CN104311578A - 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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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title abstract description 39
- 229910052742 iron Inorganic materials 0.000 title abstract description 5
- ZCLRACWELYCDDI-UHFFFAOYSA-N 3-formyl-4-hydroxy-5-methylbenzoic acid Chemical compound CC1=CC(C(O)=O)=CC(C=O)=C1O ZCLRACWELYCDDI-UHFFFAOYSA-N 0.000 title abstract 4
- 238000010668 complexation reaction Methods 0.000 title 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- -1 3-methyl-5-carboxylsalicylidene Chemical group 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- WBYRVEAPTWYNOX-UHFFFAOYSA-N [Fe].[Cd] Chemical compound [Fe].[Cd] WBYRVEAPTWYNOX-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 6
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000006850 spacer group Chemical group 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 5
- 230000005291 magnetic effect Effects 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 150000001450 anions Chemical class 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 6
- 239000007789 gas Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000005595 deprotonation Effects 0.000 description 2
- 238000010537 deprotonation reaction Methods 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 241000238366 Cephalopoda Species 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 230000005290 antiferromagnetic effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- PFCLRYYQHJCBIC-UHFFFAOYSA-N cadmium(2+) iron(3+) Chemical compound [Fe+3][Cd++] PFCLRYYQHJCBIC-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 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
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
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- 238000002050 diffraction method Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
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- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/03—Sideramines; The corresponding desferri compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
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( μ2 -O)(H2O)2]·2DMF·H2O,其中L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,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,RSC Adv. 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. C 2010,114,1580)。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(µ2 -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) Å3。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0.12 mmol,六水合三氯化铁0.06 mmol和H4L 0.06 mmol 放入聚四氟乙烯反应釜中,以6 mL 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77 K时N2的吸附等温线图;
图7是273 K与293 K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(0.12 mmol),六水合三氯化铁(0.06 mmol)和H4L (0.06 mmol)
放入聚四氟乙烯反应釜中,以6 mL 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Oxford Diffraction Gemini R Ultra衍射仪上收集,Mo Kα射线 (λ = 0.71069 Å),293 K。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) Å3。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-Sorb 2800S自动体积吸附仪) 。如图6,测得77 K时对N2的吸附量为52.20 cm3/g;Langmuir表面积为153.08 m2/g。273 K和293 K时对CO2 的吸附能力分别为 49.64 cm3/g 和39.97 cm3/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. Growth Des. 2014,14,2866)。
(3)配合物的磁学性能研究(Quantum Design, MPMS-5
SQUID magnetometer,1000 Oe)。
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(30m long × 0.25mm i.d.,WondaCAP 17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 (Å) | 13.1740(5) |
b (Å) | 32.548(1) |
c (Å) | 33.0390(9) |
α(°) | 90 |
β(°) | 97.479(6) |
γ(°) | 90 |
V (Å3) | 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(Å)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;#3 x,-y,z-1/2;#4 x-1/2,-y-1/2,z-1/2;#5 -x+3/2,-y-1/2,-z+2。
Claims (3)
1.一种1,2-环己烷二氨基-N,N'-二(3-甲基-5-羧基水杨醛)镉铁杂金属配合物,其特征在于:化学式为 [Cd2(Fe-L)2(µ2 -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) Å3,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)3-甲基-5-羧基水杨醛镉铁杂金属配合物的合成:取氯化镉0.12 mmol,六水合三氯化铁0.06 mmol和H4L 0.06 mmol 放入聚四氟乙烯反应釜中,以6 mL 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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