CN102532189B - Preparation method of super-molecule metal gel - Google Patents
Preparation method of super-molecule metal gel Download PDFInfo
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- CN102532189B CN102532189B CN201210008555.1A CN201210008555A CN102532189B CN 102532189 B CN102532189 B CN 102532189B CN 201210008555 A CN201210008555 A CN 201210008555A CN 102532189 B CN102532189 B CN 102532189B
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- gel
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- acid derivative
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Abstract
The invention provides a preparation method of super-molecule metal gel and belongs to the field of functional materials. The super-molecule metal gel is obtained by a complex formed by complexing a benzimidazole carboxylic acid derivative as well as metallic lead, cadmium, copper and zinc in H2O/CH3OH, H2O/DMSO, H2O/CH3CN, H2O/CHC13 or H2O/DMF systems under the ultrasonic condition. FT-IR spectrum and X-ray diffraction results show that the gel prepared according to the invention is formed by constraining solvent micromolecules through the coordination complex formed by the benzimidazole carboxylic acid derivative and the metallic ions; and as the gel shows the conversion nature of reversible gel-sol under the acid-base control, the gel can be used for making a controllable molecular switch.
Description
Technical field
The invention belongs to functional material field, relate to a kind of supramolecule metal gel, relate in particular to a kind of benzoglyoxaline carboxylic acid derivative and metallic lead, cadmium, copper, the supramolecule metal gel that zinc forms under ultrasonication, is mainly used in making controlled molecular switch.
Background technology
In recent years, supermolecular gel develops into a class and has the intelligence/functional nanomaterials of broad prospect of application gradually.At present most of supermolecular gel utilization of research is hydrogen bond or packing of molecules effect, coordinate bond this in supramolecular chemistry no less important to act on the application of gel on synthetic not enough far away.After introducing metal ion, can bring the new performances such as photoelectricity, catalysis, redox to gel, therefore the research of supramolecule metal gel is also being heated up in recent years.
Summary of the invention
The object of this invention is to provide a kind of preparation method of supramolecule metal gel.
The preparation method of supramolecule metal gel of the present invention is at H
2o/CH
3oH, H
2o/DMSO, H
2o/CH
3cN, H
2o/CHCl
3or H
2in O/DMF system, under ultrasound condition, benzoglyoxaline carboxylic acid derivative and metallic lead, cadmium, copper, zinc complexing forms title complex and obtains.
Described benzoglyoxaline carboxylic acid derivative is N, N '-bis-carboxymethyl-2-ethyl benzo imidazole (being designated as L1) or N, N '-dicarboxyl methyl-2-propyl benzoglyoxaline (being designated as L2).
Described H
2o/CH
3oH, H
2o/DMSO, H
2o/CH
3cN, H
2o/CHCl
3or H
2in O/DMF system, H
2o and CH
3oH, DMSO, CH
3cN, CHCl
3or its volume ratio of DMF is 2:1 ~ 1:1.
Described metallic lead, cadmium, copper, zinc derive from metallic lead, cadmium, copper, the vitriol of zinc or nitrate.
The mol ratio of described benzoglyoxaline carboxylic acid derivative and metallic lead, cadmium, copper, zinc is 1:0.4 ~ 1:3.
Below with benzoglyoxaline carboxylic acid derivative (L1, L2) and Cadmium Sulphate at H
2o/CH
3the gel forming in OH system is example, and structure and the performance of the supramolecule metal gel (G1, G2) of by infared spectrum, X-ray diffractogram etc. being prepared by the present invention describe.
1, electron-microscope scanning: Fig. 1 is gel G1(a) and electronic scanning displaing micro picture G2(b).Can be seen by Fig. 1, gel G1, G2 are fibrous.
2, infared spectrum: Fig. 2 is the infrared figure of compound L 1 and gel G1.Clearly seen compared with L1 that by Fig. 2 the obvious blue shift of the infrared absorption peak of gel G1 illustrates that cadmium metal and compound L 1 have formed coordinate bond.
3, X-ray diffractogram: Fig. 3 is the X-ray diffractogram of compound L 1 and gel G1.The X-ray diffractogram of comparative compound L1 and G1 can draw, forms after gel, and the arrangement between molecule is more orderly, shows that compound L 1 and metal complex have formed title complex.
Above-mentioned conclusion add EDTA(ethylenediamine tetraacetic acid (EDTA), a kind of important complexing agent in the gel forming in order further to verify) then room temperature placement of solid, after for some time, gel dissolves gradually, finally forms clear solution; And then adding cadmium metal in this solution, gel recovers again.This experiment shows, EDTA is a complexing agent stronger than L1, and when adding after EDTA, it and cadmium metal form title complex, thereby have destroyed original L1 and Cd
2+coordinate bond; While again adding cadmium, excessive cadmium has formed title complex with L1 again, thereby forms gel.
Above-mentioned FT-IR spectrum and X-ray diffraction result show, gel prepared by the present invention is that benzoglyoxaline carboxylic acid derivative and metal ion form coordination compound and hold onto small solvent molecule and form gel.
4, the reversible transformation of the gel-sol under soda acid control experiment
In gel G1, add appropriate amount of acid room temperature to leave standstill for some time, find that gel slowly subsides, finally become solution; Then in this solution, add the alkali of equivalent, more ultrasonic, by forming gel.Same operation first adds alkali in G1, and gel becomes solution gradually, becomes again gel after acid adding.As can be seen here, gel G1 can realize the reversible transformation of gel-sol under soda acid control.Utilize this character of gel can make controlled molecular switch.
By benzoglyoxaline carboxylic acid derivative and metallic lead, cadmium, copper, zinc is at H
2o/DMSO, H
2o/CH
3cN, H
2o/CHCl
3or H
2the analysis of other title complex metal gel that in O/DMF system, complexing forms, finds its structure and performance and gel G1 always: gel is fibrous; Arrangement between gel molecular is orderly, and gel can realize the reversible transformation of gel-sol under soda acid control, and therefore, gel prepared by the present invention can be used for making controlled molecular switch.
Brief description of the drawings
Fig. 1 is that the gel picture a under scanning electron microscope is G1, and b is G2;
The infrared figure of Fig. 2 compound L 1 and gel G1;
Fig. 3 is the X-ray diffractogram of compound L 1 and gel G1.
Embodiment
Below by specific embodiment, the preparation of gel of the present invention is described further.
The preparation of embodiment 1, gel G1
(1) compound L 1(N, N '-bis-carboxymethyl-2-ethyl benzo imidazole) preparation:
In the three neck round-bottomed flasks that reflux condensing tube is housed, get 4.00g(42mmol) Mono Chloro Acetic Acid, and with behind NaOH solution adjusting pH value to 8 ~ 10, add 3.49 g(14mmol) 2-ethyl benzo imidazole, reflux, constantly regulates pH value during this time, make the pH value of system maintain 8 ~ 10, until pH value stabilization constant after, then continue backflow 30min, cooling, add concentrated hydrochloric acid to adjust pH=2 ~ 3, have a large amount of white precipitates to generate.Hold over night, suction filtration, washs respectively 3 times with distilled water and acetone, and rear water recrystallization, obtains white solid.
Fusing point: 279 ~ 281 ° of C productive rates: 70%.
1H?NMR?(400MHz?D
2O,?ppm)?δ:?7.45～7.56?(m,?4H,?),?4.65～5.01?(d,?4H),?3.03～3.05?(d,?2H),?1.10～1.14?(t,?3H),?IR?(KBr)?v:?1730?(C=O),?1676?(C=O),?3442?(O-H),?1532?(C=C),?1475?(C?=?N);?
13C?NMR?(100MHz?D
2O,?ppm)?δ:?10.31,?17.42,?47.61,?112.61,?127.09,?131.38,?155.28,?171.30。
(2) preparation of gel G1
Compound L 1 and Cadmium Sulphate are mixed with amount of substance 1:1, add in the mixing solutions of suitable water and methyl alcohol (volume ratio of water and methyl alcohol is 1:1), by the supersound process of 40 kHz 6 seconds, room temperature was placed and is formed white fibrous gel.The gel heating rework solution state forming.
The preparation of embodiment 2, gel G2
(1) compound L 2(N, N '-dicarboxyl methyl-2-propyl benzoglyoxaline) preparation:
In the three neck round-bottomed flasks that reflux condensing tube is housed, get 4.00g(42mmol) Mono Chloro Acetic Acid, and with behind NaOH solution adjusting pH value to 8 ~ 10, add 3.86 g(14mmol) 2-propylbenzimidazole, reflux, constantly regulates pH value during this time, make the pH value of system maintain 8 ~ 10, until pH value stabilization constant after, then continue backflow 30min, cooling, add concentrated hydrochloric acid to adjust pH=2 ~ 3, have a large amount of white precipitates to generate.Hold over night, suction filtration, washs respectively 3 times with distilled water and acetone, and then water recrystallization, obtains white solid.
Fusing point: 285 ~ 286
oc productive rate: 66%.
1H?NMR?(400MHz?D
2O,?ppm)?δ:?7.46～7.57?(m,?4H),?4.56～4.75?(d,?4H),?1.57～1.63?(m?2H),?2.99～3.03?(m,?2H),?0.85～0.90?(m,?3H),?IR(KBr);?IR?(KBr)?v:?1749?(C=O),?1632?(C=O),?3437(O-H),?1526?(C=C),?1474?(C?=?N);?
13C?NMR?(100MHz?D
2O,?ppm)?δ:?13.12,?20.25,?25.29,?68.70,?112.67,?126.96,?131.46,?153.86,?175.41。
(2) preparation of gel G2
Compound L 2 and Cadmium Sulphate are mixed with amount of substance 1:1, join in the mixing solutions of appropriate water and methyl alcohol (volume ratio of water and methyl alcohol is 2:1), by the supersound process of 40 kHz 6 seconds, room temperature was placed and is formed white fibrous gel.The gel heating rework solution state forming.
The preparation of embodiment 3, gel G1
(1) compound L 1(N, N '-dicarboxyl methyl-2-propyl benzoglyoxaline) preparation: with embodiment 1.
(2) preparation of gel G1
Compound L 1 and copper sulfate are mixed with amount of substance 1:1, join H
2(H in the mixing solutions of O/DMSO
2the volume ratio of O and DMSO is 2:1), by the supersound process of 40 kHz 6 seconds, room temperature was placed the fibrous gel G1 that forms white.The gel heating rework solution state forming.
The preparation of embodiment 4, gel G2
(1) compound L 2(N, N '-dicarboxyl methyl-2-propyl benzoglyoxaline) preparation: with embodiment 2.
(2) preparation of gel G2
Compound L 2 and copper sulfate are mixed with amount of substance 1:0.6, join H
2o/CH
3(H in the mixing solutions of CN
2o and CH
3the volume ratio of CN is 1:1), by the supersound process of 40 kHz 6 seconds, room temperature was placed the fibrous gel that forms white.The gel heating forming can rework solution state.
The preparation of embodiment 5, gel G1
(1) compound L 1(N, N '-dicarboxyl methyl-2-propyl benzoglyoxaline) preparation: with embodiment 1.
(2) preparation of gel G1
Compound L 1 and zinc nitrate are mixed with amount of substance 1:3, join H
2o/CHCl
3mixing solutions in (H
2o and CHCl
3volume ratio be 1:1), by the supersound process of 40 kHz 6 seconds, room temperature was placed the fibrous gel G1 that forms white.The gel heating forming can rework solution state.
The preparation of embodiment 6, embodiment 4, gel G2
(1) compound L 2(N, N '-dicarboxyl methyl-2-propyl benzoglyoxaline) preparation: with embodiment 2.
(2) preparation of gel G2
Compound L 2 and zinc nitrate are mixed with amount of substance 1:0.4, join H
2(H in the mixing solutions of O/DMF
2the volume ratio of O and DMF is 1:1), by the supersound process of 40 kHz 6 seconds, room temperature was placed the fibrous gel that forms white.The gel heating rework solution state forming.
Claims (3)
1. a preparation method for supramolecule metal gel is at H
2o/CH
3oH, H
2o/DMSO, H
2o/CH
3cN, H
2o/CHCl
3or H
2in O/DMF system, under ultrasound condition, benzoglyoxaline carboxylic acid derivative and cadmium metal, copper, zinc complexing form title complex and obtain;
Described benzoglyoxaline carboxylic acid derivative is N, N '-bis-carboxymethyl-2-ethyl benzo imidazole or N, N '-dicarboxyl methyl-2-propyl benzoglyoxaline; Described cadmium metal, copper, zinc derive from cadmium metal, copper, the vitriol of zinc or nitrate.
2. the preparation method of supramolecule metal gel as claimed in claim 1, is characterized in that: described H
2o/CH
3oH, H
2o/DMSO, H
2o/CH
3cN, H
2o/CHCl
3or H
2in O/DMF system, H
2o and CH
3oH, DMSO, CH
3cN, CHCl
3or the volume ratio of DMF is 2:1 ~ 1:1.
3. the preparation method of supramolecule metal gel as claimed in claim 1, is characterized in that: the mol ratio of described benzoglyoxaline carboxylic acid derivative and cadmium metal, copper, zinc is 1:0.4 ~ 1:3.
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| CN103242370A (en) * | 2013-05-07 | 2013-08-14 | 西南石油大学 | Metal organic gel based on tetrazole compounds |
| CN103240060A (en) * | 2013-05-20 | 2013-08-14 | 西北师范大学 | Metal organogel as well as preparation and application thereof in treatment of dyeing wastewater |
| CN103554171B (en) * | 2013-10-12 | 2015-11-25 | 安庆师范学院 | A kind of lead chloride-1-aminopyridine presence of Schiff-base complex and preparation method thereof |
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| CN1850787A (en) * | 2006-05-19 | 2006-10-25 | 北京化工大学 | Supermolecular intercalation 2-phenylbenzimidazole-5-sulfonic acid, and its preparing method and use |
| EP1798250B1 (en) * | 2005-12-16 | 2008-09-03 | INTERUNIVERSITAIR MICROELEKTRONICA CENTRUM vzw (IMEC) | Molecules suitable for binding to a metal layer for covalently immobilizing biomolecules |
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2012
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1798250B1 (en) * | 2005-12-16 | 2008-09-03 | INTERUNIVERSITAIR MICROELEKTRONICA CENTRUM vzw (IMEC) | Molecules suitable for binding to a metal layer for covalently immobilizing biomolecules |
| CN1850787A (en) * | 2006-05-19 | 2006-10-25 | 北京化工大学 | Supermolecular intercalation 2-phenylbenzimidazole-5-sulfonic acid, and its preparing method and use |
Non-Patent Citations (6)
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| Jing Huang等，.Dynamic functionalised metallogel: An approach to immobilised catalysis with improved activity.《Journal of Molecular Catalysis A: Chemical》.2009,第317卷第97-103页. * |
| Microwave-assisted synthesis, crystal structure and toxicity of L-aspartic acid zinc spiral linear supramolecular polymer;Zhang Youming等,;《Science in China Ser. B Chemistry》;20041231;第47卷(第4期);第295-300页 * |
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| 刘勇.离子液体金属配合物及其超分子金属凝胶的研究.《西北师范大学硕士论文》.2011,第29、57-58页. |
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