CN114106019A - 吡唑-3-甲酸铜配合物的晶体结构及其磁性质 - Google Patents
吡唑-3-甲酸铜配合物的晶体结构及其磁性质 Download PDFInfo
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- 230000005291 magnetic effect Effects 0.000 title claims abstract description 16
- 239000013078 crystal Substances 0.000 title claims abstract description 10
- JVZRCNQLWOELDU-UHFFFAOYSA-N 4-Phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000002500 ions Chemical class 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 15
- 230000005290 antiferromagnetic effect Effects 0.000 claims abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000003993 interaction Effects 0.000 claims abstract description 4
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- -1 pyrazole-3-formic acid anions Chemical class 0.000 claims abstract description 4
- 230000003247 decreasing effect Effects 0.000 claims 1
- 150000004699 copper complex Chemical class 0.000 abstract description 3
- 239000000696 magnetic material Substances 0.000 abstract description 3
- KOPFEFZSAMLEHK-UHFFFAOYSA-N 1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1C=CNN=1 KOPFEFZSAMLEHK-UHFFFAOYSA-N 0.000 description 10
- 239000003446 ligand Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- UCVLLINNDSWSFF-UHFFFAOYSA-L copper;1h-pyrazole-5-carboxylate Chemical compound [Cu+2].[O-]C(=O)C=1C=CNN=1.[O-]C(=O)C=1C=CNN=1 UCVLLINNDSWSFF-UHFFFAOYSA-L 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
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- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
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- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/0009—Antiferromagnetic materials, i.e. materials exhibiting a Néel transition temperature
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Abstract
本发明公开了吡唑‑3‑甲酸铜配合物的晶体结构及其磁性质研究。该铜配合物属于正交晶系，空间群为Pcab，中心金属离子为Cu(II)离子。该配合物最小结构单元包含两个Cu(ΙΙ)离子，两个个4‑苯基吡啶中性分子，两个吡唑‑3‑甲酸阴离子和两个游离的水分子。磁性研究表明该配合物中Cu(II)离子之间存在弱的反铁磁相互作用。本发明成功的合成了吡‑3‑甲酸铜配合物并培养出单晶，解析其晶体结构，进行了变温磁化率测试，为磁性材料的研究与应用提供了一定的依据。
Description
技术领域
本发明属于配合物性质研究技术领域，特别涉及一种吡唑-3-甲酸铜配合物的晶体结构及其磁性质研究。
背景技术
羧基在磁性配合物中是一种优异的桥联基团，其能够通过单齿、桥式双齿、鳌合双齿等配位模式与金属中心离子合成单核、多核、链状或层状配合物。另外。羧基上氧原子还可参与形成氢键，有利于配合物骨架更加稳定。因此有机羧酸配体被广泛用于合成结构优异且具有特殊性质的配合物，研究者们采用芳香羧酸类配体和金属离子配位合成具有应用价值或潜在价值的配合物。
分子基磁体是通过化学方法将自旋载体通过桥连配体以特定的方式组合而形成的具有自发磁化行为的化合物，在量子计算、高密度信息储存、光磁和电磁材料等领域备受重视，有望成为新一代的磁性材料。配合物磁性的研究已成为跨越物理、化学、材料科学和生命科学等诸多学科的最为活跃的前沿研究领域之一。
发明内容
本发明的目的是提供吡唑-3-甲酸铜配合物的结构及其磁性质。
本发明的思路：利用吡唑-3-甲酸、4-苯基吡啶为配体与三水合硝酸铜通过水热法获得铜配合物。
吡唑-3-甲酸铜配合物的结构见附图1。该配合物属于正交晶系，空间群为Pcab，中心金属离子为Cu(II)离子，晶胞参数：
α＝90°，β＝90°，γ＝90°，
Z＝8，Dc＝1.647g·cm-3，μ＝1.58mm-1，F(000)＝1416。配合物最小结构单元包含两个Cu(ΙΙ)离子，两个吡唑-3-甲酸阴离子，两个4-苯基吡啶中性分子和两个游离的水分子。金属中心Cu(II)离子均是五配位的，五个配位原子在中心离子周围形成了不规则的四方锥构型。吡唑-3-甲酸通过四齿螯合桥连的方式与金属Cu(II)离子配位，4-苯基吡啶通过单齿的形式与金属离子Cu(II)离子配位，共同构成了该配合物的二维层状结构，通过层与层之间的4-苯基吡啶的π-π堆积作用，构成了该配合物的三维结构。
铜配合物的磁性质研究：
吡唑-3-甲酸铜配合物的磁性研究如附图2所示，在1000Oe的外加磁场下，在300-2K温度范围内测定配合物的变温磁化率。在300K时，χMT为0.755cm3·K·mol-1，接近于两个未发生耦合作用的高自旋Cu(II)(S＝1/2,g＝2.0)的理论自旋值0.750cm3·K·mol-1。随着温度的不断降低，χMT值呈下降趋势，温度降到2K时达到最小值0.006cm3·K·mol-1，这表明配合物中Cu(II)离子之间存在一定程度的反铁磁相互作用。对配合物的χM -1-T在50-300K范围内进行线性拟合，可知其符合居里-外斯定律[χM＝C/(T-θ)]，计算得到居里常数C＝2.11cm3·K·mol-1，外斯常数θ＝-535.6K，θ<0，证明配合物Cu(II)离子之间存在弱的反铁磁相互作用。
本发明成功的合成了吡唑-3-甲酸铜配合物并培养出单晶，解析了其晶体结构，并进行了变温磁化率测试，为磁性材料的研究与应用提供了一定的依据。
附图说明
图1是本发明的吡唑-3-甲酸铜配合物分子结构图。
图2是本发明的吡唑-3-甲酸铜配合物变温磁化率图。
具体结构描述
配合物属于单斜晶系，Pca空间群，晶胞参数：
α＝90°，β＝90°，γ＝90°，
Z＝8，Dc＝1.647g·cm-3，μ＝1.577mm-1，F(000)＝1416.0。
晶体衍射表明，配合物的最小结构单元包含两个个Cu(ΙΙ)离子，两个吡唑-3-甲酸阴离子，两个4-苯基吡啶分子和两个游离的水分子。吡唑-3-甲酸通过死吃齿螯合桥连的方式参与配位，中性4-苯基吡啶分子通过单齿的方式参与配位。金属中心离子Cu(ΙΙ)1分别与来自吡唑-3-甲酸的羧基氧原子(O1)和吡唑环上的氮原子(N1)配位，与另一个吡唑-3-甲酸上的氮原子(N2A)和羧基氧原子(O2A)配位，与4-苯基吡啶的一个氮原子(N3)配位。Cu(ΙΙ)1A与Cu(ΙΙ)1配位方式相同，均为五配位模式。五个原子在Cu(ΙΙ)离子周围形成了不规则的四方锥构型，中心铜离子通过吡唑-3-甲酸的桥联作用形成了二维层状结构。另外，配合物通过4-苯基吡啶的π-π堆积作用，形成了铜配合物的三维空间结构。
Claims (2)
1.一种吡唑-3-甲酸铜配合物的晶体结构，该配合物属于正交晶系，空间群为Pcab，中心金属离子为Cu(II)离子，其最小结构单元由两个Cu(II)离子，两个吡唑-3-甲酸阴离子，两个4-苯基吡啶中性分子和两个游离的水分子组成。
2.如权利要求1中所述的吡唑-3-甲酸铜配合物的磁性质研究，在变温磁化率测试的300-2K温度范围内，随着温度的不断降低，χMT值一直呈下降的趋势，这一现象说明磁交换参数J<0，即配合物中Cu(II)离子之间是反铁磁的相互作用；再对配合物的χM -1-T在50-300K范围内进行线性拟合，可知其符合居里-外斯定律[χM＝C/(T-θ)]，计算得到居里常数C＝2.11cm3·K·mol-1，外斯常数θ＝-535.6K，θ<0；进一步证明配合物Cu(II)离子之间存在弱的反铁磁相互作用。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003053895A2 (en) * | 2001-12-12 | 2003-07-03 | E.I. Du Pont De Nemours And Company | Copper deposition using copper formate complexes |
| CN105348304A (zh) * | 2015-10-18 | 2016-02-24 | 桂林理工大学 | 单核吡唑-3-甲酸铜配合物及其制备方法 |
| CN109336910A (zh) * | 2018-11-03 | 2019-02-15 | 桂林理工大学 | 吡唑-4-甲酸铜配合物及制备方法 |
| CN109503632A (zh) * | 2018-11-03 | 2019-03-22 | 桂林理工大学 | 吡唑-3-甲酸铜配合物及制备方法 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003053895A2 (en) * | 2001-12-12 | 2003-07-03 | E.I. Du Pont De Nemours And Company | Copper deposition using copper formate complexes |
| CN105348304A (zh) * | 2015-10-18 | 2016-02-24 | 桂林理工大学 | 单核吡唑-3-甲酸铜配合物及其制备方法 |
| CN109336910A (zh) * | 2018-11-03 | 2019-02-15 | 桂林理工大学 | 吡唑-4-甲酸铜配合物及制备方法 |
| CN109503632A (zh) * | 2018-11-03 | 2019-03-22 | 桂林理工大学 | 吡唑-3-甲酸铜配合物及制备方法 |
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