CN104341458A - 一种Co(II)-氮氧自由基配合物及其制备方法 - Google Patents
一种Co(II)-氮氧自由基配合物及其制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000010668 complexation reaction Methods 0.000 title description 4
- 150000003254 radicals Chemical class 0.000 claims abstract description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N anhydrous n-heptane Natural products CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract 2
- 239000013078 crystal Substances 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 abstract 1
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- 150000004700 cobalt complex Chemical class 0.000 description 2
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- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000005298 paramagnetic effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PZSXCNWLLFEOPM-UHFFFAOYSA-N [F].C(CC)(=O)O Chemical compound [F].C(CC)(=O)O PZSXCNWLLFEOPM-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
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Abstract
本发明涉及一种Co(II)-氮氧自由基配合物及其制备方法。该配合物的化学式为[Co(hfac)2(NIT-5-Br-3Py)]2,其中hfac=六氟乙酰丙酮,NIT-5-Br-3Py=2-(5-溴-3-吡啶)-4,4,5,5-四甲基咪唑啉-3-氧化-1-氧基自由基;它具有二聚体的结构。将Co(hfac)2·2H2O的无水正庚烷溶液和NIT-5-Br-3Py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Co(II)-氮氧自由基配合物及其制备方法。
技术背景
八十年代以来,分子材料的研究高速发展,其中分子铁磁体的设计与合成是竞争最激烈的研究领域之一。所谓分子铁磁体是指使用制备分子化合物的方法合成具有磁体一样性质的分子集合体,使其在某临界温度(Tc)下具有自发的磁化作用。分子铁磁体与以往的合金类磁体相比,具有体积小,比重轻,结构多样,易于复合与加工成型等特点,从而有更广泛的用途。
目前,已发现的具有分子铁磁性的体系主要有三类:一,有机体系,顺磁中心是自由基;二,无机体系,顺磁中心是顺磁金属离子;三,金属-自由基体系,顺磁中心是有机自由基和金属离子。近年来,氮氧自由基-金属配合物越来越引起人们的广泛关注,已有多篇综述文章发表。氮氧自由基配合物与纯有机物及合金相比,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,使之成为分子材料中最有潜在应用前景的一类体系。与一般的配合物相比,自由基是一个具有顺磁中心的配体,它与具有顺磁性的金属离子配位后得到的配合物显示出磁与光、磁与电及磁与化学相关联的不寻常的性质。八十年代初人们合成了第一个有晶体结构数据的氮氧自由基配合物,之后人们进行了长期不懈的探索。直到九十年代中叶前,人们关注和研究的重点基本集中在通过加入有吸电子能力的配体如:六氟乙酰丙酮(hfac)、五氟丙酸(pfpr)等,来增强金属与自由基配位的可能性以便得到更好的具有磁相互作用的配合物,这些工作取得了一定的成果。
与此同时,过渡金属Co(II)离子配合物也受到越来越多的重视。由于Co(II)离子旋-轨耦合导致的很强的磁各向异性,因而Co(II)离子是合成分子磁体的理想选择。
发明内容
本发明的目的是提供了一种Co(II)-氮氧自由基配合物及其制备方法。该配合物具有零维四核结构,具有较好的应用前景。
本发明提供的钴配合物的化学式为[Co(hfac)2(NIT-5-Br-3Py)]2,其中hfac=六氟乙酰丙酮,NIT-5-Br-3Py=2-(5-溴-3-吡啶)-4,4,5,5-四甲基咪唑啉-3-氧化-1-氧基自由基。
本发明公开的钴配合物属于三斜晶系,P-1空间群。分子结构如图1所示,是二聚体结构。Co(II)离子是六配位的拉长八面体构型,两个hfac提供的三个氧原子(O3,O4,O6)和一个自由基提供的一个氧原子(O1)构成赤道平面。另一个自由基提供的一个氮原子(N1A)和一个hfac提供的一个氧原子(O5)处于轴向上。在配合物中,两个自由基以顺式与Co(II)配位,形成O1-Co1-N1A的角度为88.1(3)°。自由基的N-O键长为(配位)和(未配位)。自由基的五原子部分O-N-C-N-O近似一个平面,与吡啶环成29.7°
本发明的制备方法如下:
将Co(hfac)2·2H2O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-5-Br-3Py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[Co(hfac)2(NIT-5-Br-3Py)]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Co(hfac)2·2H2O(52mg,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-5-Br-3Py(31mg,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,几天后得到的浅棕色晶体,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:[Co(hfac)2(NIT-5-Br-3Py)]2的分子结构图。
Claims (5)
1.一种Co(II)-氮氧自由基配合物,该配合物的化学式为[Co(hfac)2(NIT-5-Br-3Py)]2,其中hfac=六氟乙酰丙酮,NIT-5-Br-3Py=2-(5-溴-3-吡啶)-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Co(II)-氮氧自由基配合物,其特征在于它的二聚体结构为:
Co(II)离子是六配位的拉长八面体构型,两个hfac提供的三个氧原子(O3,O4,O6)和一个自由基提供的一个氧原子(O1)构成赤道平面;另一个自由基提供的一个氮原子(N1A)和一个hfac提供的一个氧原子(O5)处于轴向上;在配合物中,两个自由基以顺式与Co(II)配位,形成O1-Co1-N1A的角度为88.1(3)°;自由基的N-O键长为(配位)和(未配位);自由基的五原子部分O-N-C-N-O近似一个平面,与吡啶环成29.7°。
3.根据权利要求1所述的Co(II)-氮氧自由基的制备方法,其特征在于它包括下述步骤:
1)按计量将Co(hfac)2·2H2O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-5-Br-3Py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Co(II)-氮氧自由基配合物的制备方法,其特征在于所述的Co(hfac)2·2H2O和NIT-5-Br-3Py的摩尔比为1∶1,且NIT-5-Br-3Py要先溶于二氯甲烷溶液中。
5.根据权利要求3所述的Co(II)-氮氧自由基配合物的制备方法,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 |
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CN109517011A (zh) * | 2018-12-07 | 2019-03-26 | 南开大学 | 具有6.3t矫顽力的钴-萘环氮氧自由基分子磁体材料及其制备方法 |
CN115651032A (zh) * | 2022-09-30 | 2023-01-31 | 洛阳师范学院 | 一种基于甲氧基嘧啶氮氧自由基配体的磁性Co配合物及其制备方法 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN109517011A (zh) * | 2018-12-07 | 2019-03-26 | 南开大学 | 具有6.3t矫顽力的钴-萘环氮氧自由基分子磁体材料及其制备方法 |
CN115651032A (zh) * | 2022-09-30 | 2023-01-31 | 洛阳师范学院 | 一种基于甲氧基嘧啶氮氧自由基配体的磁性Co配合物及其制备方法 |
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