CN104311578B - 1,2-环己烷二氨基-n,n’-二(3-甲基-5-羧基水杨醛)镉铁杂金属配合物及其制备方法 - Google Patents
1,2-环己烷二氨基-n,n’-二(3-甲基-5-羧基水杨醛)镉铁杂金属配合物及其制备方法 Download PDFInfo
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- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 16
- WBYRVEAPTWYNOX-UHFFFAOYSA-N [Fe].[Cd] Chemical compound [Fe].[Cd] WBYRVEAPTWYNOX-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- -1 3-methyl-5-carboxylsalicylidene Chemical group 0.000 title claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 150000001450 anions Chemical class 0.000 abstract description 6
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- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 36
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
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- 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
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- 239000000539 dimer Substances 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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Abstract
一种1,2-环己烷二氨基-N,Nˊ-二(3-甲基-5-羧基水杨醛)镉铁杂金属配合物及其制备方法，属于化学技术领域，配合物为下述化学式：[Cd2(Fe-L)2(<i>μ2</i>-O)(H2O)2]·2DMF·H2O，其中L为去质子化的1,2-环己烷二氨基-N,Nˊ-二(3-甲基-5-羧基水杨醛)阴离子，DMF为二甲基甲酰胺。配合物采用溶剂热方法制备。本发明的配合物对可见光照射下的2-氯酚表现出较好的光催化降解能力。并且表现了较好的气体吸附和磁学性质。
Description
技术领域
本发明属于化学技术领域，涉及一种杂金属配合物及其制备方法。
背景技术
席夫碱（L）由于具有优异的配位能力而被广泛研究（J.M.Falkowski，C.Wang，S.Liu，W.B.Lin，Angew.Chem.Int.Ed. 2011，50，8674；S.Jung，M.Oh，Angew.Chem.Int.Ed. 2008，47，2049）。一些基于此类配体的杂金属配合物已被成功合成，这些配合物多基于Mn-L，Co-L，Ni-L或Cu-L为基本构筑单元，再与其它金属反应制得（R.Kitaura，G.Onoyama，H.Sakamoto，R.Matsuda，S.Noro，S.Kitagawa，Angew.Chem.Int.Ed.2004，43，2684）。
由于水热条件下Fe(III)的水解导致结晶困难，基于Fe-L配体的杂金属配合物的研究极少（A.Bhunia，Y.Lan，V.Mereacre，M.T.Gamer，A.K.Powell，P.W.Roesky，Inorg.Chem. 2011，50，12697；Z.W.Yang，C.F.Zhu，Z.J.Li，Y.Liu，G.H.Liu，Y.Cui，Chem.Commun. 2014，50，8775；Y.W.Ren，Y.C.Shi，J.X.Chen，S.R.Yang，C.R.Qi，H.F.Jiang，RSCAdv. 2013，3，2167）。尤其是基于含羧酸席夫碱的镉(II)-铁(III)杂金属配合物的研究至今还无人报道。
近年来光催化降解有机污染物已引起人们的广泛重视（M.W.Porambo，H.R.Howard，A.L.Marsh，J.Phys.Chem.C2010，114，1580）。其中2-氯酚是一种典型的污染物，它在废水中很难降解，所以我们选择2-氯酚作为光催化的研究对象。
发明内容
本发明要解决的技术问题是公开一种1,2-环己烷二氨基-N,N'-二(3-甲基-5-羧基水杨醛)镉铁杂金属配合物。
本发明同时还公开了这种镉铁杂金属配合物的制备方法。
1,2-环己烷二氨基-N,N'-二(3-甲基-5-羧基水杨醛)镉铁杂金属配合物具有下述化学式，即：[Cd2(Fe-L)2(μ 2 -O)(H2O)2]·2DMF·H2O，其中L4-为去质子化的1,2-环己烷二氨基-N,N'-二(3-甲基-5-羧基水杨醛)阴离子配体。
配合物晶体属于单斜晶系，空间群为C2/c，晶胞参数为a=13.1740(5)，b=32.548(1)，c=33.0390(9)，α=90，β=97.479(6)，γ=90°，V=14046.2(8)?3。基本结构是一个新颖的具有孔道的三维网络结构。
所述的1,2-环己烷二氨基-N,N'-二(3-甲基-5-羧基水杨醛)镉铁杂金属配合物的制备方法，包括如下步骤：
（1）H4L配体的制备：3-甲基-5-羧基水杨醛和二氨基环己烷混合，以四氢呋喃为溶剂，在室温下搅拌制得，其中3-甲基-5-羧基水杨醛和二氨基环己烷摩尔量比为2:1；四氢呋喃加入量为相应3-甲基-5-羧基水杨醛摩尔量的50-100倍；
H4L配体
（2）1,2-环己烷二氨基-N,N'-二(3-甲基-5-羧基水杨醛)镉铁杂金属配合物的合成：取氯化镉0.12mmol，六水合三氯化铁0.06mmol和H4L0.06mmol放入聚四氟乙烯反应釜中，以6mL二甲基甲酰胺/水为混合溶剂，其中胺与水的摩尔比为2:1，放置在烘箱中，加热到100℃恒温72小时，然后以每小时10℃降到室温可得到红色菱形晶体，产率50%。
本发明镉铁杂金属有机配合物对可见光照射下的2-氯酚表现出较好的光催化降解能力，并且表现了较好的气体吸附和磁学性质，通过简单的溶剂热合成得到，具有制备方法简单、重复性强、产品性能稳定等特点。
附图说明
图1是配合物中金属的配位环境图；
图2是四核镉簇结构图；
图3是铁二聚体结构图；
图4是配合物的三维孔道结构图；
图5是配合物及其活化后的粉末衍射示意图；
图6是77K时N2的吸附等温线图；
图7是273K与293K时CO2的吸附等温线图；
图8是配合物的χ m -1和χ m T随温度变化的曲线图；
图9是配合物光催化降解2-氯酚随时间变化的曲线图。
具体实施方式
将3-甲基-5-羧基水杨醛和二氨基环己烷混合，以四氢呋喃为溶剂，在室温下搅拌制得到H4L配体，其中3-甲基-5-羧基水杨醛和二氨基环己烷摩尔量比为2:1；四氢呋喃加入量为相应3-甲基-5-羧基水杨醛摩尔量的50-100倍；
将氯化镉(0.12mmol)，六水合三氯化铁(0.06mmol)和H4L(0.06mmol)放入聚四氟乙烯反应釜中，以6mL二甲基甲酰胺/水（摩尔比2:1）为混合溶剂，放置在烘箱中，加热到100℃恒温72小时，然后以每小时10℃降到室温可得到红色菱形晶体，即3-甲基-5-羧基水杨醛镉铁杂金属配合物，产率50%。
主要的红外吸收峰为：3418(s)，2935(m)，2861(m)，1617(s)，1566(s)，1522(m)，1448(m)，1387(s)，1335(s)，1288(s)，1252(m)，1024(w)，978(w)，919(w)，792(m)，763(m)，624(w)，583(m)。
配合物的相关表征
（1）配合物的晶体结构测定
配合物的衍射数据是在OxfordDiffractionGeminiRUltra衍射仪上收集，MoKα射线(λ=0.71069?)，293K。使用技术扫描进行校正。晶体结构是通过SHELEXL-97程序以直接法解出，用全矩阵最小二乘法使用SHELEXL-97进行精修。非氢原子的温度因子用各向异性进行修正。详细的晶体测定数据见表1；重要的键长和键角数据见表2；晶体结构见图1-图4。
发明的配合物其特征在于所述配合物晶体属于单斜晶系，空间群为C2/c，晶胞参数为a=13.1740(5)，b=32.548(1)，c=33.0390(9)，α=90，β=97.479(6)，γ=90°，V=14046.2(8)?3。单胞中存在两个Fe-L构筑单元，三个独立的Cd(II)离子，一个μ 2-O阴离子，两个配位水分子，两个游离的DMF分子和一个游离的水分子。三个镉离子都是6-配位的扭曲八面体构型，被L4-阴离子的羧酸基团连接为[Cd4(COO)8(H2O)2]四核簇。两个铁离子都为5-配位的四方锥构型，分别嵌于两个去质子化的L4-阴离子内部的N2O2中，被一个μ 2-O阴离子连接为Fe 2 (L) 2 (μ 2-O)二聚体。四核镉簇和铁二聚体被L4-阴离子进一步桥联为三维孔道结构。
（2）配合物的气体吸附性质研究
配合物首先在真空和150°C条件下保持5小时，进行活化（相纯度见图5），然后进行气体吸附性质测试(V-Sorb2800S自动体积吸附仪)。如图6，测得77K时对N2的吸附量为52.20cm3/g；Langmuir表面积为153.08m2/g。273K和293K时对CO2的吸附能力分别为49.64cm3/g和39.97cm3/g（图7）。在报导的孔道化合物中，这个吸附数值处于中等水平（J.H.Cui，Y.Z.Li，Z.J.Guo，H.G.Zheng，Chem.Commun.2013，49，555，Y.M.Huang，B.G.Zhang，J.G.Duan，W.L.Liu，X.F.Zheng，L.L.Wen，X.H.Ke，D.F.Li，Cryst.GrowthDes.2014，14，2866）。
（3）配合物的磁学性能研究（QuantumDesign,MPMS-5SQUIDmagnetometer，1000Oe）。
测试表明配合物具有典型的反铁磁相互作用（图8）。
（4）配合物的光催化2-氯酚研究（30mlong×0.25mmi.d.，WondaCAP17毛细管色谱，GC-2014C，Shimadzu，FID探测器）。
在可见光照射下（图9），配合物对溶液中2-氯酚的浓度起到明显的降解作用。在pH=3的条件下，配合物对2-氯酚光降解的能力为46%。
表1为配合物的主要晶体学数据
| formula | C54H56N6O18Fe2Cd2 |
| Mr | 1413.55 |
| crystal system | monoclinic |
| space group | C2/c |
| a (?) | 13.1740(5) |
| b (?) | 32.548(1) |
| c (?) | 33.0390(9) |
| α(°) | 90 |
| β(°) | 97.479(6) |
| γ(°) | 90 |
| V (?3) | 14046.2(8) |
| Z | 8 |
| D calc (g cm-3) | 1.337 |
| F(0 0 0) | 5712 |
| R int | 0.1506 |
| GOF on F 2 | 1.135 |
| R1 [I>2σ(I)] | 0.0940 |
| wR2 (all data) | 0.2048 |
表2为配合物的主要键长(?)和键角[°]*
| Fe(1)-O(13) | 1.781(6) | Fe(1)-O(2) | 1.915(7) |
| Fe(1)-O(1) | 1.935(7) | Fe(1)-N(2) | 2.102(7) |
| Fe(1)-N(1) | 2.089(8) | Fe(2)-O(13)#1 | 1.758(6) |
| Fe(2)-O(3) | 1.920(7) | Fe(2)-O(4) | 1.940(7) |
| Fe(2)-N(4) | 2.086(8) | Fe(2)-N(3) | 2.116(7) |
| Cd(1)-O(7) | 2.204(7) | Cd(1)-O(9) | 2.367(6) |
| Cd(1)-O(5)#1 | 2.365(7) | Cd(2)-O(10) | 2.135(9) |
| Cd(2)-O(12)#4 | 2.191(14) | Cd(2)-O(6)#3 | 2.228(10) |
| Cd(2)-O(8) | 2.285(11) | Cd(2)-O(1W) | 2.326(10) |
| Cd(2)-O(5)#3 | 2.437(7) | Cd(3)-O(11)#4 | 2.206(16) |
| Cd(3)-O(9) | 2.331(7) | Cd(3)-O(2W) | 2.435(17) |
| O(13)-Fe(1)-O(2) | 109.9(3) | O(13)-Fe(1)-O(1) | 112.1(3) |
| O(2)-Fe(1)-O(1) | 90.8(3) | O(13)-Fe(1)-N(2) | 106.8(3) |
| O(2)-Fe(1)-N(2) | 86.5(3) | O(1)-Fe(1)-N(2) | 139.4(3) |
| O(13)-Fe(1)-N(1) | 98.4(3) | O(2)-Fe(1)-N(1) | 150.4(3) |
| O(1)-Fe(1)-N(1) | 86.3(3) | N(2)-Fe(1)-N(1) | 76.9(3) |
| O(13)#1-Fe(2)-O(3) | 113.6(3) | O(13)#1-Fe(2)-O(4) | 109.7(3) |
| O(3)-Fe(2)-O(4) | 89.6(3) | O(13)#1-Fe(2)-N(4) | 105.1(3) |
| O(3)-Fe(2)-N(4) | 140.1(3) | O(4)-Fe(2)-N(4) | 86.2(3) |
| O(13)#1-Fe(2)-N(3) | 101.3(3) | O(3)-Fe(2)-N(3) | 86.1(3) |
| O(4)-Fe(2)-N(3) | 147.7(3) | N(4)-Fe(2)-N(3) | 77.1(3) |
| O(7)-Cd(1)-O(7)#2 | 103.8(5) | O(7)-Cd(1)-O(9)#2 | 168.1(3) |
| O(7)-Cd(1)-O(9) | 88.1(3) | O(9)#2-Cd(1)-O(9) | 80.0(3) |
| O(7)-Cd(1)-O(5)#3 | 99.3(3) | O(7)-Cd(1)-O(5)#1 | 85.8(3) |
| O(9)-Cd(1)-O(5)#1 | 81.6(2) | O(9)-Cd(1)-O(5)#3 | 92.1(2) |
| O(5)#3-Cd(1)-O(5)#1 | 171.8(4) | O(10)-Cd(2)-O(12)#4 | 94.9(6) |
| O(10)-Cd(2)-O(6)#3 | 174.2(4) | O(12)#4-Cd(2)-O(6)#3 | 90.7(5) |
| O(10)-Cd(2)-O(8) | 84.6(4) | O(12)#4-Cd(2)-O(8) | 178.4(5) |
| O(6)#3-Cd(2)-O(8) | 89.9(4) | O(10)-Cd(2)-O(1W) | 86.4(4) |
| O(12)#4-Cd(2)-O(1W) | 91.1(6) | O(6)#3-Cd(2)-O(1W) | 95.1(4) |
| O(8)-Cd(2)-O(1W) | 87.3(5) | O(10)-Cd(2)-O(5)#3 | 120.8(3) |
| O(12)#4-Cd(2)-O(5)#3 | 98.8(4) | O(6)#3-Cd(2)-O(5)#3 | 56.5(3) |
| O(8)-Cd(2)-O(5)#3 | 82.7(3) | O(1W)-Cd(2)-O(5)#3 | 149.7(4) |
| O(11)#4-Cd(3)-O(11)#5 | 179.5(11) | O(11)#4-Cd(3)-O(9)#2 | 88.2(4) |
| O(11)#4-Cd(3)-O(9) | 92.2(5) | O(11)#5-Cd(3)-O(9) | 88.2(4) |
| O(9)#2-Cd(3)-O(9) | 81.4(3) | O(11)#5-Cd(3)-O(2W) | 89.3(8) |
| O(11)#4-Cd(3)-O(2W) | 90.3(8) | O(9)-Cd(3)-O(2W) | 90.8(4) |
| O(9)-Cd(3)-O(2W)#2 | 172.0(4) | O(2W)#2-Cd(3)-O(2W) | 97.1(8) |
*对称代码#1-x+1，-y，-z+2；#2-x+1，y，-z+3/2；#3x，-y，z-1/2；#4x-1/2，-y-1/2，z-1/2；#5-x+3/2，-y-1/2，-z+2。
Claims (3)
1.一种1,2-环己二胺-N,N'-二(3-甲基-5-羧基邻羟亚苄基)镉铁杂金属配合物，其特征在于：化学式为[Cd2(Fe-L)2(μ 2 -O)(H2O)2]·2DMF·H2O。
2.根据权利要求1所述的杂金属配合物，其特征在于：它的晶体属于单斜晶系，空间群为C2/c，晶胞参数为a=13.1740(5)，b=32.548(1)，c=33.0390(9)，α=90，β=97.479(6)，γ=90°，V=14046.2(8)?3，基本结构是一个具有孔道的三维网络结构。
3.根据权利要求1所述的镉铁杂金属配合物制备方法，其特征在于包括如下步骤：
（1）H4L配体的制备：3-甲基-5-羧基水杨醛和二氨基环己烷混合，以四氢呋喃为溶剂，在室温下搅拌制得，其中3-甲基-5-羧基水杨醛和二氨基环己烷摩尔量比为2:1；四氢呋喃加入量为相应3-甲基-5-羧基水杨醛摩尔量的50-100倍；
（2）1,2-环己二胺-N,N'-二(3-甲基-5-羧基邻羟亚苄基)镉铁杂金属配合物的合成：取氯化镉0.12mmol，六水合三氯化铁0.06mmol和H4L0.06mmol放入聚四氟乙烯反应釜中，以6mL二甲基甲酰胺/水为混合溶剂，其中胺与水的摩尔比为2:1，放置在烘箱中，加热到100℃恒温72小时，然后以每小时10℃降到室温即得。
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