CN104945423B - 一种双金属克酮酸配合物及其制备方法 - Google Patents
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Abstract
本发明涉及一种双金属克酮酸配合物及其制备方法，配合物为：[TbK(C5O5)2(H2O)6]·2H2O，其中C5O5 2‑为克酮酸阴离子。该配合物的制备是将克酮酸、TbCl3和KOH分别溶解于水，将三者混合，搅拌，室温静置，3天后有橘黄色块状晶体析出，过滤收集产品。该配合物结构中包含一维链状金属单元，金属离子之间表现为反铁磁相互作用；该配合物结晶于极性空间群，室温下具有铁电性，另外用波长为372nm的光激发该固态配合物，样品可发射较强荧光。因此，该配合物同时具有反铁磁性、铁电性和荧光性质，是一种潜在的光电磁多功能材料。
Description
技术领域
本发明涉及金属配合物，特别涉及一种含钾和铽的双金属配合物，具体属于一种基于钾(I)和铽(III)混合离子与克酮酸构筑的具有光电磁性质的配合物及其制备方法。
背景技术
基于分子材料拓展的多功能材料中，集合磁性和铁电性的多铁材料是目前很多生产技术的本质所在，具有重要的理论意义和潜在的应用价值，其中，无机-有机配合物型的多铁材料近年来逐步进入了人们的视线，由于其兼具无机多铁材料和有机多铁材料的优点，是一种可具有多重双稳态特性的多功能材料，因此受到越来越多科研工作者的关注。目前，由稀土元素构成的多铁材料主要为无机物，如稀土锰氧化合物(如TbMnO3或TbMn2O5)和稀土铁氧化合物(如Tb3Fe5O12)，由于存在较强的磁电耦合作用，是多铁材料研究的焦点之一，但包含稀土元素的无机-有机配合物类多铁材料的研究仍为空白。
发明内容
本发明的目的正是针对上述技术现状，提供一种可以作为多铁及光电磁多功能材料的双金属克酮酸配合物及其制备方法。
本发明提供的一种双金属克酮酸配合物，结构简式为：[TbK(C5O5)2(H2O)6]·2H2O，其中C5O5 2-为克酮酸阴离子；结构式为：
该配合物的晶体属于正交晶系，空间群为Cmc21，晶胞参数为： α＝β＝γ＝90.00°。该配合物的不对称结构单元是由一个Tb3+、两个克酮酸阴离子、一个K+、六个配位水分子和两个游离水分子组成。其中，Tb3+是为九配位，呈现单帽四方反棱柱的配位模式，与Tb3+配位的氧原子分别来自两个克酮酸、五个配位水，Tb-O键的键长范围为碱金属K+是十配位，呈现双帽十二面体的配位模式，与K+配位的氧原子来自四个克酮酸和六个配位水。该配合物是一个三维结构，沿a轴方向，通过配体克酮酸，Tb3+和K+相间连成了一维长链；随后，通过O7，O6和O8原子，一维长链向b轴和c轴方向拓展，形成三维网络结构。
X射线粉末衍射证实晶体样品均一稳定。热重分析结果表明，该配合物的骨架结构在250℃以下可以稳定存在。通过2000Oe外磁场作用下的变温磁化率实验数据得出金属离子间存在反铁磁相互作用，利用居里-韦斯定律对χm -1-T的实验值进行拟合，得到θ＝-3.33K，表明配合物金属离子间存在反铁磁相互作用。室温条件下配合物的单晶样品在外加电场E＝6V时，饱和极化强度Ps＝0.44μC/cm2，剩余极化强度Pr＝0.22μC/cm2，矫顽场Ec＝2.11V，表明室温条件下配合物为铁电体。室温条件下配合物的固体荧光发射光谱显示，当激发波长为372nm时，样品可发射较强荧光。
本发明提供的一种双金属克酮酸配合物的制备方法，包括如下步骤：
(1)将摩尔比为1:1:1～1.5(优选1:1:1～1.2)的TbCl3、KOH和克酮酸分别溶解于水，将三者混合；
(2)室温搅拌均匀，室温静置，3天后有橘黄色块状晶体充分析出，过滤，收集产品。
本发明的优点和效果：
本发明涉及的双金属克酮酸配合物是用常规化学合成方法得到，制备方法工艺简单，晶体样品纯度高，生长快，收率高。本发明提供的双金属配合物是基于克酮酸配体构筑的，在2000Oe外磁场下通过变温磁化率实验数据得出金属离子间存在反铁磁相互作用，θ＝-3.33K；该配合物结晶于极性空间群，室温时具有铁电性；另外用波长为372nm的光激发该固态配合物，样品可发较强荧光。该配合物同时具有反铁磁性、铁电性和荧光性质，可用作光电磁多功能材料。
附图说明
图1[TbK(C5O5)2(H2O)6]·2H2O的不对称单元结构图。(为了图片清晰，省略了溶剂分子)
图2配合物在298K的X射线粉末衍射图(实验及模拟图)。
图3配合物的热重分析图。
图4配合物在2000Oe外磁场作用下的磁性质及其拟合曲线图。
图5配合物单晶样品在室温下的电滞回环。
图6配合物在298K的荧光光谱图(激发及发射谱)。
具体实施方式
实施例1.分别取70μL克酮酸溶液(0.025mol/L)、50μL TbCl3溶液(0.0375mol/L)和50μL KOH溶液(0.0375mol/L)，将三者混合于96孔板中，25℃搅拌后，25℃静置，3天后,96孔板底部有橘黄色块状晶体析出，过滤收集，产率为35％。
配合物的结构测定：
将晶体样品固定在Bruker SMART 1000CCD面探衍射仪上，以石墨单色器MoKα为辐射光源，收集样品对波长为的X-Ray衍射数据。以ω扫描方式，衍射数据经LP因子和经验吸收校正。全部X-Ray衍射图还原为衍射指标后，用SHELXTL-NT 5.10版程序包，直接法确定X-Ray衍射强度的位相，初始结构经全矩阵最小二乘法做数轮修正，找出全部非氢原子坐标，确认残余峰不再有非氢原子后，做各向异性温度因子处理。C原子采用理论加氢，水分子中O原子上的氢由差值Fourier合成给出， 并固定在母原子上。详细的晶体测定数据见表1。结构见图1。
表1 配合物的晶体学数据
粉末衍射：
X-射线粉末衍射结果表明，晶体样品物相均一，实验衍射图谱与依据晶体结构模拟的粉末衍射图谱一致，见图2。
配合物的热重分析：
热重曲线在29℃-196℃之间形成一个平台，质量损失为20.27％，可归结为配合物在此期间失去了2个游离水和5个配位水(理论值20.87％)；对应的差热曲线形成了一个吸热峰，表明配合物在失去游离水和配位水的过程也为吸热反应。此后配合物相对稳定，从360℃开始热重曲线开始下降，在422℃出现拐点，质量损失为12.54％，可归结为配合物在此期间失去了最后一个配位水和一个CO2(理论值12.5％)，此CO2来源于克酮酸的分解，即在此期间配合物的骨架开始分解，此后骨架分解仍在继续。对应的差热曲线形成了一个吸热峰，表明配合物的骨架坍塌也为吸热反应，见图3。
配合物的磁性质：
变温磁化率与温度的乘积随温度变化的曲线如图4所示，从图中可以看出，室温时χmT值为12.89cm3·K·mol-1，随着温度的降低，χmT值逐渐降低，至1.8K时降至5.43cm3·K·mol-1。利用居里-韦斯定律拟合χm -1-T(图4插图)，可以得到C＝13.07cm3·mol-1,θ＝-3.33K，负的θ值表明金属离子间为反铁磁相互作用。
配合物的铁电性质:
电滞回线曲线呈现出了较好的S型，外加电场E＝6V时，饱和极化强度Ps＝0.44μC/cm2，剩余极化强度Pr＝0.22μC/cm2，矫顽场Ec＝2.11V，说明配合物具有一定的铁电性，见图5。
配合物的发光性质：
室温下测定了配合物的固体荧光发射光谱(图6)。从图中可看出，在波长为372nm的光激发下，配合物分别在在468nm、505nm、530nm处有较强的发射峰。
Claims (3)
1.一种双金属克酮酸配合物，其特征在于，结构简式为：[TbK(C5O5)2(H2O)6]·2H2O，其中C5O5 2-为克酮酸阴离子；配合物的晶体测定数据见表1：
表1配合物的晶体学数据
2.如权利要求1所述的一种双金属克酮酸配合物的制备方法，其特征在于，包括如下步骤：分别取70μL 0.025mol/L克酮酸溶液、50μL 0.0375mol/L TbCl3溶液和50μL0.0375mol/LKOH溶液，将三者混合于96孔板中，25℃搅拌后，25℃静置，3天后,96孔板底部有橘黄色块状晶体析出，过滤收集，产率为35％。
3.如权利要求1所述的一种双金属克酮酸配合物作为光电磁多功能材料的应用。
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