CN102532189A - Preparation method of super-molecule metal gel - Google Patents
Preparation method of super-molecule metal gel Download PDFInfo
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- CN102532189A CN102532189A CN2012100085551A CN201210008555A CN102532189A CN 102532189 A CN102532189 A CN 102532189A CN 2012100085551 A CN2012100085551 A CN 2012100085551A CN 201210008555 A CN201210008555 A CN 201210008555A CN 102532189 A CN102532189 A CN 102532189A
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- carboxylic acid
- 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 the 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, the supramolecule metal gel that copper, zinc form under ultrasonication is mainly used in and makes controlled molecular switch.
Background technology
In recent years, supermolecular gel develops into one type of intelligence/functional nanomaterials with broad prospect of application gradually.At present most of supermolecular gel utilization of research is hydrogen bond or packing of molecules effect, co-ordination bond this in supramolecular chemistry no less important to act on the application of gel on synthetic then not enough far away.Owing to can bring new performances such as photoelectricity, catalysis, redox to gel after introducing metals ion, so the research of supramolecule metal gel also obtains heating up in recent years.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind 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 the O/DMF system, under ultrasound condition, benzoglyoxaline carboxylic acid derivative and metallic lead, cadmium, copper, the zinc complexing forms title complex and gets.
Said benzoglyoxaline carboxylic acid derivative is N, N '-two ethyloics-2-ethyl benzo imidazole (being designated as L1) or N, N '-two ethyloics-2-propyl group benzoglyoxaline (being designated as L2).
Said H
2O/CH
3OH, H
2O/DMSO, H
2O/CH
3CN, H
2O/CHCl
3Or H
2In the O/DMF system, H
2O and CH
3OH, DMSO, CH
3CN, CHCl
3Or its volume ratio of DMF is 2:1 ~ 1:1.
Said metallic lead, cadmium, copper, zinc derive from metallic lead, cadmium, copper, the vitriol of zinc or nitrate salt.
The mol ratio of said 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 that forms in the OH system is an example, describes through structure and the performance to the supramolecule metal gel (G1, G2) of the present invention's preparation such as infared spectrum, X-ray diffractogram.
1, electron-microscope scanning: Fig. 1 is the electronic scanning displaing micro picture of gel G1 (a) and G2 (b).Can see that by Fig. 1 gel G1, G2 are fibrous.
2, infared spectrum: Fig. 2 is the infrared figure of compound L 1 and gel G1.See clearly with L1 by Fig. 2 and to compare that the obvious blue shift of the infrared absorption peak of gel G1 explains that cadmium metal and compound L 1 have formed co-ordination 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, and behind the formation gel, the arrangement between the molecule is more orderly, shows that compound L 1 and metal complex have formed title complex.
In order further to verify above-mentioned conclusion, in the gel that forms, added the room temperature placement then of EDTA (YD 30, a kind of important complexing agent) solid, after for some time, gel dissolves gradually, forms clear solution at last; And then in this solution, adding cadmium metal, gel recovers again.This experiment shows that EDTA is a complexing agent stronger than L1, and after adding EDTA, it forms title complex with cadmium metal, thereby has destroyed original L1 and Cd
2+Co-ordination bond; When adding cadmium once more, excessive cadmium has formed title complex with L1 again, thereby forms gel.
Above-mentioned FT-IR spectrum and X-ray diffraction result show that the gel of the present invention's preparation is that benzoglyoxaline carboxylic acid derivative and metals ion form coordination compound and hold onto small solvent molecule formation gel.
4, the reversible transition experiment of the gel-sol under the soda acid control
In gel G1, add the appropriate amount of acid room temperature and leave standstill for some time, find that gel slowly subsides, become solution at last; In this solution, add the alkali of equivalent then, ultrasonic again, by forming gel.Same operation adds alkali earlier in G1, gel becomes solution gradually, adds acid and becomes gel afterwards again.This shows, but gel G1 can realize the inverse conversion of gel-sol under soda acid control.Utilize this character of gel can make controlled molecular switch.
Through 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 complexing forms in the O/DMF system, find its structure and performance and gel G1 always: promptly gel is fibrous; Arrangement between the gel molecular is orderly, but and gel can realize the inverse conversion of gel-sol down in soda acid control, therefore, the gel that the present invention prepares can be used for making controlled molecular switch.
Description of drawings
Fig. 1 is G1 for the gel picture a under the scanning electron microscope, 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
Further specify through the preparation of specific embodiment below gel of the present invention.
The preparation of embodiment 1, gel G1
(1) preparation of compound L 1 (N, N '-two ethyloics-2-ethyl benzo imidazole):
In three neck round-bottomed flasks of reflux condensing tube are housed, get 4.00g (42mmol) Mono Chloro Acetic Acid, and, add 3.49 g (14mmol) 2-ethyl benzo imidazole with behind NaOH solution adjusting pH value to 8 ~ 10; Reflux, during constantly regulate the pH value, make the pH value of system maintain 8 ~ 10; After the pH value stabilization is constant, continue backflow 30min again, cooling; Add concentrated hydrochloric acid and transfer pH=2 ~ 3, have a large amount of white precipitates to generate.Hold over night, suction filtration washs respectively 3 times with zero(ppm) water and acetone, and back 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, adds in the mixing solutions of suitable water and methyl alcohol (volume ratio of water and methyl alcohol is 1:1), with the supersound process of 40 kHz 6 seconds, the room temperature placement i.e. the white fibrous gel of formation.The gel heating rework solution state that forms.
The preparation of embodiment 2, gel G2
(1) preparation of compound L 2 (N, N '-two ethyloics-2-propyl group benzoglyoxaline):
In three neck round-bottomed flasks of reflux condensing tube are housed, get 4.00g (42mmol) Mono Chloro Acetic Acid, and, add 3.86 g (14mmol) 2-propyl group benzoglyoxaline with behind NaOH solution adjusting pH value to 8 ~ 10; Reflux, during constantly regulate the pH value, make the pH value of system maintain 8 ~ 10; After the pH value stabilization is constant, continue backflow 30min again, cooling; Add concentrated hydrochloric acid and transfer pH=2 ~ 3, have a large amount of white precipitates to generate.Hold over night, suction filtration washs respectively 3 times with zero(ppm) water and acetone, and the water recrystallization obtains white solid then.
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 an amount of water and methyl alcohol (volume ratio of water and methyl alcohol is 2:1), with the supersound process of 40 kHz 6 seconds, the room temperature placement i.e. the white fibrous gel of formation.The gel heating rework solution state that forms.
The preparation of embodiment 3, gel G1
(1) preparation of compound L 1 (N, N '-two ethyloics-2-propyl group benzoglyoxaline): 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), with the supersound process of 40 kHz 6 seconds, room temperature was placed the fibrous gel G1 that promptly forms white.The gel heating rework solution state that forms.
The preparation of embodiment 4, gel G2
(1) preparation of compound L 2 (N, N '-two ethyloics-2-propyl group benzoglyoxaline): 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), with the supersound process of 40 kHz 6 seconds, room temperature was placed the fibrous gel that promptly forms white.But the gel that forms heating rework solution state.
The preparation of embodiment 5, gel G1
(1) preparation of compound L 1 (N, N '-two ethyloics-2-propyl group benzoglyoxaline): 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), with the supersound process of 40 kHz 6 seconds, room temperature was placed the fibrous gel G1 that promptly forms white.But the gel that forms heating rework solution state.
The preparation of embodiment 6, embodiment 4, gel G2
(1) preparation of compound L 2 (N, N '-two ethyloics-2-propyl group benzoglyoxaline): 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), with the supersound process of 40 kHz 6 seconds, room temperature was placed the fibrous gel that promptly forms white.The gel heating rework solution state that forms.
Claims (5)
1. the preparation method of a supramolecule metal gel is at H
2O/CH
3OH, H
2O/DMSO, H
2O/CH
3CN, H
2O/CHCl
3Or H
2In the O/DMF system, under ultrasound condition, benzoglyoxaline carboxylic acid derivative and metallic lead, cadmium, copper, zinc complexing form title complex and get.
2. the preparation method of supramolecule metal gel according to claim 1, it is characterized in that: said benzoglyoxaline carboxylic acid derivative is N, N '-two ethyloics-2-ethyl benzo imidazole or N, N '-two ethyloics-2-propyl group benzoglyoxaline.
3. the preparation method of supramolecule metal gel according to claim 1 is characterized in that: said H
2O/CH
3OH, H
2O/DMSO, H
2O/CH
3CN, H
2O/CHCl
3Or H
2In the O/DMF system, H
2O and CH
3OH, DMSO, CH
3CN, CHCl
3Or the volume ratio of DMF is 2:1 ~ 1:1.
4. the preparation method of supramolecule metal gel according to claim 1, it is characterized in that: said metallic lead, cadmium, copper, zinc derive from metallic lead, cadmium, copper, the vitriol of zinc or nitrate salt.
5. the preparation method of supramolecule metal gel according to claim 1, it is characterized in that: the mol ratio of said benzoglyoxaline carboxylic acid derivative and metallic lead, cadmium, copper, zinc is 1:0.4 ~ 1:3.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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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 |
CN103554171A (en) * | 2013-10-12 | 2014-02-05 | 安庆师范学院 | Lead chloride-1-aminopyridyl schiff base complex and preparation method thereof |
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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 |
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ZHANG YOUMING等,: "Microwave-assisted synthesis, crystal structure and toxicity of L-aspartic acid zinc spiral linear supramolecular polymer", 《SCIENCE IN CHINA SER. B CHEMISTRY》 * |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN103554171A (en) * | 2013-10-12 | 2014-02-05 | 安庆师范学院 | Lead chloride-1-aminopyridyl schiff base complex and preparation method thereof |
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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