的甲醇溶液置于另一侧,再将用硒氰酸钾的甲醇溶液饱和的琼脂填充于H型管的横向连接部位，H型管两侧竖向立管分别用甲醇填充致满;
S2、将H型管置于暗处，几周后在横向连接部位析出黄色块状晶体；
S3、将步骤S2所得的晶体用甲醇洗涤，自然干燥，得成品。
本发明的优点是：该配位聚合物呈现骤变的温控的高低自旋转换现象，磁滞温度区间大约20K，在分子热磁开关材料和信息存储材料方面具有潜在的应用价值。
附图说明
图1为本发明实施例一种一维自旋交叉分子磁性材料的中性一维链分子结构。
图2为本发明实施例一种一维自旋交叉分子磁性材料的变温磁化率图。
图3为本发明实施例一种一维自旋交叉分子磁性材料的由室温到低温再到室温的变温磁化率图。
图4为本发明实施例一种一维自旋交叉分子磁性材料经X-射线单晶衍射仪进行结构表征的晶体学结构参数。
具体实施方式
为了使本发明的目的及优点更加清楚明白，以下结合实施例对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明实施例提供了一种一维自旋交叉分子磁性材料，所述材料的分子式C51H56FeN14O9Se2；化学式为：[FeL2(SeCN)2]n·4nDMF·nCH3OH (L 代表间苯二甲双-4-吡啶基酰胺)。
所述磁性材料的晶体结构为：晶体属于单斜晶系，空间群为C2/c，晶胞参数为a =25.1307(14) Å，b = 14.3256(8) Å ， c = 17.0759(11) Å, α ＝ 90°，β ＝118.119(8)°，γ＝ 90°。
提供了一种一维自旋交叉分子磁性材料的制备方法,包括如下步骤：
S1、材料制备是在常温常压下进行的。将配体L（63.6 mg, 0.2mmol的DMF溶液3 ML置于双臂H型管的一侧，水合高氯酸亚铁(27.5mg, 0.1mmol)的甲醇溶液3 ML置于另一侧,再将用硒氰酸钾(28.8mg, 0.2 mmol)的甲醇溶液饱和的琼脂填充于H型管的横向连接部位，H型管两侧竖向立管分别用甲醇填充致满;
S2、将H型管置于暗处，大约2-3周后在横向连接部位析出黄色块状晶体；
S3、将步骤S2所得的晶体用甲醇洗涤，自然干燥，得成品。
将制备所得材料用磁化率仪进行磁学性质的测量，测量结果见图3；用X-射线单晶衍射仪进行结构表征，所得材料的晶体学结构参数见图4。

Claims (6)

1.一种基于吡啶酰胺配体的二价铁一维自旋交叉配位聚合物磁性材料，其特征在于，所述材料的分子式为C51H56FeN14O9Se2；化学式为：[FeL2(SeCN)2]n·4nDMF·nCH3OH，L代表间苯二甲(双-4-吡啶基)酰胺；所述磁性材料的晶体结构为：晶体属于单斜晶系，空间群为C2/c，晶胞参数为a = 25.1307(14) Å，b = 14.3256(8) Å，c = 17.0759(11) Å，α ＝ 90°，β＝ 118.119(8)°，γ ＝ 90°，所述磁性材料的结构为：
Figure DEST_PATH_IMAGE002
。
2.如权利要求1所述的一种基于吡啶酰胺配体的二价铁一维自旋交叉配位聚合物磁性材料的制备方法，其特征在于，包括如下步骤：S1、材料制备是在常温常压下进行的，将配体L的DMF溶液置于双臂H型管的一侧，水合高氯酸亚铁的甲醇溶液置于另一侧，再将用硒氰酸钾的甲醇溶液饱和的琼脂填充于H型管的横向连接部位，H型管两侧竖向立管分别用甲醇填充致满；S2、将H型管置于暗处，几周后在横向连接部位析出黄色块状晶体；S3、将步骤S2所得的晶体用甲醇洗涤，自然干燥，得成品。
3.如权利要求2所述的制备方法，其特征在于，所述L代表间苯二甲(双-4-吡啶基)酰胺。
4.如权利要求2所述的制备方法，其特征在于，所述DMF代表N,N-二甲酰胺。
5.如权利要求2所述的制备方法，其特征在于，所述配体L的物质的量为0.2mmol；所述DMF的用量为3mL；所述水合高氯酸亚铁的物质的量为0.1mmol；所述甲醇的用量为3mL；所述硒氰酸钾的物质的量为0.2mmol。
6.如权利要求2所述的制备方法，其特征在于，所述H型管置于暗处的时间为2-3周。
CN201710877924.3A 2017-09-26 2017-09-26 一种一维自旋交叉分子磁性材料及其制备方法 Expired - Fee Related CN107674212B (zh)

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