CN106883252B - 一种具有高磁熵变的环形钆配合物及其制备方法 - Google Patents
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Abstract
本发明涉及磁制冷材料领域，具体指一种具有高磁熵变的环形钆配合物及其制备方法。该配合物的化学式为[Gd6(H3L)6(benzoate)6]·4H2O，benzoate为苯甲酸根，H5L为双(2‑羟乙基)氨基‑三(羟甲基)甲烷，其制备方法是：将H5L、苯甲酸及硝酸钆混合后加入己腈和甲醇，搅拌溶解并混匀后得到混合溶液，之后将上述混合溶液置于130℃下反应12小时后降温，过滤分离析出的晶体，再经洗涤、干燥后制得。本发明的优点在于：该配合物具备显著的磁热效应，具有作为磁制冷工质方面的潜在应用价值，并且制备工艺较为简单，为制备具有高磁热效应的稀土元素配合物提供了方向。
Description
技术领域
本发明涉及磁制冷材料领域，具体指一种具有高磁熵变的环形钆配合物及其制备方法。
背景技术
磁制冷材料因其潜在的应用也受到了越来越多的关注与研究。虽然诸多原因的限制使磁制冷基础理论尚未成熟，但磁制冷终将因其高效、无污染等特点成为未来颇具潜力的一种新的制冷方式，而对具有较优异磁制材料的研究也必将为磁制冷开辟更加广阔的前景，目前较为热门的磁制冷材料研究方向集中在稀土钆元素方面。
我国是稀土资源大国，稀土盐作为组装功能配位材料的前驱体，材料易得，加工方便，且在自组装过程中可展现配位数不等的配位模式。各种稀土元素离子中，Gd3+离子具有最大的基态自旋，并且各向同性，是研制分子基磁制冷剂的理想选择。尽管如此，目前稀土钆基磁制冷材料的研究还十分有限，在这些研究中，稀土钆基磁制冷材料表现出了丰富多变的结构和优秀的低温磁制冷性能。
发明内容
本发明利用含多羟基的螯合配体与钆金属离子进行自组装配位，可制备出结构新颖的环形钆配合物，该配合物具有较高的磁熵变。
本发明所述具有高磁熵变的环形钆配合物的化学式为
[Gd6(H3L)6(benzoate)6]·4H2O，benzoate为苯甲酸根，H5L为双(2-羟乙基)氨基-三(羟甲基)甲烷，结构式为：
Gd原子采取八配位双帽三角棱柱的配位方式，每个配体上的N原子、2个μ2-O原子和2个η1-O原子占据同一Gd原子上的5个配位点，每个Gd原子又通过配体上的μ2-氧桥与相邻2个Gd原子连接形成环状六核钆稀土簇，每个Gd原子上最后的一个配位点被苯甲酸根占据；所述环形钆配合物属于三方晶系，R-3空间群，晶胞参数为
α＝β＝90°，γ＝120°，晶胞体积为
选用的配体为双(2-羟乙基)氨基-三(羟甲基)甲烷，分子式是C8H19NO5，含有5个羟基，结构式为：
是分子生物学领域的常用试剂，可作为多羟基螯合配体，与钆离子实现自组装配位。
本发明还包括一种制备上述具有高磁熵变的环形钆配合物的方法，包括如下步骤：
1)将H5L、苯甲酸及硝酸钆按照1:1:1的摩尔比例混合后放入容器中，以混合物中的H5L为基准，分别按照40ml/mmol和10ml/mmol的比例添加己腈和甲醇，充分搅拌溶解并混匀后得到混合溶液；
2)将上述混合溶液置于130℃下反应12小时后降温，过滤分离析出的晶体，再经洗涤、干燥后制得具有高磁熵变的环形钆配位物晶体。
本发明所述具有高磁熵变的环状钆配合物具备显著的磁热效应，具有作为磁制冷工质方面的潜在应用价值，并且制备工艺较为简单，为制备具有高磁热效应的稀土元素配合物提供了方向。
附图说明
图1：本发明所述具有高磁熵变的环形钆配合物的单晶衍射解析结构图；
图2：本发明所述具有高磁熵变的环形钆配合物的磁化率随温度变化曲线；
图3：本发明所述具有高磁熵变的环形钆配合物的磁熵变化实验图。
具体实施方式
下面结合实施例及相关实验对本发明所述具有高磁熵变的环形钆配合物及其制备方法作进一步说明。
实施例
称取209mg双(2-羟乙基)氨基-三(羟甲基)甲烷、122mg苯甲酸和451mgGd(NO3)3·6H2O，溶于40mL已腈和10mL甲醇中，常温搅拌30分钟，将混合溶液移于具有聚四氟乙烯内衬的不锈钢反应釜，再将该反应釜置于烘箱内，130℃下反应12小时后降温，过滤分离析出的无色晶体，用蒸馏水洗涤去除游离态的Gd3+杂质，再经干燥后得到最终产品。基于金属Gd计算得到的产率约为60％，产品的元素分析结果为：Anal.Calcd for C90H140N6O46Gd6:H4.73％，C 36.21％，N 2.81％；found H 4.49％，C 37.78％，N 3.02％，表明了实际制取的产品结构与单晶衍射所确定的结构基本一致。
实施例制得的环状钆配合物的性质表征：
1)配合物的结构测定：
从实施例制备的产品中选取合适尺寸的单晶，采用上海光源BL17B高通量晶体结构线站进行结构分析，利用特定光源收集衍射数据，通过仪器自带程序HKL3000完成数据经验吸收校正。最终结构解析及精修则通过SHELXS-14程序由人工完成，其间利用全矩阵最小二乘法(full-matrix least-squares refinement based on F2)定出所有非氢原子并完成各向异性精修。另外，配体上氢原子则通过理论加氢完成
如图1所示，检测结果表明，该环形钆配合物的化学式为[Gd6(H3L)6(benzoate)6]·4H2O，Gd原子采取八配位双帽三角棱柱的配位方式，每个配体上的N原子、2个μ2-O原子和2个η1-O原子占据同一Gd原子上的5个配位点，每个Gd原子又通过配体上的μ2-氧桥与相邻2个Gd原子连接形成环状六核钆稀土簇，每个Gd原子上最后的一个配位点被苯甲酸根占据。该环形钆配合物属于三方晶系，R-3空间群，晶胞参数为
α＝β＝90°，γ＝120°，晶胞体积为
在图1中，与Gd原子Gd(1)螯合的配体上的N原子、2个μ2-O原子O(1)、O(2)，以及2个η1-O原子O(3)、O(4)占据了Gd(1)的5个配位点，O(1)、O(2)还将Gd(1)与相邻的两个Gd原子Gd(2)和Gd(3)桥连。
2)配合物的磁制冷性质表征：
将约25-35mg实施例中制备的钆配合物材料装于特定胶囊中，置于超导量子干涉磁强计进行相关测试，外加场强为1000Oe，温度范围为2-300K。
如图2所示，室温时磁化率数值为46.56cm3K mol-1，与六核无相互作用的钆的磁化率数值比较吻合。随着温度的降低，磁化率数值基本维持为常数，但在低于50K的温度下，磁化率数值开始减小。降低的磁化率数值可能是由于金属离子间的反铁磁相互作用或零场分裂效应导致。根据居里-外斯定律χ＝C/(T-θ)，推算出θ值为-1.43K，表明钆离子间呈现了弱的反铁磁相互作用，如图2中附带的参照小图所示。
利用超导离子干涉仪器MPMS，通过不同温度和场强下通过磁化强度测试数据计算出的磁熵变值ΔSm如图3所示，在2K和ΔH为7T时，该钆配合物的-ΔSm数值可以达到29.9Jkg-1K-1，表明该钆配合物具有显著的磁热效应，在低温磁制冷方面有潜在的应用。
Claims (2)
1.一种具有高磁熵变的环形钆配合物，其特征在于，化学式为[Gd6(H3L)6(benzoate)6]·4H2O，benzoate为苯甲酸根，H5L为双(2-羟乙基)氨基-三(羟甲基)甲烷，Gd原子采取八配位双帽三角棱柱的配位方式，每个配体上的N原子、2个μ2-O原子和2个η1-O原子占据同一Gd原子上的5个配位点，每个Gd原子又通过配体上的μ2-氧桥与相邻2个Gd原子连接形成环状六核钆稀土簇，每个Gd原子上最后的一个配位点被苯甲酸根占据；所述环形钆配合物属于三方晶系，R-3空间群，晶胞参数为
α＝β＝90°，γ＝120°，晶胞体积为
2.一种制备如权利要求1所述的具有高磁熵变的环形钆配合物的方法，其特征在于，包括下列步骤：
1)将H5L、苯甲酸及硝酸钆按照1:1:1的摩尔比例混合后放入容器中，以混合物中的H5L为基准，分别按照40ml/mmol和10ml/mmol的比例添加己腈和甲醇，充分搅拌溶解并混匀后得到混合溶液；
2)将上述混合溶液置于130℃下反应12小时后降温，过滤分离析出的晶体，再经洗涤、干燥后制得具有高磁熵变的环形钆配位物晶体。
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