CN101298497B - Preparation of doping optical non-linear chromophore coordination high polymer - Google Patents
Preparation of doping optical non-linear chromophore coordination high polymer Download PDFInfo
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- CN101298497B CN101298497B CN200810034053XA CN200810034053A CN101298497B CN 101298497 B CN101298497 B CN 101298497B CN 200810034053X A CN200810034053X A CN 200810034053XA CN 200810034053 A CN200810034053 A CN 200810034053A CN 101298497 B CN101298497 B CN 101298497B
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Abstract
The invention, pertaining to the field of non-linear optical materials, relates to a preparation method for a coordination polymer doped with optical non-linear chromophores. The invention adds 5-formyl-8-hydroxyquinoline and 3, 5-diaminobenzoic acid by molar weight ratio of 2: 1 to toluene, circle heats the mixture for more than 48 hours and then washes the mixture with alcohol and trichloromethane after filtration; mixes the non-linear chromophore with 8-hydroxyquinoline according to the molar weight proportion required to prepare non-linear chromophore modified 8-hydroxyquinoline by thermal chemical method; adds the 5-formyl-8-hydroxyquinoline and the non-linear chromophore modified 8-hydroxyquinoline to methanol and then adds sufficient coordination salt required for coordination under severe stirring condition, waits for the solution to clarify. The optical non-linear chromophore of the invention is connected with the coordination polymer by a coordination bond. The invention has the advantages of good stability, simple process and low cost without phase separation.
Description
Technical field
The present invention relates to a kind of preparation of doping optical non-linear chromophore coordination high polymer, belong to the nonlinear optical material field.
Background technology
At present, because latent effect in fields such as all-optical switch, light conversion, optical signal processing and optical communications, non-linear susceptibility is big, the fast material of third-order non-linear response causes increasing concern, and wherein organic polymer, organo-metallic coordination polymer are becoming the focus of research.
The organic polymer nonlinear optical material has the non-linear chromophore with big pi-conjugated structure usually, by designing, changing the change that these chromophores can realize the material nonlinearity performance, helps the excellent nonlinear optical material of exploration.And most of polymer can be handled (spin-coating method, dip-coating method etc.) preparation amorphous membrance by liquid phase, and device technology is simple.But organic polymer material also has its limitation as nonlinear material.
The organic polymer nonlinear material mainly is divided three classes: 1) non-linear chromophore physical doping polymer; 2) grafting of non-linear chromophore side chain is to polymer; 3) non-linear chromophore connects high polymer main chain.Back two classes all need can start with the high polymer monomer of organic chromophore grafting from preparation, and synthetic route is long, and the adjustment to overall performance each time all needs from the beginning to operate complex steps.
Organo-metallic coordination polymer has advantages such as big molecule hyperpolarizability and ultrafast nonlinear response because of it very attractive.But the easy crystallization of most of organo-metallic coordination polymer, so device need prepare the single crystal of this class material.The complicated process of preparation of this monocrystalline will obtain the monocrystalline difficulty very that matter is measured, size is big.
Summary of the invention
The object of the present invention is to provide a kind of preparation of doping optical non-linear chromophore coordination high polymer, made material both have organic coordination polymer performance, doping optical non-linear chromophore is realized the adjusting of material property again.
Doping optical non-linear chromophore provided by the present invention is realized by technological process shown in Figure 1 to the preparation method of coordination high polymer, now is presented below:
(1) with 5-aldehyde radical-oxine and 3, the 5-diaminobenzoic acid joins in the toluene with 2: 1 ratio of molar weight, and reflux 24～72 hours is filtered the back also respectively with ethanol and trichloromethane washing;
(2) the non-linear chromophore base is mixed with oxine in the ratio of required grafting molar weight, concentrated hydrochloric acid is the non-linear chromophore based solvent, and sodium hydroxide is the oxine solvent, prepares non-linear chromophore modification oxine by thermochemical method;
(3) 5-aldehyde radical-oxine and non-linear chromophore modification oxine are joined in the methyl alcohol, under the vigorous stirring, add the required capacity metal-complexing salt of coordination, treat the solution clarification.
Described 5-aldehyde radical-oxine all has synthetic at the traditional literature report, preferable methods is the back flow reaction recrystallization method.
Described metal-complexing salt preferred soluble metal aluminium salt or soluble metal molysite are as aluminum chloride, aluminum nitrate, aluminium hydroxide, iron trichloride, iron nitrate etc.
The preferred 4-N of described non-linear chromophore base, N dimethylamine base phenol, its grafting molar weight is 1: 1.
The described thermochemical method preferred reaction time stirred 1 hour, with pH value to 3～7 of dilute hydrochloric acid conditioned reaction liquid, with ethyl alcohol recrystallization.
Doping optical non-linear chromophore provided by the present invention has the following advantages to the method for coordination high polymer:
(1) can realize the adjusting of this coordination high polymer overall performance by changing kind, the valence state of metal ion.
(2) can realize the doping of different chromophores by with different optical non-linear chromophore modification oxines.
(3) optical non-linear chromophore is connected with coordination high polymer by coordinate bond, and being separated can not appear in good stability.
(4) doping way is simple, and preparation gained material can pass through collosol and gel legal system film, and technology is simple, and cost is low.
Description of drawings
Fig. 1 doping optical non-linear chromophore provided by the present invention is to the operational path of the method for coordination high polymer.
The mass spectrum of Fig. 2 5-aldehyde radical-oxine.The synthetic target product of proof.
Fig. 33,5-diamino (the oxine)-benzoic proton nmr spectra that records in the deuterated dimethyl sulfoxide solvent.Confirm synthetic target product.
The proton nmr spectra that in the deuterated dimethyl sulfoxide solvent, records of Fig. 4 5-(4-N, silomate base benzene) azo-oxine.Confirm synthetic target product.
The Z-scan curve of the aluminium coordination high polymer film of Fig. 5 embodiment 1 preparation, first peak Hou Gu shows that this material is self-defocusing.Nonlinear refractive index n that as calculated must this material
2=-1.28 * 10
-8Esu.
The Z-scan curve of the iron coordination high polymer film of Fig. 6 embodiment 2 preparations, first paddy postpeak shows that this material is self-focusing.Nonlinear refractive index n that as calculated must this material
2=-1.84 * 10
-8Esu.
The mix structural representation of two chinoline coordination high polymers of azo modification quinoline of Fig. 7 the present invention.
Embodiment
Mode illustrates the present invention by the following examples, but is not limited only to following examples.
25g analytical pure oxine is dissolved in the 100mL dehydrated alcohol, adds NaOH solution (50gNaOH is dissolved in the 70mL deionized water), mix and cool off the back and drip trichloromethane (25mL dripped off in 1 hour).After trichloromethane drips, intensification stirring and refluxing reaction 18 hours.Steam excessive trichloromethane and ethanol on Rotary Evaporators, residual residue is dissolved in the 600mL deionized water, regulates pH value to 5～6 with dilute hydrochloric acid, and the precipitation generation is arranged, suction filtration and behind the deionized water wash throw out placed 80 ℃ of oven dryings.Dried solid grinding powder with the Petroleum ether extraction of 90～120 ℃ of boiling ranges 48 hours, with the extracting solution cooling, filters and collects precipitate, with the dehydrated alcohol recrystallization in the fat extraction device.Obtain 2.1g5-aldehyde radical-oxine.Mass spectral characteristi the results are shown in Figure 2.
With 0.27g 5-aldehyde radical-oxine and 0.618g 3, the 5-diaminobenzoic acid joins in the toluene, reflux 48 hours.The filtered while hot products therefrom, and respectively with ethanol and trichloromethane washing.Treat 80 ℃ of following dryings.Get 0.72g 3,5-diamino (oxine)-phenylformic acid.Proton nmr spectra characterization result (see figure 3): 1H NMR (500MHz, DMSO-d6): δ 13.12 (br, 1H), 10.68 (br, 2H), 9.92 (d, 2H), 9.13 (s, 2H), 8.96 (d, 2H), 8.16 (d, J=7.8Hz, 2H), 7.76-7.73 (m, 4H), 7.59 (s, 1H), 7.24 (2H) .Anal.Calcdfor C27H18N4O4:C 70.12% for d, J=7.8Hz; H 3.92%; N 12.11%.Found:C 69.30%; H 4.04%; N 12.07%.
With 2.72g 4-N, N dimethylamine base phenol and 12mL concentrated hydrochloric acid join in the flask that the 20ml deionized water is housed, and flask is positioned in the cold ethanol bath (5 ℃).2.90g oxine and 6g NaOH are dissolved in the 100ml deionized water, this drips of solution is added in the flask.Stirred 1 hour, with the pH value to 5 of dilute hydrochloric acid conditioned reaction liquid.Filter the collecting precipitation thing, clean repeatedly with deionized water.Drying, the product ethyl alcohol recrystallization.Productive rate 62%.Proton nmr spectra characterization result (see figure 4): 1H NMR (500MHz, DMSO-d6): δ 10.45 (br, 1H), 9.27 (d * d, J=14Hz, 1H), 8.97 (d * d, 1H), and 7.91-7.86 (m, 3H), 7.72 (d * d, J=14Hz, 1H), 7.20 (d, 1H), 6.86 (d, 2H), 3.7 (s, 6H).
With 0.115g 3,5-diamino (oxine)-phenylformic acid, 0.0182g 5-(4-N, silomate base benzene) azo-oxine and 0.08g Aluminium chloride hexahydrate add in the 20mL methyl alcohol, and vigorous stirring is treated the solution clarification.
With spin-coating legal system film.Under the 1064nm wavelength, obtain the nonlinear refractive index n of this material with the Z-scan technology
2=-1.28 * 10
-8Esu.See Fig. 5.
Will be by the 0.115g 3 of embodiment 1 preparation, 5-diamino (oxine)-phenylformic acid, 0.0182g5-(4-N, silomate base benzene) azo-oxine and 0.06g FERRIC CHLORIDE ANHYDROUS are added in the 20mL methyl alcohol, and vigorous stirring is treated the solution clarification.
With spin-coating legal system film.Under the 1064nm wavelength, obtain the nonlinear refractive index n of this material with the Z-scan technology
2=-1.84 * 10
-8Esu.See Fig. 6.
Claims (5)
1. a preparation of doping optical non-linear chromophore coordination high polymer comprises the steps:
(1) with 5-aldehyde radical-oxine and 3, the 5-diaminobenzoic acid joins in the toluene with 2: 1 ratio of molar weight, and reflux 24～72 hours is filtered the back also respectively with ethanol and trichloromethane washing;
(2) with non-linear chromophore base 4-N, N dimethylamine base phenol mixes with oxine in 1: 1 ratio of required grafting molar weight, concentrated hydrochloric acid is the non-linear chromophore based solvent, and sodium hydroxide is the oxine solvent, prepares non-linear chromophore modification oxine by thermochemical method;
(3) step (1) products therefrom and non-linear chromophore modification oxine join in the methyl alcohol, under the vigorous stirring, add required capacity metal-complexing salt soluble metal aluminium salt or the soluble metal molysite of coordination, treat the solution clarification.
2. by the described a kind of preparation of doping optical non-linear chromophore coordination high polymer of claim 1, it is characterized in that described 5-aldehyde radical-oxine adopts the preparation of back flow reaction recrystallization method.
3. by the described a kind of preparation of doping optical non-linear chromophore coordination high polymer of claim 1, it is characterized in that described soluble metal aluminium salt is aluminum chloride, aluminum nitrate or aluminium hydroxide.
4. by the described a kind of preparation of doping optical non-linear chromophore coordination high polymer of claim 1, it is characterized in that described soluble metal molysite is iron trichloride or iron nitrate.
5. by the described a kind of preparation of doping optical non-linear chromophore coordination high polymer of claim 1, it is characterized in that described thermochemical method preferred reaction time stirring 1 hour, with pH value to 3～7 of dilute hydrochloric acid conditioned reaction liquid, with ethyl alcohol recrystallization.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1427001A (en) * | 2002-09-27 | 2003-07-02 | 山西至诚科技有限公司 | Preparation method of organic electro luminous material 8-hydroxy quinoline aluminium |
| CN1594382A (en) * | 2004-06-18 | 2005-03-16 | 中国科学院广州化学研究所 | Linear copolymer containing 8-hydroxyquinoline metal complex and its preparation and use |
| CN1597669A (en) * | 2004-07-19 | 2005-03-23 | 太原理工大学 | 8- hydroxy quinoline bryhtening blue light and preparation method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1427001A (en) * | 2002-09-27 | 2003-07-02 | 山西至诚科技有限公司 | Preparation method of organic electro luminous material 8-hydroxy quinoline aluminium |
| CN1594382A (en) * | 2004-06-18 | 2005-03-16 | 中国科学院广州化学研究所 | Linear copolymer containing 8-hydroxyquinoline metal complex and its preparation and use |
| CN1597669A (en) * | 2004-07-19 | 2005-03-23 | 太原理工大学 | 8- hydroxy quinoline bryhtening blue light and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 周亚东,曾和平,靖慧莲,袁国赞,欧阳新华.8-羟基喹啉金属配合物在电致发光器件中的应用研究进展.《有机化学》.2006,第26卷(第6期),783-792. * |
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