CN101798320A - Gasochromic rare earth complex and preparation method and application thereof - Google Patents
Gasochromic rare earth complex and preparation method and application thereof Download PDFInfo
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- CN101798320A CN101798320A CN201010101757A CN201010101757A CN101798320A CN 101798320 A CN101798320 A CN 101798320A CN 201010101757 A CN201010101757 A CN 201010101757A CN 201010101757 A CN201010101757 A CN 201010101757A CN 101798320 A CN101798320 A CN 101798320A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 62
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000010668 complexation reaction Methods 0.000 title 1
- -1 rare earth salt Chemical class 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 68
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 57
- 238000013329 compounding Methods 0.000 claims description 39
- 238000002845 discoloration Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 230000002441 reversible effect Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000003446 ligand Substances 0.000 abstract 3
- 239000000463 material Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000013461 design Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical group C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000002650 habitual effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- HYHLXSWZHRFFJZ-UHFFFAOYSA-N iodomethane;oxolane Chemical compound IC.C1CCOC1 HYHLXSWZHRFFJZ-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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Abstract
The invention discloses a gasochromic rare earth complex. The structure of the gasochromic rare earth complex is obtained by the coordination of rare earth metal Eu (III) and a tripod type ligand MeNTB. The invention also discloses a preparation method of the above complex, comprising: carrying out coordination on rare earth salt and MeNTB ligand at the molar ratio of 1:2 to obtain the gasochromic rare earth complex. The gasochromic phenomenon obtained by the complex of the invention has high signal strength, speed, stability and repeatability; moreover, the response strength, response range and response time can be further improved by decorating the ligand and selecting metal; in addition, the complex can be used for designing gasochromic switches and logic gate devices and has wide application prospect.
Description
Technical field
The present invention relates to the design of a kind of rare earth compounding and preparation method thereof and device, specifically a kind of preparation of the luminescent rare earth complexes for methyl alcohol and acetonitrile steam sensitivity and based on the method for design of the gas-discoloration switch and the logical gate device of this title complex with gas-discoloration phenomenon.
Background technology
In recent years, the gas-discoloration material is because receive much concern in the application of aspects such as molecular recognition and chemical sensor.Wherein, based on the gas-discoloration material of metal-organic coordination compound because of having characteristics such as chemically modified is strong, responding range is wide, speed is fast, Heat stability is good, thereby opened up the brand-new world of a slice in the design in this field with in using.But up to the present, example based on a metal-organic complex gas-discoloration is limited to the particularly title complex of precious metal of transition metal such as Pd, Pt, Ir, Au substantially, and the preparation complexity of its luminosity and monochromaticity, response efficiency, stability and title complex etc. all is lower than the needed performance perameter of practical application.And,, further restricted the production and the popularization of such material because most metal that is used to prepare the gas-discoloration material is more rare.Existing technology can not satisfy the demand of market to the gas-discoloration material far away.Therefore, exploitation is suitable for mass-produced high-quality luminescent properties gas-discoloration material, has important practical significance and economic worth.
Summary of the invention
The objective of the invention is to overcome the deficiency of existing gas-discoloration a metal-organic complex, the material with gas-discoloration phenomenon that a kind of raw material sources are extensive, luminance purity is high, sensitivity is stable is provided.
Another object of the present invention provides this kind preparation methods.
A further object of the present invention provides the application of this material.
The present invention is achieved through the following technical solutions above-mentioned purpose:
A kind of novel gas-discoloration material---rare earth compounding is provided, it is characterized in that being made of rare earth and part MeNTB, part MeNTB is a tripod-type, and structural formula is:
Above-mentioned trivet part MeNTB (N-substituted tris (N-alkylbenzimidazol-2-ylmethyl) amine) can effectively utilize tripod to hang in the coordination N atom of benzoglyoxaline group and center is wrapped in rare earth ion on the arm, forms good rare earth luminous coordination environment.
The preparation method of above-mentioned rare earth compounding is that to utilize mol ratio be 1: 2 rare-earth salts and the coordination reaction of MeNTB part, obtains the rare earth compounding of gas-discoloration.May further comprise the steps specifically: rare-earth salts and part MeNTB are dissolved in respectively in the solvent, obtain the MeNTB solution that rare earths salt that volumetric molar concentration is 0.008～0.01mol/l and volumetric molar concentration are 0.016～0.02mol/l; According to the mol ratio of rare-earth salts and MeNTB is 1: 2 above-mentioned two kinds of solution of mixed, places 1～2 day, light yellow crystallite product is filtered obtain the target title complex.Wherein rare earths salt and MeNTB solution are to be dissolved in the organic solvent by rare-earth salts or MeNTB to obtain; The organic solvent that is adopted can be methyl alcohol, ethanol or acetonitrile etc.
This rare earth compounding can be by organic steam in the environment existence whether, reversible or irreversibly control the luminous of rare earth compounding.Reversibly control the luminous of rare earth compounding by methanol steam; Or irreversibly control the luminous of rare earth compounding by acetonitrile steam.Rare earth compounding is exposed in the methanol steam fluorescence intensity of the regulation and control rare earth compounding by regulating methanol steam concentration; Or rare earth compounding is exposed in the acetonitrile steam, strengthen the fluorescence intensity of rare earth compounding by the increase of acetonitrile vapour concentration.
It is reversible that this title complex strengthens for the fluorescence of methanol steam, promptly removes methanol steam and with behind the nitrogen purging, fluorescence intensity is returned to original state, and after continuing to feed methyl alcohol, fluorescence strengthens again, and this process is capable of circulation back and forth.But the fluorescence enhancing for acetonitrile can not be reversible.
This rare earth compounding can be applied in gas-discoloration switch or logical gate device.
Compared with prior art, the present invention has following beneficial effect:
(1) rare earth compounding provided by the invention adopts rare earth to substitute habitual metal as one of raw material, and rare earth compounding has overcome a metal-organic complex luminosity, response efficiency and stable insufficient problem; And because China is the favourable resource of rare earth big country, this has significant advantage under the Natural resources condition of China as starting material with rare earth, for a new approach has been opened up in the preparation of novel gas-discoloration material.
(2) rare earth compounding provided by the invention sends the emission of Eu (III) ionic characteristic red colo(u)r streak shape under the exciting of 370nm UV-light, illuminant colour purity height, and feature is obvious; For the responsive gas-discoloration phenomenon of the steam of methyl alcohol and acetonitrile, strength of signal, speed, stability and circulation ratio are all very high; In addition, can also be expected to become a kind of novel elite clone that obtains gas-discoloration by the modification of part and the selection of metal are further improved response intensity, responding range and time of response.Utilize exploitation to have the RE compound material of gas-discoloration phenomenon and be applied to device and will have bigger potentiality and value.
(3) method for preparing rare earth compounding provided by the present invention is easy, productive rate is high and stablize, overcome the problem of existing gas-discoloration a metal-organic complex complex manufacturing, make this novel gas-discoloration material production and apply and have more wide prospect.
(4) utilize gas-discoloration rare earth compounding provided by the invention can design gas-discoloration switch and logical gate device easily, do not need complicated plant and instrument, saved the energy, the response device of preparing is good, reproduction degree height.
Description of drawings
The crystalline structure figure of gained title complex in Fig. 1 embodiment of the invention.
The fluorogram of gained title complex in Fig. 2 embodiment of the invention.
Gas-discoloration photo (left side) initial sample of gained title complex in Fig. 3 embodiment of the invention, (in) be exposed to methyl alcohol atmosphere, (right side) is exposed to acetonitrile atmosphere.
The wiring diagram of designed device (left side) logical gate (right side) one way switch in Fig. 4 embodiment of the invention.
Embodiment
Below further specify technical scheme of the present invention by specific embodiment.
1. the preparation of part:
(1) in the round-bottomed flask of 250ml, adds 16.2g (0.15mol) O-Phenylene Diamine and 9.6g (0.05mol) amine triacetic acid, stir after adding 60ml ethylene glycol, oil bath is heated to 140-200 degree backflow 8-12 hour, can adorn water trap in the reaction process water that generates is drawn reaction system; After having reacted, 200ml water is injected in cooling while stirring slightly, filters, and ethyl alcohol recrystallization (using activated carbon decolorizing in case of necessity) gets product NTB (productive rate 85%).
(2) tetrahydrofuran (THF) that 1.02g (0.0025mol) NTB and 50ml handled with sodium Metal 99.5 in the 150ml three-necked bottle, under the nitrogen gas stream protection, add 0.3g (0.0077mol in batches, because the water that does not eliminate in the oxidation of potassium and the solvent, it is slightly excessive that potassium metal requires) potassium metal, up to there not being hydrogen to produce, refluxed then 1-2 hour, system becomes white opacity; Add the methyl iodide tetrahydrofuran solution (0.0075ml) that is equivalent to 3 times of NTB equivalents by dropping funnel this moment again, continues to reflux 3 hours, and cooling is poured in the water, filters, and gained yellow solid crude product gets light yellow product with ethyl alcohol recrystallization.Productive rate 80%.
2. the preparation of rare earth compounding
Get 0.1mmol part MeNTB and be dissolved in the 5ml methyl alcohol, add 3ml 0.025mmol Eu (ClO again
4)
3Methanol solution, obtain light yellow crystallite rapidly, after one day product filtered and obtains the target title complex.
Utilize this part and Eu (III) ion to carry out coordination, obtain having the rare earth compounding of ML2 configuration, its structure as shown in Figure 1.
The test of title complex luminescent properties: measure on the FLS920 type fluorescence analyser of Britain EDINBURGH company, sample excites down at the incident light of 370nm, sends Eu (III) ion 594,611, the feature wire emission of 620nm.
It is carried out fluorometric investigation show, under the exciting of 370nm UV-light, part absorbs energy and passes to rare earth metal, launches the characteristic red colo(u)r streak shape emission of Eu (III), as shown in Figure 2.
The test of title complex gas-discoloration phenomenon:
Title complex was exposed to methyl alcohol or acetonitrile steam following 10 minutes, and fluorescence enhanced synoptic diagram as shown in Figure 3 under the steam atmosphere.(left side) is initial sample among the figure, (in) be exposed to methyl alcohol atmosphere, (right side) is exposed to acetonitrile atmosphere.
The result shows that when this title complex touches methyl alcohol or acetonitrile steam, tangible gas-discoloration phenomenon takes place, fluorescence intensity strengthens 18.1 times and 15 times respectively, and response speed is fast, and the enhancing of fluorescence contacts moment at steam, and reaches the strongest in 5 minutes.
And then remove methyl alcohol or acetonitrile steam, and feeding nitrogen 10 minutes, the former fluorescence intensity weakens and returns to the preceding original state of logical methanol steam, and the latter's fluorescence intensity does not weaken with the removal of acetonitrile steam.
Embodiment 4
The design of gas-discoloration switch and logical gate device as shown in Figure 4.In the design of the logical gate device of a, in title complex, feed methanol steam (input 1) after, fluorescence strengthens greatly, device is in "open" state, and by output terminal 1 output signal; Stop logical methyl alcohol and after feeding nitrogen (input 2), fluorescent weakening, device are in "off" state, and by output terminal 2 output signals.In the one way switch device of b, after title complex fed acetonitrile steam (input 3), fluorescence strengthened, and device is in "open" state, stopped logical acetonitrile and after feeding nitrogen (input 2), not response of device, and institute thinks one way switch.
Claims (9)
1. the rare earth compounding of a gas-discoloration is characterized in that being made of rare earth and part MeNTB, and the structural formula of part MeNTB is:
2. the preparation method of a rare earth compounding as claimed in claim 1, it is characterized in that utilizing mol ratio is 1: 2 rare-earth salts and the coordination reaction of MeNTB part, obtains the rare earth compounding of gas-discoloration.
3. the preparation method of rare earth compounding as claimed in claim 2 is characterized in that may further comprise the steps: rare-earth salts and part MeNTB are configured as the MeNTB solution that rare earths salt that volumetric molar concentration is 0.008～0.01mol/l and volumetric molar concentration are 0.016～0.02mo1/l respectively; According to the mol ratio of rare-earth salts and MeNTB is 1: 2 above-mentioned two kinds of solution of mixed, places 1 ~ 2 day after-filtration and obtains rare earth compounding.
4. the preparation method of rare earth compounding as claimed in claim 3 is characterized in that described rare earths salt and MeNTB solution are to be dissolved in the organic solvent by rare-earth salts or MeNTB to obtain.
5. the preparation method of rare earth compounding as claimed in claim 4 is characterized in that described organic solvent is methyl alcohol, ethanol or acetonitrile.
6. the application of the described rare earth compounding of claim 1 is characterized in that by reversible with organic steam or irreversibly control the luminous of rare earth compounding.
7. the application of rare earth compounding as claimed in claim 6 is characterized in that reversibly controlling the luminous of rare earth compounding by methanol steam; Or irreversibly control the luminous of rare earth compounding by acetonitrile steam.
8. the application of rare earth compounding as claimed in claim 7 is characterized in that rare earth compounding is exposed in the methanol steam, the fluorescence intensity of the regulation and control rare earth compounding by regulating methanol steam concentration; Or rare earth compounding is exposed in the acetonitrile steam, strengthen the fluorescence intensity of rare earth compounding by the increase of acetonitrile vapour concentration.
9. the application of the described rare earth compounding of claim 1 in gas-discoloration switch or logical gate device.
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| CN201010101757A CN101798320A (en) | 2010-01-25 | 2010-01-25 | Gasochromic rare earth complex and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702821A (en) * | 2012-05-31 | 2012-10-03 | 上海海事大学 | Anti-fouling agent for fouling prevention of ocean facilities and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702821A (en) * | 2012-05-31 | 2012-10-03 | 上海海事大学 | Anti-fouling agent for fouling prevention of ocean facilities and preparation method thereof |
| CN102702821B (en) * | 2012-05-31 | 2015-05-20 | 上海海事大学 | Anti-fouling agent for fouling prevention of ocean facilities and preparation method thereof |
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Application publication date: 20100811 |