CN105399774A - 一种含有双三唑丁烷与吡嗪二酸的锰配合物及其制备方法 - Google Patents
一种含有双三唑丁烷与吡嗪二酸的锰配合物及其制备方法 Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 43
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 15
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 title claims abstract description 6
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title claims description 9
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 title claims description 7
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 title abstract 4
- -1 1,4-bi(1H-1,2,4-triazole) butane Chemical group 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 5
- 150000002500 ions Chemical class 0.000 claims description 26
- 235000013844 butane Nutrition 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 7
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- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 239000004693 Polybenzimidazole Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
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Abstract
本发明涉及一种含有双三唑丁烷和2,3-吡嗪二酸的锰配合物的合成方法。其配合物的化学式为[Mn(btb)0.5(pzdc)(H2O)2]·H2O,其中H2pzdc=2,3-吡嗪二酸,btb=1,4-二(1H-1,2,4-三氮唑)丁烷,简称双三唑丁烷,它具有二维网状结构。合成方案为按计量比分别将双三唑丁烷与Mn(CH3COO)2·4H2O配置成水溶液,混合后在常温下搅拌1h,之后加入2,3-吡嗪二酸水溶液,继续常温下搅拌2h。之后过滤溶液,滤液静置,缓慢挥发,约两周后可得到目标产品。
Description
技术领域
本发明属于金属配合物科学及技术领域,具体涉及一种含双三唑丁烷与吡嗪二酸的锰配合物及其制备方法。
技术背景
金属配合物是由可以给出孤对电子或多个不定域电子的配体与具有空轨道的金属离子,以一定的组成和空间构型所形成的的化合物。现今研究最多的是过渡性金属配合物,而其中以Mn(II)离子为中心的金属配合物,由于其结构及性质的特殊性,已成为研究的热点,尤其是在磁学、催化、医学领域方面。
在催化领域,合成的一种席夫碱锰(II)配合物对于醛和硝基甲烷的Henry反应具有明显的催化作用,而且具有反应条件温和、操作简单、产率高、催化剂用量少、且对环境友好等优点[张鹏,有机化学,2013,33,1834];在医学领域,以多苯并咪唑配体为主配体,合成了锰的单、双核两个配合物,研究结果表明,在近中性条件下两个配合物都能促使DNA凝聚且凝聚程度随配合物浓度的增加而增大[黄雪英等,高等化学学报,2012,33,1151];在磁性研究方面,乙腈溶液中合成的混合价四核锰配合物在整体上表现为反铁磁性耦合作用,但在低温下的具有较为复杂的磁相互作用[任颜卫等,化学学报,2005,10,919];而采用溶剂扩散法制备了锰(II)的两个单核配合物,使用循环伏安法研究电化学性质,表明两配合物在DMF溶液中均存在较好的氧化还原性[丁瑜等,化学学报,2009,14,1579]。
金属配合物的设计合成条件对配合物本身的结构影响很大,而配合物的结构又对它的性质有很大影响。此发明中,选用具有多种配位方式的二元羧酸以及具有柔性结构的双三唑丁烷为配体,与锰离子形成一种新型的、结构新颖的混配体金属配合物。
发明内容
本发明的目的是提供一种新型的含双三唑丁烷与吡嗪二酸的锰配合物及其制备方法。该配合物具有二维链状结构,具有广泛的应用前景。
本发明提供的锰配合物的化学式为[Mn(btb)0.5(pzdc)(H2O)2]·H2O,其中H2pzdc=2,3-吡嗪二酸,btb=1,4-二(1H-1,2,4-三氮唑)丁烷,简称双三唑丁烷。
本发明公开的锰配合物的结构如图1所示,它们的二级结构单元为:
晶体属于单斜晶系,空间群为P21/c,晶胞参数为: a=90°,β=111.787(7)°,γ=90°。该配合物分子中含有1个Mn(II)离子、1个pzdc2-阴离子、0.5个btb配体、2个配位水分子及1个游离水分子,Mn(II)离子的配位数为6,pzdc2-阴离子的N4和O1原子以螯合方式与Mn(II)配位,形成一个由Mn1-N4-C5-C9-O1组成的不规则的五元环结构;同时与另一个pzdc2-阴离子的O4A原子、一个btb的N5原子配位及两个配位水氧原子O5和O6配位。如此,以Mn离子为金属中心形成一个畸形的八面体构型,其中N4、O1、O6与N3原子处于八面体的赤道平面上,所形成的4个键角N4-O1-O6、O1-O6-N3、O6-N3-N4和N3-N4-O1分别为98.96(1)°、80.46(1)°、85.04(1)°和93.83(1)°,其和为358.29(4)°,与360°极为接近,基本处于同一平面。每个pzdc2-阴离子都与两个Mn(II)离子配位,在省略btb配体情况下,pzdc2-阴离子与Mn(II)离子交替连接,沿a轴方向形成一维Z字链结构,配体分子btb以μ2桥联方式连接两条一维Z字链上的两个Mn(II)离子,在ab面上形成2D层状结构,其中每个结构单元由4个Mn(II)离子、4个pzdc2-配体阴离子和2个btb配体分子交替连接形成(图2)。
本发明的制备方法如下:
按计量比分别将btb配体与Mn(CH3COO)2·4H2O配置成水溶液,混合后在常温下搅拌1h后,2,3-吡嗪二酸的水溶液,继续常温下搅拌2h。之后过滤溶液,滤液静置,缓慢挥发,约两周后可以得到目标产品。Mn(CH3COO)2·4H2O、btb和H2pzdc的质量之比为:3.06∶7.2∶1。
附图说明
图1[Mn(btb)0.5(pzdc)(H2O)2]·H2O的晶体结构;
图2晶体的二维网状结构。
表1配合物的晶体学数据
具体实施方案
实施例1配合物的合成:
将Mn(CH3COO)2·4H2O(0.1mmol,0.0245g)和btb(0.3mmol,0.0576g)的水溶液(各5ml)混合,常温搅拌1小时后,加入H2pzdc(0.05mmol,0.008g)的水溶液(5mL)。继续常温搅拌两小时后,过滤,滤液静置,缓慢挥发,约一周后可以得到黄色针状晶体。基于金属Mn元素含量计算产率为40%。
实施例2配合物的结构测定:
晶体结构测定采用BRUKERSMART1000X-射线衍射仪,使用经过石墨单色化的Mokα射线为入射辐射,以ω-2θ扫描方式收集衍射点,经过最小二乘法修正得到晶胞参数,从差值Fourier电子密度图利用SHELXL-97直接法解得晶体结构,并经Lorentz和极化效应修正。所有的H原子由差值Fourier合成并经理想位置计算确定。详细的晶体测定数据见表1。结构见图1、图2;图1:[Mn(btb)0.5(pzdc)(H2O)2]·H2O的晶体结构。图2:晶体的二维网状结构。
Claims (5)
1.一种含有双三唑丁烷与2,3-吡嗪二酸的锰配合物及其制备方法,配合物的化学式为[Mn(btb)0.5(pzdc)(H2O)2]·H2O,其中H2pzdc=2,3-吡嗪二酸,btb=1,4-二(1H-1,2,4-三氮唑)丁烷,简称双三唑丁烷。
2.根据权利要求1所述的带有双三唑丁烷和吡嗪二酸的锰配合物,其特征在于它的二级结构单元为:晶体属于单斜晶系,空间群为P21/c,晶胞参数为: α=90°,β=111.787(7)°,γ=90°。该配合物分子中含有1个Mn(II)离子、1个阴离子、0.5个btb配体、2个配位水分子及1个游离水分子,Mn(II)离子的配位数为6,阴离子的N4和O1原子以螯合方式与Mn(II)配位,形成一个由Mn1-N4-C5-C9-O1组成的不规则的五元环结构;同时与另一个阴离子的O4A原子、一个btb的N5原子配位及两个配位水氧原子O5和O6配位。如此,以Mn离子为金属中心形成一个畸形的八面体构型,其中N4、O1、O6与N3原子处于八面体的赤道平面上,所形成的4个键角N4-O1-O6、O1-O6-N3、O6-N3-N4和N3-N4-O1分别为98.96(1)°、80.46(1)°、85.04(1)°和93.83(1)°,其和为358.29(4)°,与360°极为接近,基本处于同一平面。每个阴离子都与两个Mn(II)离子配位,在省略btb配体情况下,阴离子与Mn(II)离子交替连接,沿a轴方向形成一维Z字链结构,配体分子btb以μ2桥联方式连接两条一维Z字链上的两个Mn(II)离子,在ab面上形成2D层状结构,其中每个结构单元由4个Mn(II)离子、4个配体阴离子和2个btb配体分子交替连接形成(图2)。
3.根据权利要求1所述的带有btb和吡嗪二酸的锰配合物的制备方法,其特征在于它包括以下步骤:
1)按计量比分别将Mn(CH3COO)2·4H2O和btb配置成水溶液;
2)混合两种溶液,室温下搅拌1h后;
3)按计量比向溶液中加入2,3-吡嗪二酸水溶液,继续室温下搅拌2h;
4)将所得溶液过滤,滤液在空气中静置、缓慢挥发,约一周后得目标产品。
4.根据权利要求3所述的含有双三唑丁烷和吡嗪二酸的锰配合物的制备方法,其特征在于所述的Mn(CH3COO)2·4H2O、btb和H2pzdc的质量之比为:3.06∶7.2∶1。
5.根据权利要求3所述的锰配合物的制备方法,其特征在于所述的反应条件是在室温下,利用磁力搅拌。
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CN106496578A (zh) * | 2016-10-01 | 2017-03-15 | 桂林理工大学 | 邻苯二甲酸锰聚合物及其制备方法 |
CN109320729A (zh) * | 2018-09-19 | 2019-02-12 | 常州大学 | 基于吡嗪多羧酸配体构筑金属锰有机框架化合物的方法及应用 |
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CN104876953A (zh) * | 2015-05-20 | 2015-09-02 | 天津工业大学 | 一种含有双三唑丁烷与吡嗪二酸的镉配合物及其制备方法 |
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CN104876953A (zh) * | 2015-05-20 | 2015-09-02 | 天津工业大学 | 一种含有双三唑丁烷与吡嗪二酸的镉配合物及其制备方法 |
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CN109320729A (zh) * | 2018-09-19 | 2019-02-12 | 常州大学 | 基于吡嗪多羧酸配体构筑金属锰有机框架化合物的方法及应用 |
CN109320729B (zh) * | 2018-09-19 | 2021-04-30 | 常州大学 | 基于吡嗪多羧酸配体构筑金属锰有机框架化合物的方法及应用 |
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