CN104402915A - 一种Tm(Ⅲ)-氮氧自由基配合物及其制备方法 - Google Patents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
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Abstract
本发明涉及一种Tm(III)-氮氧自由基配合物及其制备方法。该配合物的化学式为[Tm(hfac)3(NIT-Ph-O-CH2-CH2-Br)2]，其中hfac＝六氟乙酰丙酮，NIT-Ph-O-CH2-CH2-Br＝2-(4-(2’-溴乙基)苯氧基)-4，4，5，5-四甲基咪唑啉-3-氧化-1-氧基自由基；它具有零维结构。将Tm(hfac)3·2H2O的无水正庚烷溶液与NIT-Ph-O-CH2-CH2-Br的二氯甲烷溶液混合，反应30分钟后，冷至室温过滤，滤液放冰箱中，几天后可得目标产品。
Description
技术领域
本发明属于配合物科学与技术领域，特别涉及一种Tm(III)-氮氧自由基配合物及其制备方法。
技术背景
因配合物兼具无机化合物和有机化合物的特点，其组成的复杂性、金属和配体种类的多样性、配位环境的可调性，使之成为分子铁磁体中最有潜在应用前景的一类体系。由于稳定氮氧自由基本身是自旋载体，又有配位功能，使之成为分子基铁磁体的有效构件。自由基-金属配合物的研究对分子铁磁体的合成及偶合机制的阐明提供了丰富的内容和途径。
稀土元素是由15种镧系元素(La，Ce，Pr，Nd，Pm，Sm，Eu，Gd，Tb，Dy，Ho，Er，Tm，Yb，Lu)和IIIB族的钪(Sc)、钇(Y)两种元素组成。其中镧系元素具有相同的电子层结构，它们在4f轨道上的电子数从0到14之间变化。除了La3+和Lu3+离子之外，在一定条件下，镧系元素离子的电子可以在4f轨道间跃迁，内层4f轨道的电子在不同能级之间的跃迁产生了大量的吸收和发射光谱信息，其中每种离子的电子的f-f有辐射跃迁相应形成了这种离子的特征发射光谱，稀土元素的成单电子又与该种元素化合物的磁性直接相关，因此，在光学和磁学等方面具有独特的性质。自Weissman发现用近紫外光可以激发某些含共轭体系有机配体的稀土配合物可以产生荧光以来，稀土荧光配合物的研究一直是一个极其活跃的研究领域，并已成为当前化学、物理，生物及材料科学研究的重要内容之一。稀土离子具有独特的电子结构和成键特征，它与有机配体形成的配合物具有与其它无机化合物不同的发光机制，且其发光性能可通过改变有机配体的组成和结构加以调控，所发出的荧光兼有稀土离子发光强度高、颜色纯正和有机化合物所需激发能量低、荧光效率高、易溶于有机溶剂的优点，为人们探索新的发光材料提供了新思路。因此稀土金属-氮氧自由基的研究有着广阔的前景。
发明内容
本发明的目的是提供了一种Tm(III)-氮氧自由基配合物及其制备方法。该配合物具有零维结构，具有较好的应用前景。
本发明提供的配合物的化学式为[Tm(hfac)3(NIT-Ph-O-CH2-CH2-Br)2]，其中hfac＝六氟乙酰丙酮，NIT-Ph-O-CH2-CH2-Br＝2-(4-(2′-溴乙基)苯氧基)-4，4，5，5-四甲基咪唑啉-3-氧化-1-氧基自由基。
本发明公开的配合物属于三斜晶系，P-1空间群。它是由一个金属和两个自由基构成(见图1)。Tm(III)离子为配位数为八的变形十二面体构型，其中六个配位点由三个hfac的六个氧(O1，O2，O3，O4，O5，O6)占据，两个配位点由两个自由基N-O部分的氧(O10和O11)配位。自由基未配位部分的N-O键长为和自由基配位部分的N-O键长为和Tm1-O10和Tm1-O11键长分别为2.334(3)和Tm1-O1-6(六个O原子来自三个hfac)的键长范围为 两个自由基的五原子部分O-N-C-N-O近似一个平面，与各自相邻苯环分别成24.59°和32.17°的角。
本发明的制备方法如下：
将Tm(hfac)3·2H2O溶于无水正庚烷中，加热回流一小时。将溶液放置冷至65℃，然后加入NIT-Ph-O-CH2-CH2-Br的二氯甲烷溶液，反应30分钟后，冷至室温过滤，滤液放冰箱中，几天后得到深蓝色晶体，即为目标产品。
附图说明
图1[Tm(hfac)3(NIT-Ph-O-CH2-CH2-Br)2]的分子结构
表1配合物的晶体学数据
具体实施方式
实施例1配合物的合成：
将Tm(hfac)3·2H2O(82mg，0.1mmol)溶于15mL沸腾的无水正庚烷中，此溶液加热回流一小时。将溶液放置冷至65℃，然后加入含NIT-Ph-O-CH2-CH2-Br(36mg，0.1mmol)的5mL二氯甲烷溶液，反应30分钟后，冷至室温过滤，滤液放冰箱中，几天后得到深兰色晶体，，即为目标产物。
实施例2配合物的结构测定：
选取合适尺寸的晶体，用Bruker Smart/Rigaku 007型X-射线单晶衍射仪，在室温下，采用经石墨单色器单色化的MoKα射线作为入射光源，以扫描方式收衍射数据。非氢原子用直接法解出，并对它们的坐标及其各向异性热参数进行用全矩阵最小二乘法修正。氢原子的位置由理论加氢得到，并使用骑式换型位置参数和固定的各向同性热参数加入结构精修。所有的计算使用SHELXS-97和SHELXL-97程序包进行。有关衍射分析的实验条件、结构解析、修正方法和晶体学数据见表1，结构见图1，图1：[Tm(hfac)3(NIT-Ph-O-CH2-CH2-Br)2]的分子结构图。
Claims (5)
1.一种Tm(III)-氮氧自由基配合物，该配合物的化学式为[Tm(hfac)3(NIT-Ph-O-CH2-CH2-Br)2]，其中hfac＝六氟乙酰丙酮，NIT-Ph-O-CH2-CH2-Br＝2-(4-(2′-溴乙基)苯氧基)-4，4，5，5-四甲基咪唑啉-3-氧化-1-氧基自由基。
2.根据权利要求1所述的配合物，其特征在于它的结构为：
它是由一个金属和两个自由基构成；Tm(III)离子为配位数为八的变形十二面体构型，其中六个配位点由三个hfac的六个氧(O1，O2，O3，O4，O5，O6)占据，两个配位点由两个自由基N-O部分的氧(O10和O11)配位；自由基未配位部分的N-O键长为1.271(4)(N1-O9)和1.262(4)(N4-O12)；自由基配位部分的N-O键长为1.293(4)(N2-O10)和1.310(4)(N3-O11)；Tml-O10和Tml-O11键长分别为2.334(3)和2.264(3)，Tml-O1-6(六个O原子来自三个hfac)的键长范围为2.293(2)-2.344(3)；两个自由基的五原子部分O-N-C-N-O近似一个平面，与各自相邻苯环分别成24.59°和32.17°的角。
3.根据权利要求1所述的配合物的制备方法，其特征在于它包括下述步骤：
1)按计量将Tm(hfac)3·2H2O溶于沸腾的无水正庚烷中，此溶液加热回流一小时；
2)将溶液冷至65℃，然后加入NIT-Ph-O-CH2-CH2-Br的二氯甲烷溶液，反应30分钟后，冷至室温过滤，几天后得到目标产品。
4.根据权利要求3所述的配合物的制备方法，其特征在于所述的Tm(hfac)3·2H2O和NIT-Ph-O-CH2-CH2-Br的摩尔比为1∶1，且NIT-Ph-O-CH2-CH2-Br要先溶于二氯甲烷溶液中。
5.根据权利要求3所述的配合物的制备方法，其特征在于所述的过滤后的滤液放在冰箱中，以培养晶体。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108358954A (zh) * | 2018-01-17 | 2018-08-03 | 南开大学 | 一种手性稀土-氮氧自由基单链磁体及其制备方法 |
| CN111471187A (zh) * | 2020-04-16 | 2020-07-31 | 太原工业学院 | 一维链状Gd-喹啉氮氧自由基配位聚合物及其制备方法 |
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- 2014-10-31 CN CN201410598777.2A patent/CN104402915A/zh active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108358954A (zh) * | 2018-01-17 | 2018-08-03 | 南开大学 | 一种手性稀土-氮氧自由基单链磁体及其制备方法 |
| CN108358954B (zh) * | 2018-01-17 | 2019-10-29 | 南开大学 | 一种手性稀土-氮氧自由基单链磁体及其制备方法 |
| CN111471187A (zh) * | 2020-04-16 | 2020-07-31 | 太原工业学院 | 一维链状Gd-喹啉氮氧自由基配位聚合物及其制备方法 |
| CN111471187B (zh) * | 2020-04-16 | 2021-10-22 | 太原工业学院 | 一维链状Gd-喹啉氮氧自由基配位聚合物及其制备方法 |
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Application publication date: 20150311 |