CN101445510B - Pyridine macrocyclic crown ether-based stilbene compound - Google Patents
Pyridine macrocyclic crown ether-based stilbene compound Download PDFInfo
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- CN101445510B CN101445510B CN2009100016687A CN200910001668A CN101445510B CN 101445510 B CN101445510 B CN 101445510B CN 2009100016687 A CN2009100016687 A CN 2009100016687A CN 200910001668 A CN200910001668 A CN 200910001668A CN 101445510 B CN101445510 B CN 101445510B
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- pyridine
- crown ether
- metal ion
- stilbene compound
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Abstract
The invention relates to an organic conjugated compound, in particular to a pyridine macrocyclic crown ether substitute-based stilbene compound, which can form a complex compound with alkali metal ion, alkaline-earth metal ion, transition metal ion and rare metal ion. The stilbene compound of the invention is applied to the fields of dye sensitization solar batteries, organic photoelectron luminescence materials, fluorescent dyes, laser dyes, metal ion molecular probes and the like.
Description
Technical field
The present invention relates to a kind of organic conjugate compound, particularly the stilbene compound that replaces based on pyridine macrocyclic crown ether.
Technical background
The organic conjugate micromolecular compound of stibene class has important use at chemical analysis, dyestuff, medicine, electronic information material and new energy materials etc.Such as triarylamine, benzoxazole, 1,3,4-oxadiazole, 1,3, the stibene derivative that cavity transmission group such as 4-thiadiazoles and triazole and electric transmission group replace can be used as electroluminescent organic material, and has the characteristics of blue emission and luminescent chromaticity purity.This area professional inserts conjugation aromatic hydrocarbons in the middle of knowing the crown ether loop chain, can change crown ether to cationic complex performance and chemical colour reaction function.In recent years, there is crown ether cycle to link patent and academic paper that conjugation aromatic hydrocarbons produces new class organic complex photoelectric material outward again, finds that aromatic ligand and some rare metal ionic complex compound triplet state stable existence time and fluorescence quantum efficiency are far superior to the organic conjugate compound.In 2008, US7393598 disclosed the aza-crown ether ring and has linked tolane or triphenyl diacetylene outward, and the side base adds carboxylate anion's " anchor " in addition, with Eu
3+, Dy
3+And Tb
3+Complex compound.This complex compound is solid-state to have one dimension, the multi-faceted charge transmission of two and three dimensions down, and the carboxylate anion's in the molecule " anchor " existence makes this complex compound at nanometer SiO
2, nano-TiO
2, the individual layer sticking power on the metal electrode increases substantially, but also self assembled monolayer shape or multilayer molecular structure charge transport material.This complex compound has shown the superiority as electroluminescent material.Yet US7393598 does not disclose the luminous efficiency of complex compound, because its described Azacrown ether containing and Eu
3+, Dy
3+And Tb
3+The complex compound that forms only is the substituting group of tolane or triphenyl diacetylene luminescence unit.
Based on above-described realistic problem, the inventor thinks that pyridine nucleus and Schiff's base form conjugated system, and can form the complex compound of fluorescent emission or fluorescent quenching as the crown ether that structural unit constitutes with metal ion, itself and stibene type organic conjugate compound are linked, formation has the electric charge transmission type complex compound novel material of fluorescent emission or fluorescent quenching characteristic, has using value in fields such as organic dye sensitized solar cell, electroluminescent organic material, cationic chemical probe, fluorescence dye, laser dyes and probe biomolecules.
Given this, one of purpose of the present invention just provides a kind of novel stilbene compound based on the pyridine macrocyclic crown ether replacement; Its two preparation method who provides the stilbene compound based on pyridine macrocyclic crown ether of the present invention.
Summary of the invention
The invention provides a kind of stilbene compound that replaces based on pyridine macrocyclic crown ether, have chemical structure shown in the general formula (I):
R is selected from H, CH in its formula of (I)
3, a kind of among CN, ph or the COOH.
The stilbene compound that replaces based on pyridine macrocyclic crown ether provided by the invention has following characteristics:
1. of the present invention based on pyridine macrocyclic crown ether by two nitrogen-atoms of a nitrogen-atoms of pyridine, two Schiff's base and two Sauerstoffatoms and 18-hat-6 that nitrogen-atoms is formed of dioxygen ethylamine, can form stable complex compound with alkalimetal ion, alkaline-earth metal ions, transition metal ion and rare metal ion.
2. of the present invention have 2 based on pyridine macrocyclic crown ether, the two aryl Schiff's base substituted pyridines structures of 6-, and the complex compound that forms with metal ion of the present invention has fluorescent emission and fluorescent quenching characteristic.
3. the stilbene compound molecule that replaces based on pyridine macrocyclic crown ether of the present invention has the dipolar configuration feature.
General formula provided by the invention (I) is based on the stilbene compound that pyridine macrocyclic crown ether replaces, and it is characterized in that can be synthetic by following route:
Substituted phenylethylene is selected from a kind of in vinylbenzene, 4-vinyl toluene, 4-cyano-styrene, 4-styryl phenyl or the 4-vinyl benzoic acid in the synthetic route wherein of the present invention.
Catalyzer refers to the complex compound of triphenylphosphine and palladium or Palladous chloride.
Specific embodiment
By following embodiment stilbene compound and the preparation method who replaces based on pyridine macrocyclic crown ether provided by the invention further specified, its purpose is to understand better content of the present invention.Therefore, the unlisted stilbene compound that replaces based on pyridine macrocyclic crown ether should not be considered as limiting the scope of the invention among the embodiment.
The preparation of embodiment 1 formula (I-1) compound
The preparation of the step same form (II) intermediate: take by weighing 0.2 mole of N, N-dihydroxy ethyl-4-bromaniline and 0.42 mole of Tosyl chloride are dissolved in 180 milliliters of pyridines, and stirring down, 30～80 ℃ of reactions of temperature control finished in 6 hours.In reaction product system impouring 500 ml waters, filter collecting precipitation, can make formula (II) intermediate 97 grams, yield 86%.
The preparation of step 2 formula (III) intermediate: the pyridine-2 that takes by weighing 0.05 mole, the Ortho-Aminophenol of 6-dicarbaldehyde and 1.05 moles is dissolved in 200 milliliters of dehydrated alcohols, stirring reaction under the room temperature, there is yellow mercury oxide to separate out gradually, after-filtration was collected yellow mercury oxide in 48 hours, vacuum-drying makes formula (III) intermediate 13.5 gram yellow powders, yield 85%.148.5～151.0 ℃ of fusing points.
The preparation of step 3 formula (IV): take by weighing each 10 gram of the prepared formula of step 2 (III) intermediate and Anhydrous potassium carbonate respectively and be dispersed in 50 milliliter 1, in the 4-dioxane, after stirring heats up 80 ℃ and eliminates water, add 1 of prepared 20 gram formula (II) intermediates of step 1,450 milliliters of 4-dioxane solution, 80 ℃ of reactions of temperature control are after 48 hours, distillation reclaims 1,400 milliliters of 4-dioxane solvents in distillation residue impouring while hot 200 ml waters, filter and collect brown precipitate.It is in 20% the hydrochloric acid that brown precipitate is dissolved in mass percent, thereafter functional quality percentage ratio is 8% ammoniacal liquor neutralization, slowly separate out yellow mercury oxide, the yellow mercury oxide that filters out uses N, dinethylformamide/alcohol mixed solvent carries out recrystallization, after the vacuum-drying, make yellow powder shape formula (IV) compound 11.9 grams, yield 62%.
Ultimate analysis: C
29H
25BrN
4O
2Measured value (calculated value): C64.16 (64.33), H4.55 (4.65), N10.17 (10.35), Br14.45 (14.76).
H
1-NMR(DMSO-d
6)δ：4.13～4.37(m，8H)，6.88～8.13(m，15H)，9.73(s，2H)。
EI-MS(m/e)：540.12(M，100％)。
The preparation of step 4 formula (I-1):
Get formula (IV) product 10 grams that step 3 makes and be dissolved in 50 milliliters of N, in the dinethylformamide, add triethylamine 30 grams successively,, stirred down back flow reaction 20 hours Ethenylbenzene formic acid 3 grams, dichloro bi triphenyl phosphine palladium catalyst 0.5 gram.Reaction finishes, add 1 gram sodium sulphite, continue to stir 2 hours, remove by filter black precipitate, in filtrate cooling back impouring 200 ml waters, functional quality percentage ratio is in 20% the hydrochloric acid and mass percent is in 8% the aqueous solution and regulates the pH value respectively, separate out yellow mercury oxide, filter out yellow mercury oxide, vacuum-drying, promptly make yellow powder 8.1 grams of formula (I-1) compound, yield 62%.264～265 ℃ of fusing points
Ultimate analysis: C
38H
32N
4O
4Measured value (calculated value): C74.96 (74.98), H5.25 (5.30), N9.17 (9.20).
H
1-NMR(DMSO-d
6)δ：3.73～4.17(m，8H)，6.88～8.26(m，21H)，9.93(s，2H)，11.03(s，1H)。
EI-MS(m/e)：609.24(M+1，44％)，608.24(M，100％)，610.25(M-18，11％)。
Uv-visible absorption spectroscopy (aqueous solution, pH=8.3): λ max=372nm.
Fluorescence spectrum (aqueous solution, pH=8.3): λ max=456nm.
The preparation of embodiment 2 formulas (I-2) compound
According to preparation method and the schedule of operation of embodiment 1, the raw material of step 4 among the embodiment 1 is changed to cyano-styrene Ethenylbenzene formic acid, just can make (I-2) provided by the invention compound, outward appearance is a yellow powder, 104～107 ℃ of fusing points.
Ultimate analysis: C
38H
31N
5O
2Measured value (calculated value): C77.36 (77.40), H5.28 (5.30), N11.87 (11.88).
H
1-NMR(DMSO-d
6)δ：3.77～4.31(m，8H)，6.88～8.26(m，21H)，9.93(s，2H)。
EI-MS(m/e)：589.25(M，100％)。
Uv-visible absorption spectroscopy (N, dinethylformamide solution): λ max=368nm.
Fluorescence spectrum (N, dinethylformamide solution): λ max=451nm.
Embodiment 3 formulas (I-1) compound and Cu
2+, Zn
2+, and Ni
2+The preparation and the spectral response curve of title complex
As macrocyclic crown ether part (L), prepare itself and Cu with formula (I-1) compound respectively
2+, Zn
2+And Ni
2+Title complex.Get 1.2 gram formula (I-1) compounds and be dissolved in the 50 ml water deionizations with 0.5 gram Gerhardite, 0.6 gram zinc nitrate hexahydrate or 0.6 gram Nickelous nitrate hexahydrate respectively, stirred 24 hours under the room temperature.After add the deionized water weaker concn respectively 10
-4About mol, mensuration formula (I-1) compound and cupric nitrate, zinc nitrate and nickelous nitrate title complex aqueous solution uv-visible absorption spectroscopy, its λ max is respectively 341nm, 363nm and 375nm.When excitation wavelength is 350nm, only observe formula (I-1) compound and Zn
2+The title complex aqueous solution have fluorescence emitting characteristics, fluorescence spectrum λ max is 431nm.
Claims (1)
1. stilbene compound that replaces based on pyridine macrocyclic crown ether, the formula shown in (I) that it is characterized in that having formula:
Wherein R is selected from CN or COOH.
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| CN2009100016687A CN101445510B (en) | 2009-01-10 | 2009-01-10 | Pyridine macrocyclic crown ether-based stilbene compound |
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| Publication Number | Publication Date |
|---|---|
| CN101445510A CN101445510A (en) | 2009-06-03 |
| CN101445510B true CN101445510B (en) | 2011-01-12 |
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| CN106929008B (en) * | 2017-03-14 | 2019-03-08 | 南方科技大学 | Potassium ion fluorescent probe and preparation method and application thereof |
| CN111961437B (en) * | 2020-09-09 | 2021-08-17 | 湖南大学 | Application of condensation compound of pillar aromatic hydrocarbon and crown ether hybrid macrocycle as adhesive |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7393598B2 (en) * | 2004-03-10 | 2008-07-01 | Hcf Partners, L.P. | Light emitting molecules and organic light emitting devices including light emitting molecules |
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2009
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7393598B2 (en) * | 2004-03-10 | 2008-07-01 | Hcf Partners, L.P. | Light emitting molecules and organic light emitting devices including light emitting molecules |
Non-Patent Citations (3)
| Title |
|---|
| Laura Valencia, et al.The synthesis of three novel pendant armed macrocyclic ligands. The X-ray crystal structure of a cadmium complex derived from the first oxaazamacrocycle bearing two alkylated aromatic amine functions.《Polyhedron》.2001,第20卷3091-3099. * |
| 何永炳等.含吡啶环系西佛碱大环配合物和氮杂大环自由配体的合成.《有机化学》.1998,第18卷347-351. * |
| 张田林等.双极型均二苯乙烯发光材料的合成和光电特性.《材料科学与工程学报》.2007,第25卷(第5期),704-708. * |
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