CN102618086A - Method for preparing trapezoidal broadband absorption carbene squaraine dye with one-step method - Google Patents
Method for preparing trapezoidal broadband absorption carbene squaraine dye with one-step method Download PDFInfo
- Publication number
- CN102618086A CN102618086A CN2012100587740A CN201210058774A CN102618086A CN 102618086 A CN102618086 A CN 102618086A CN 2012100587740 A CN2012100587740 A CN 2012100587740A CN 201210058774 A CN201210058774 A CN 201210058774A CN 102618086 A CN102618086 A CN 102618086A
- Authority
- CN
- China
- Prior art keywords
- carbene
- cyanine dye
- wide band
- prepares
- single stage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 Cc(cc1)nc2c1c(*)cc(*)c2* Chemical compound Cc(cc1)nc2c1c(*)cc(*)c2* 0.000 description 1
Images
Landscapes
- Indole Compounds (AREA)
Abstract
The invention relates to a method for preparing a trapezoidal broadband absorption carbene squaraine dye with a one-step method. The method comprises the following steps of: fully mixing functional carbine, a squaric acid, a ligand and a solvent at the room temperature; undergoing a reflowing reaction at the temperature of 60-130 DEG C for 10-120 hours; and after the reaction, purifying to obtain the carbene squaraine dye, wherein the mass ratio of the functional carbine to the squaric acid is (20-10):(4-1). The preparation method provided by the invention is easy and practicable, has a good economic benefit, and is suitable for industrial production; and the carbene squaraine dye prepared with the method can be widely applied in the fields of nonlinear optics, photodynamics therapy, optical database storage, laser printing, biological probes, near infrared mapping, solar cells, and the like.
Description
Technical field
The invention belongs to the preparation field of ultraviolet-visible-near infrared wide band side acid cyanines absorbing material, particularly relate to a kind of single stage method and prepare the method that trapezoidal wide band absorbs the carbene indolenium squaraine cyanine dye.
Background technology
Ultraviolet-visible light is meant the hertzian wave between the wavelength 200-700nm, and the near infrared light zone is meant the hertzian wave between the 700-1500nm.Has the molecule of three wave band absorptive functions of ultraviolet-visible-near infrared owing to have wide absorption bands; Have good spectral absorption performance and spectrum and cover the survey scope, can be widely used in a plurality of fields such as military affairs, infrared camouflage, species analysis, medical detection, sensitization, photopolymerization, nonlinear optical material, solar cell.
First since the synthetic compound side's acid of JACS J.A.C.S report, be that raw material synthesize obtain a large amount of non-indolenium squaraine cyanine dye with it from nineteen fifty-nine Cohen S etc.Indolenium squaraine cyanine dye undergoes an unusual development rapidly since then; Indolenium squaraine cyanine dye and en acid cyanine dyes are owing to have unique conjugated system; D-π-A-π-D and D-π-A structure; Have good optical character,, absorption big and emission wavelength ranges wide (from seeing near infrared region) like absorbancy, simultaneously high luminous quantum efficiency be easy to carry out advantages such as molecular designing, modification and cause both at home and abroad and pay close attention to widely.
Up to the present the material that independent ultraviolet-visible absorbs and the material of adsorbing close infrared light are more; Prepare also simple relatively; Have strong absorption in the visible region like azo class and en acid cyanines material, the sour cyanines class in side, phthalocyanines material have strong near infrared absorption performance.But the material that has ultraviolet-visible-near infrared absorption simultaneously still seldom.
Chinese patent CN1511883A discloses a kind of novel indolenium squaraine cyanine dye, and structural formula is:
Its absorption bands is at 700～1100nm, and absorption bands has covered near infrared region;
CN101395228A discloses quinaldine based en acid cyanines 400～550nm and symmetry, the sour cyanines of asymmetric side again, in the 650-800nm scope, has good absorption;
CN101824042A discloses a kind of triphenylamine-two thieno-indene derivative, and structural formula is:
The absorption spectrum of its molecular solution and film has tangible absorption at 200～850nm wave band;
CN101880477A discloses a kind of POSS base hydridization side's acid squarine near-infrared absorption dye, and its structure type is dumbbell shape, line style, network-type or cross-linking type, and absorption bands is positioned at 650～1200nm;
The research of broadband absorbing material at present is less, and research has the following disadvantages:
1, absorption bands is single, only has absorption at ultraviolet-visible wave band or near-infrared band, can not reach broadband absorption simultaneously;
2, synthesis procedure is complicated, and separation and purification is loaded down with trivial details, is difficult to carry out suitability for industrialized production.Most at present wide band absorbing material synthesis step relative complex, separation and purification etc. separate through means such as column chromatographies, and separation and purification is difficulty very.Be difficult to produce on a large scale.
Summary of the invention
Technical problem to be solved by this invention provides a kind of single stage method and prepares the method that trapezoidal wide band absorbs the carbene indolenium squaraine cyanine dye; This method is simple; Mild condition; Aftertreatment is simple, and this dyestuff absorbs carbene side's acid cyanines high molecular dye for the wide band that has absorption at ultraviolet-visible-near infrared region.
A kind of single stage method of the present invention prepares the method that trapezoidal wide band absorbs the carbene indolenium squaraine cyanine dye, comprising:
With function carbene, side acid, part and solvent thorough mixing at room temperature, carry out back flow reaction 10-120h at 60～130 ℃ then, after reaction finished, purifying promptly obtained carbene side's acid cyanines; Wherein the function carbene is 20～10 with the mass ratio of side's acid: 4～1.
Described function carbene comprises at least two kinds copolymerization alkynes class monomer, and structural formula is (C
2H
2R
1)
N1(C
2H
2R
2)
N2, n wherein
1, n
2Be 20～200 integer, n
1: n
2=1: 5, R
1Be hydrogen, halogen, hydroxyl, alkynyl, aryl, C
1-C
20Alkyl, alicyclic radical, alkoxyl group, vinyl, allyl group or styryl; R
2Be the quinoline ring
Wherein X, Y, Z be selected from respectively-H ,-NO
3,-COOH ,-SO
3H ,-CN; Perhaps pyridine ring
Wherein X, Y, Z be selected from respectively-H ,-NO
3,-COOH ,-SO
3H ,-CN.
Described function carbene is 15～10: 2～1 with the mass ratio of side's acid.
Described solvent is one or more in hexanaphthene, toluene, YLENE, methyl alcohol, ethanol, benzene, THF, dioxane, N, DMSO 99.8MIN., the methylene dichloride, and the mass ratio of itself and function carbene is 100～2: 1.
Described part is propyl carbinol, Virahol or USP Kosher.
The volume ratio of described solvent and part is 100～1: 1, is preferably 10～1: 1.
Described purifying is for realizing through decompress filter, water washing process.
The structure type of the carbene indolenium squaraine cyanine dye of gained is a ladder structure.
The carbene indolenium squaraine cyanine dye of gained is applied to fields such as nonlinear optics, photodynamic therapy, light data storage, Laser Printing, bioprobe, near-infrared photography and solar cell.
Between the reaction period of the present invention; The color of solution is along with the carrying out of reaction reddens gradually; Purpling is green again, quinoline in the carbene side chain or pyridine ring, and at first the square acid-respons with esterification generates en acid cyanines; Then quinoline on en acid cyanines and another carbene side chain or pyridine ring continue the sour cyanines in reaction generation symmetry side, form ladder structure.The formation of the sour cyanines in side is followed the tracks of through online ultraviolet-visible spectrophotometer, through controlling reaction time, reaches the purpose of the content ratio of sour cyanines in adjusting side and en acid cyanines, reaches carbene indolenium squaraine cyanine dye absorption spectrum is controlled.
Carbene macromole, side sour bridge linkage group and the alcohols part of the present invention through having quinoline or pyridine side group comprises reactions such as hydrolysis, condensation, preparation carbene indolenium squaraine cyanine dye; Through controlling reaction time, conditioned reaction degree, quinoline in the carbene side chain or pyridine ring; At first the square acid-respons with esterification generates en acid cyanines; Then quinoline on en acid cyanines and another carbene side chain or pyridine ring continue the sour cyanines in reaction generation symmetry side, form ladder structure, the different reaction times; The corresponding different ens acid cyanines/sour cyanines content ratio in side, the side group through making the carbene the main chain sour cyanines in the side of having and the sour cyanines of en simultaneously reach the purpose of wide band absorption.Only need through simple suction filtration simultaneously, washing can reach the purpose of purifying.
Beneficial effect
(1) carbene side's acid cyanines preparation technology of the present invention is simple, through single step reaction, obtains wide band absorption carbene side's acid cyanines high molecular dye that ultraviolet-visible-near infrared region has absorption;
(2) structure of this carbene side acid cyanines can pass through controlling reaction time, and the structure that obtains on molecular level is constructed, and makes to contain the sour cyanines of different ratios content en/sour cyanines side group in side, the absorption spectrum ranges of regulatory molecule on the carbene main chain;
(3) mild condition of this reaction, easy reaction, aftertreatment is simple, only need get final product purified product through washing, very helps large-scale industrial production.
Description of drawings
Fig. 1 is the nuclear magnetic spectrogram of carbene side's acid cyanines wide band absorbing dye of embodiments of the invention 1 preparation;
Fig. 2 is the ir spectra of carbene side's acid cyanines wide band absorbing dye of embodiments of the invention 1 preparation;
Fig. 3 is that uv-visible absorption spectra in carbene side's acid cyanines wide band absorbing dye reaction process of embodiments of the invention 1 preparation is with the change curve in reaction times; Wherein 1～8 representes 1～8h respectively;
Fig. 4 is the Tg curve of carbene side's acid cyanines wide band absorbing dye of embodiments of the invention 1 preparation;
Fig. 5 is the spectrum of carbene side's acid cyanines wide band absorbing dye of embodiments of the invention 1 preparation.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Take by weighing 861mg (1mmol reactive group) P2 (concrete structure is seen reaction formula) and 45.6mg side acid (0.4mmol) respectively; Place the 50mL round-bottomed flask; Add 7.5mL propyl carbinol and 7.5mL toluene again, back flow reaction behind the thorough mixing (uv-visible absorption spectra is followed the tracks of reaction mechanism, and is as shown in Figure 3); Solution colour reddens gradually, begins to become little green at last again; Absorption spectrum all has stronger absorption in the Visible-to-Near InfaRed zone, termination reaction behind the reaction 48h, and after the cooling room temperature, decompress filter gets thick product.Crude product repeatedly with the acid of the deionized water wash side of removing, is obtained the macromolecule product of greyish-green.
Reaction formula is following:
X=1 wherein, Y=5.
Take by weighing 811mg (1mmol reactive group) P2 (concrete structure is seen reaction formula) and 45.6mg side acid (0.4mmol) respectively; Place the 50mL round-bottomed flask; Add 7.5mL propyl carbinol and 7.5mL toluene again; Back flow reaction behind the thorough mixing (uv-visible absorption spectra tracking reaction mechanism), solution colour reddens gradually, begins to become little green at last again; Absorption spectrum all has stronger absorption in the Visible-to-Near InfaRed zone, termination reaction behind the reaction 48h, and after the cooling room temperature, decompress filter gets thick product.Crude product repeatedly with the acid of the deionized water wash side of removing, is obtained henna macromolecule product.
Reaction formula:
X=1 wherein, Y=5.
Claims (10)
1. a single stage method prepares the method that trapezoidal wide band absorbs the carbene indolenium squaraine cyanine dye, comprising:
With function carbene, side acid, part and solvent thorough mixing at room temperature, carry out back flow reaction 10-120h at 60～130 ℃ then, after reaction finished, purifying promptly obtained the carbene indolenium squaraine cyanine dye; Wherein the function carbene is 20～10 with the mass ratio of side's acid: 4～1.
2. a kind of single stage method according to claim 1 prepares the method that trapezoidal wide band absorbs the carbene indolenium squaraine cyanine dye, and it is characterized in that: described function carbene comprises at least two kinds copolymerization alkynes class monomer, and structural formula is (C
2H
2R
1)
N1(C
2H
2R
2)
N2, n wherein
1, n
2Be 20～200 integer, n
1: n
2=1: 5, R
1Be hydrogen, halogen, hydroxyl, alkynyl, aryl, C
1-C
20Alkyl, alicyclic radical, alkoxyl group, vinyl, allyl group or styryl; R
2Be the quinoline ring
Wherein X, Y, Z be respectively-H ,-NO
3,-COOH ,-SO
3H ,-CN in arbitrary group; Perhaps pyridine ring
Wherein X, Y, Z be respectively-H ,-NO3 ,-COOH ,-SO3H ,-CN in arbitrary group.
3. a kind of single stage method according to claim 1 prepares the method that trapezoidal wide band absorbs the carbene indolenium squaraine cyanine dye, it is characterized in that: described function carbene is 15～10: 2～1 with the mass ratio of side's acid.
4. a kind of single stage method according to claim 1 prepares the method that trapezoidal wide band absorbs the carbene indolenium squaraine cyanine dye; It is characterized in that: described solvent is one or more in hexanaphthene, toluene, YLENE, methyl alcohol, ethanol, benzene, THF, dioxane, N, DMSO 99.8MIN., the methylene dichloride, and the mass ratio of itself and function carbene is 100～2: 1.
5. a kind of single stage method according to claim 1 prepares the method that trapezoidal wide band absorbs the carbene indolenium squaraine cyanine dye, and it is characterized in that: described part is propyl carbinol, Virahol or USP Kosher.
6. a kind of single stage method according to claim 1 prepares the method that trapezoidal wide band absorbs the carbene indolenium squaraine cyanine dye, and it is characterized in that: the volume ratio of described solvent and part is 100～1: 1.
7. a kind of single stage method according to claim 1 prepares the method that trapezoidal wide band absorbs the carbene indolenium squaraine cyanine dye, and it is characterized in that: the volume ratio of described solvent and part is 10～1: 1.
8. a kind of single stage method according to claim 1 prepares the method that trapezoidal wide band absorbs the carbene indolenium squaraine cyanine dye, it is characterized in that: described purifying is realized through decompress filter, water washing process.
9. a kind of single stage method according to claim 1 prepares the method that trapezoidal wide band absorbs the carbene indolenium squaraine cyanine dye, and it is characterized in that: the structure type of the carbene indolenium squaraine cyanine dye of gained is a ladder structure.
10. a kind of single stage method according to claim 1 prepares the method that trapezoidal wide band absorbs the carbene indolenium squaraine cyanine dye, and it is characterized in that: the carbene indolenium squaraine cyanine dye of gained is applied to nonlinear optics, photodynamic therapy, light data storage, Laser Printing, bioprobe, near-infrared photography and solar cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100587740A CN102618086B (en) | 2012-03-07 | 2012-03-07 | Method for preparing trapezoidal broadband absorption carbene squaraine dye with one-step method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100587740A CN102618086B (en) | 2012-03-07 | 2012-03-07 | Method for preparing trapezoidal broadband absorption carbene squaraine dye with one-step method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102618086A true CN102618086A (en) | 2012-08-01 |
| CN102618086B CN102618086B (en) | 2013-12-11 |
Family
ID=46558311
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100587740A Expired - Fee Related CN102618086B (en) | 2012-03-07 | 2012-03-07 | Method for preparing trapezoidal broadband absorption carbene squaraine dye with one-step method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102618086B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4830786A (en) * | 1986-02-27 | 1989-05-16 | Syntex (U.S.A.) Inc. | Squaraine dyes |
| US5026905A (en) * | 1984-08-28 | 1991-06-25 | Syntex (U.S.A.) Inc. | Fluorescent dyes |
| US5039818A (en) * | 1986-02-27 | 1991-08-13 | Syntex (U.S.A.) Inc. | Squaraine dye |
| EP0940450A1 (en) * | 1996-05-03 | 1999-09-08 | Perkin-Elmer Corporation | Energy transfer dyes with enhanced fluorescence |
| US6605740B2 (en) * | 2001-04-02 | 2003-08-12 | Spyros Theodoropulos | Fluorescent dyes for the labeling of biological substrates |
| CN1511883A (en) * | 2002-12-31 | 2004-07-14 | 中国人民解放军63971部队 | Novel squarylium cyanine dye containing quinoxalinone structure |
| CN101346438A (en) * | 2005-12-30 | 2009-01-14 | 科学与工业研究委员会 | Amphipathic squarylium cyanine dyes, its preparation method and use thereof |
| CN101395228A (en) * | 2006-01-06 | 2009-03-25 | 科学与工业研究委员会 | Quinaldine based semisquaraines and squaraine dyes, process for preparation thereof and use thereof |
| CN101763945A (en) * | 2009-06-12 | 2010-06-30 | 江南大学 | Preparation of squaraine dye-sensitized nanocrystalline film electrode |
-
2012
- 2012-03-07 CN CN2012100587740A patent/CN102618086B/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5026905A (en) * | 1984-08-28 | 1991-06-25 | Syntex (U.S.A.) Inc. | Fluorescent dyes |
| US4830786A (en) * | 1986-02-27 | 1989-05-16 | Syntex (U.S.A.) Inc. | Squaraine dyes |
| US5039818A (en) * | 1986-02-27 | 1991-08-13 | Syntex (U.S.A.) Inc. | Squaraine dye |
| EP0940450A1 (en) * | 1996-05-03 | 1999-09-08 | Perkin-Elmer Corporation | Energy transfer dyes with enhanced fluorescence |
| US6605740B2 (en) * | 2001-04-02 | 2003-08-12 | Spyros Theodoropulos | Fluorescent dyes for the labeling of biological substrates |
| CN1511883A (en) * | 2002-12-31 | 2004-07-14 | 中国人民解放军63971部队 | Novel squarylium cyanine dye containing quinoxalinone structure |
| CN101346438A (en) * | 2005-12-30 | 2009-01-14 | 科学与工业研究委员会 | Amphipathic squarylium cyanine dyes, its preparation method and use thereof |
| CN101395228A (en) * | 2006-01-06 | 2009-03-25 | 科学与工业研究委员会 | Quinaldine based semisquaraines and squaraine dyes, process for preparation thereof and use thereof |
| CN101763945A (en) * | 2009-06-12 | 2010-06-30 | 江南大学 | Preparation of squaraine dye-sensitized nanocrystalline film electrode |
Non-Patent Citations (2)
| Title |
|---|
| 杨小兵等: "一种新型方酸菁近红外吸收染料的合成研究", 《染料与染色》 * |
| 杨成等: "新型多臂方酸菁化合物的合成及光谱性质", 《应用化学》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102618086B (en) | 2013-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rondao et al. | High-performance near-infrared luminescent solar concentrators | |
| CN102643432B (en) | Preparation method for cholesteric siloxane side-chain liquid crystal polymer | |
| CN108102408B (en) | A kind of preparation and application of the nir dye based on azepine fluorine borine | |
| CN103044952A (en) | Asymmetric porphyrin solar cell dye and preparation method thereof | |
| Sozmen et al. | Heteroleptic metallosupramolecular complexes of bodipy dyes as energy transfer cassettes | |
| CN102952413B (en) | Benzpyrole squaric acid cyanine dye and preparation method thereof | |
| CN105801465A (en) | Water-soluble indole croconium cyanine colorimetric probe, preparation method and application | |
| CN113773329A (en) | Method for realizing passive regulation and control of near-infrared reflectivity of phthalocyanine organic material | |
| CN104226335B (en) | A kind of multilevel hierarchy bismuth sulfide and its preparation method and application | |
| CN103242526A (en) | Preparation method of photoresponse type hyperbranched zinc phthalocyanine polymer | |
| Knör | Synthesis and solution spectral properties of antimony (III) phthalocyanine and dihydroxoantimony (V) phthalocyanine complexes | |
| CN101880477B (en) | POSS (Polyhedral Oligomeric Silsesquioxane) hybridized squarine near-infrared absorption dye and preparation method thereof | |
| CN108503673B (en) | Near-infrared azapyrrolidine dye and preparation method and application thereof | |
| CN102618086B (en) | Method for preparing trapezoidal broadband absorption carbene squaraine dye with one-step method | |
| CN106512004A (en) | Permethylated beta-cyclodextrin modified nano graphene/porphyrin nano-supramolecular assembly | |
| CN110128844B (en) | Indole squarylium cyanine dye and preparation method and application thereof | |
| Balcerak et al. | Latest Advances in Highly Efficient Dye-Based Photoinitiating Systems for Radical Polymerization | |
| CN103214505A (en) | Pyrromethene-boron difluoride derivative, and preparation method and application thereof | |
| CN103145984A (en) | Squaraine polytriazole with near-infrared optic absorption, and preparation method thereof | |
| CN113402505B (en) | Organic material capable of absorbing near infrared light and preparation method and application thereof | |
| CN104387790A (en) | Benzindole salt dye containing thiophene group and preparation method and application of benzindole salt dye | |
| CN109433274B (en) | Copper-containing organic metal complex-TiO2Composite material and preparation method and application thereof | |
| CN101083299A (en) | Unsymmetrical Unsymmetrical phthalocyanine material and method for making same | |
| Gao et al. | Synthesis, spectroscopy and photochemistry of novel branched fluorescent nitro-stilbene derivatives with benzopheonone groups | |
| CN102516185A (en) | Benzophenanthrene asymmetrical disk compound and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131211 Termination date: 20160307 |