CN108358954B - 一种手性稀土-氮氧自由基单链磁体及其制备方法 - Google Patents
一种手性稀土-氮氧自由基单链磁体及其制备方法 Download PDFInfo
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Abstract
一种手性稀土‐氮氧自由基单链磁体及其制备方法,所述单链磁体化学式为:[Dy(hfac)3((1R)‑(‑)‑Myrtenal‑NIT)]n,其中,n为1到正无穷的自然数。其制备方法是将六氟乙酰丙酮镝的正己烷溶液回流两小时后,加入(1R)‑(‑)‑Myrtenal‑NIT的二氯甲烷溶液反应数分钟,后经室温挥发得到目标产物。本发明的优点:通过简单的化学合成制备了一例手性稀土‑氮氧自由基配合物,该配合物表现出零场慢磁驰豫行为,磁滞回环。这种具有手性的单链磁体材料不但在高密度信息存储、量子计算机以及自旋电子器件等方面具有潜在的应用价值,并使人们能够进一步了解手性和磁现象之间的相关性及相互影响。
Description
【技术领域】
本发明属于功能性材料制备技术领域,涉及一种手性稀土-氮氧自由基配合物型单链磁体及其制备方法。
【背景技术】
磁性存储材料作为一种最重要的信息存储材料对人类的生活和生产产生了深远影响,而分子纳米磁体的出现更是极大地推动了这一领域的发展。它是一种基于单个分子或分子纳米链的超顺磁体,具有传统磁体所特有的磁双稳态和磁滞回线等性质,理论上也可以用来作为信息存储材料。且与传统磁体不同的是,它的磁体性质是建立在单个分子或单链基础上,即一个分子或一段分子链就可以代表一个“0”或“1”状态,从而存储一个bit的数据。虽然这一领域的发展已有二十余年,然而目前已经报道的分子纳米磁体都只有极低温度附近才能展现磁双稳态,这与实际应用的要求还有相当大的差距。因此,合成具有高势能垒和高阻塞温度的分子纳米磁体仍是这一领域最主要的挑战和目标。而目前已有的研究结果都说明提高自旋载体的单离子各向异性和它们之间磁耦合作用是获得高势能垒分子纳米磁体的关键。稀土离子一般具有大的轨道角动量,自旋-轨道耦合使其具有强的磁各向异性;但是由于受到外层电子的屏蔽,稀土离子间的磁耦合一般都很弱。通过引入氮氧自由基作为桥联配体及自旋载体,可以建立自由基与稀土离子间的有效磁耦合,从而增强稀土离子之间的磁耦合作用,获得高势能垒的单链磁体。
手性是在微观世界和宏观世界中都广泛存在的一种现象,研究手性物质不仅具有重要的理论意义,而且对探索合成新材料有重要的指导作用,目前手性配合物在非线性光学、医学、以及生物、磁性等领域都有重要应用。集磁性和手性于一体的双功能材料能够表现出独特的镜像和磁学性能,而手性和磁性的相互影响则更是具有重要的理论研究价值。通过将电子自旋、轨道和手性结构特征融于同一化合物中,研究配合物的分子磁化学和光电性质,实现手性分子磁体、手性自旋交叉等多功能分子材料。
目前分子磁手性化学研究受到手性合成不易控、分离困难等因素的影响而进展地较为缓慢,我们选择手性纯的氮氧自由基作为配体合成的手性稀土单链磁体,产物手性纯度高,合成过程简单,对于研究分子磁性和手性影响是一种更优的选择路径。
【发明内容】
本发明的目的是针对分子磁手性化学受到常规手性合成和分离困难的问题,提供一种以单一手性配体合成手性稀土-氮氧自由基单链磁体及其制备方法。本发明选用手性氮氧自由基合成单链磁体,该材料是六氟乙酰丙酮合镝水合物与自由基组装成的一维配合物,在70℃下反应5分钟,冷却至室温后,过滤,滤液在室温下静置一周,得到条状的浅蓝色晶体。
本发明的技术方案:
一种手性稀土-氮氧自由基单链磁体材料,其化学式为: [Dy(hfac)3((1R)-(-)-Myrtenal-NIT)]n,式中n为1到正无穷的自然数,hfac为六氟乙酰丙酮,(1R)-(-)-Myrtenal-NIT为2-((1R)-6,6-二甲基二环[3.1.1]庚-2-烯基)-4,4,5,5-四甲基咪唑啉-3-氧化-1-氧基自由基;晶体结晶在单斜晶系,空间群为P21,晶胞参数为:a=α=γ=90°,β=117.863(2)°, Z=8。该配合物的最小不对称结构单元里含有四个晶体学独立的Dy3+离子和四个(1R)-(-)-Myrtenal-NIT分子。中心Dy3+离子与来自三个hfac的六个氧原子和来自两个(1R)-(-)-Myrtenal-NIT的两个氧原子配位,每个(1R)-(-)-Myrtenal-NIT作为桥联配体连接两个Dy3+离子,形成一条无限一维链,晶体数据如表1所示。
一种手性稀土-氮氧自由基单链磁体材料的制备方法,包括以下步骤:
1)按照文献方法合成自由基(1R)-(-)-Myrtenal-NIT(Ullman procedure)和六氟乙酰丙酮镝水合物Dy(hfac)3·2H2O;
2)在50mL圆底烧瓶中,加入Dy(hfac)3·2H2O的正己烷溶液,90-110℃下搅拌回流2-3小时,缓慢降温至50-70℃后滴加(1R)-(-)-Myrtenal-NIT的二氯甲烷溶液,反应5-10分钟后,降至室温,过滤;
3)将上述滤液置于50mL烧杯中,薄膜封口,置于干燥器中。室温挥发一周,即可得目标产物。
步骤2)所述Dy(hfac)3·2H2O的正已烷溶液中,Dy(hfac)3·2H2O(质量为26.4mg)的浓度为0.0016mol/L。所述(1R)-(-)-Myrtenal-NIT的二氯甲烷溶液中, (1R)-(-)-Myrtenal-NIT(质量11.1mg)的浓度为0.008mol/L。
所述Dy(hfac)3·2H2O与(1R)-(-)-Myrtenal-NIT的摩尔比为1:1。
本发明的优点和有益效果是:
通过简单的化学合成工艺制备了一例手性稀土-氮氧自由基配合物,该配合物在零场时表现出慢磁驰豫行为,并在±2.5T之间呈现一个接近矩形的磁滞回环。这种具有手性的单链磁体材料,不但在高密度信息存储、量子计算机以及自旋电子器件等方面具有潜在的应用价值,而且使人们能够进一步了解手性和磁现象之间的相关性及相互影响。
【附图说明】
图1为该手性稀土-氮氧自由基配合物材料的单晶衍射结构图,其中:图1(a)为该材料中四种晶体学独立的Dy3+离子的配位模式图;图1(b)为 {Dy(hfac)3((1R)-(-)-Myrtenal-NIT)}单元结构图;图1(c)为该化合物从b方向观察到的空间堆积图。
图2为该材料的圆二色谱图。
图3为该材料的直流磁性测试谱图,其中:图3(a)为该材料的变温直流磁化率测试图;图3(b)为该材料在-5T到+5T的变场磁化强度数据。
图4为该材料的交流磁性测试谱图,图4(a)为该材料在零场下的变温交流磁化率的虚部测试图;图4(b)为该材料在零场下的变频交流磁化率的虚部测试图;图4(c)为该材料的零场变频交流磁化率的实部对虚部作图得到的Cole-Cole图。
【具体实施方式】
实施例:
所述的手性稀土-氮氧自由基单链磁体的制备方法,包括以下步骤:
1)(1R)-(-)-Myrtenal-NIT的合成:
25mL圆底烧瓶中,加入20mL无水甲醇溶解0.74g(5mmol)2,3-二甲基-2,3-二羟胺基丁烷,5分钟后加入0.76mL(0.75g,5mmol)(1R)-(-)-桃金娘烯醛,室温下搅拌反应两天,得到无色透明油状液体,减压除去溶剂,将油状物溶于100mL二氯甲烷后冰浴下搅拌5分钟后,加入将1.1g高碘酸钠溶于30mL水中配制的高碘酸钠溶液,冰浴下反应25分钟,后经分液、反复洗涤、干燥、减压除去溶剂,收集得到蓝色油状物;用石油醚与乙酸乙酯体积比为3:1的淋洗剂过色谱柱,收集蓝色色带,减压除去溶剂得到深蓝色的粉末晶体即为(1R)-(-)-Myrtenal-NIT,产率48%。
2)Dy(hfac)3·2H2O的合成:
冰浴搅拌下于圆底烧瓶中加入100mL乙醚、24mmol六氟乙酰丙酮,24mmol氨水,搅拌至白烟消失,用10mL水溶解8mmol六水合氯化镝DyCl3·6H2O,搅拌30分钟后加入20mL水,再搅拌10分钟,经过分液、三次洗涤有机相、三次萃取水相、合并有机相、无水硫酸镁干燥有机相,过滤,减压去除溶剂后,加入20mL正己烷回流10分钟后过滤,室温下挥发除去溶剂即得到Dy(hfac)3·2H2O,产率70%。
3)[Dy(hfac)3((1R)-(-)-Myrtenal-NIT)]n的合成:
将Dy(hfac)3·2H2O的正己烷溶液在90℃下搅拌回流两个小时后,缓慢降温至70℃,滴加(1R)-(-)-Myrtenal-NIT的二氯甲烷溶液,反应5分钟后,降至室温并过滤,滤液放置于干燥器中,室温下挥发一周时间得到浅蓝色长条状晶体,产率25%。
其中,Dy(hfac)3·2H2O的浓度为0.0016mol/L。(1R)-(-)-Myrtenal-NIT的浓度为0.008 mol/L。Dy(hfac)3·2H2O与(1R)-(-)-Myrtenal-NIT的摩尔比为1:1。
该手性稀土-氮氧自由基单链磁体的结构测定:
单晶X-射线衍射结构测定采用Oxford Supernova型-射线单晶衍射仪,使用经过石墨单色器单色化的Mo-Kα射线作为光源,以扫描方式收集衍射点,非氢原子的坐标用直接法解出,用最小二乘法对其坐标和各向异性参数进行精修。氢原子的位置由理论加氢得到,所有的计算使用SHELXL-97和SHELXL-97程序包进行。结果表明该配合物的结构式为[Dy(hfac)3((1R)-(-)-Myrtenal-NIT)]n,属于单斜晶系,空间群为P21,晶胞参数为α=γ=90°,β=117.863(2)°,晶胞体积为Z=8,Dcalcd=1.791g·cm-3。晶体测定数据见表1,单晶结构见图1。其中:图1(a)为该手性稀土-氮氧自由基配合物材料中四个晶体学独立的Dy3+的配位模式图,图1(b)为该手性稀土-氮氧自由基配合物材料从b方向观察的空间堆积图。该配合物的最小不对称单元中包含四个晶体学独立的Dy3+和四个 (1R)-(-)-Myrtenal-NIT分子,Dy3+具有八配位环境{DyO8},其中六个氧原子来自于三个 hfac,两个氧原子来自于两个(1R)-(-)-Myrtenal-NIT,每个(1R)-(-)-Myrtenal-NIT作为桥联配体连接两个Dy3+离子,形成一条无限一维链,晶体数据如表1所示。
表1配合物的晶体学数据
该手性稀土-氮氧自由基配合物的圆二色谱测试:
圆二色谱测试采用将粉末样品和烘干后的溴化钾以质量比1:100混合压片后,在JASCO J-715圆二色谱仪装置完成。
该手性稀土-氮氧自由基配合物的磁性测试:
磁性测试使用Quantum Design MPMS VSM SQUID装置完成;实验数据均采用Pascal’s常数进行抗磁校正。测试方法是:将制备的晶体研磨得到粉末样品,取10mg装入磁性测试胶囊,用VSM SQUID装置进行直流以及交流的磁性测试。
图3(a)是对该手性稀土-氮氧自由基配合物进行直流变温磁化率测试,300K时χMT值为14.14cm3mol-1K,与未耦合的一个Dy3+离子加上一个自由基的理论值接近(14.55cm3mol-1K)。图3(b)是对该金属-氮氧自由基配合物进行的在+5T到-5T之间的变场磁化强度测试,结果显示其在±2.5T之间呈现一个接近矩形的磁滞回环,随着温度的升高,磁滞回环的开口逐渐减小并在4K时闭合。
图4(a)和图4(b)分别是对该金属-氮氧自由基配合物进行零场下的变温和变频交流磁化率测试得到的虚部数据,均显示出明显的对温度和频率的依赖性,说明该配合物存在慢磁驰豫行为。图4(c)是该配合物的变频交流磁化率测试的虚部数据对实部数据作图得到的Cole-Cole图,它比较接近半圆形,用单一驰豫的德拜模型(Debye)对其进行拟合得到与数据点(圆圈)吻合较好的拟合线(实线)。
Claims (2)
1.一种手性稀土-氮氧自由基单链磁体材料的制备方法,所述单链磁体材料的化学式为:[Dy(hfac)3((1R)-(-)-Myrtenal-NIT)]n,式中n为1到正无穷的自然数,hfac为六氟乙酰丙酮基团,(1R)-(-)-Myrtenal-NIT为2-((1R)-6,6-二甲基二环[3.1.1]庚-2-烯基)-4,4,5,5-四甲基咪唑啉-3-氧化-1-氧基自由基;晶体结晶在单斜晶系,空间群为P21,晶胞参数为:为α=γ=90°,β=117.863(2)°,晶胞体积为Z=8;中心Dy3+离子与来自三个hfac的六个氧原子和来自两个(1R)-(-)-Myrtenal-NIT的两个氧原子配位,每个(1R)-(-)-Myrtenal-NIT作为桥联配体连接两个Dy3+离子,形成一条无限一维链;其特征在于:所述方法以六氟乙酰丙酮镝水合物为金属盐,以(1R)-(-)-Myrtenal-NIT为配体,以正己烷和二氯甲烷为溶剂,合成步骤包括:
1)向圆底烧瓶中加入Dy(hfac)3·2H2O的正己烷溶液,90-110℃下搅拌回流2-3小时,缓慢降温至50-70℃后滴加(1R)-(-)-Myrtenal-NIT的二氯甲烷溶液,反应5-10分钟后,降至室温,过滤;
2)将上述滤液置于烧杯中,薄膜封口,置于干燥器中;室温挥发一周,即得到目标产物。
2.根据权利要求1所述手性稀土-氮氧自由基单链磁体材料的制备方法,其特征在于:所述Dy(hfac)3·2H2O的浓度为0.0016mol/L;(1R)-(-)-Myrtenal-NIT的浓度为0.008mol/L;所述Dy(hfac)3·2H2O与(1R)-(-)-Myrtenal-NIT的摩尔比为1:1。
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