CN1887883A - V-shaped conjugated light-absorbing organic salt compound and its use - Google Patents
V-shaped conjugated light-absorbing organic salt compound and its use Download PDFInfo
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- CN1887883A CN1887883A CNA2005100120220A CN200510012022A CN1887883A CN 1887883 A CN1887883 A CN 1887883A CN A2005100120220 A CNA2005100120220 A CN A2005100120220A CN 200510012022 A CN200510012022 A CN 200510012022A CN 1887883 A CN1887883 A CN 1887883A
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Abstract
The present invention belongs to the field of organic polymer chemistry and material chemistry, and is especially V-shaped conjugated light-absorbing organic salt compound and its use. The V-shaped conjugated light-absorbing organic salt compound is prepared with corresponding organic salt and heterocyclic dialdehyde, and through condensation or reaction with halogenated compound in V-shaped conjugation system. It has the structure as shown. The V-shaped conjugated light-absorbing organic salt compound may be as photsensitizer and/or initiator for single or double photon polymerization, as single or double photon bioluminescence probe with microM level use concentration, and as second order non-linear optical material; and its crystal may be used as electro-optical material and tera Hz beat frequency generator.
Description
Technical field
The present invention belongs to organic polymer chemistry and materials chemistry field, particularly relates to V-type conjugated light-absorbing organic salt compound and uses thereof.
Background technology
Along with development of information industry, had higher requirement in fields such as high-speed light communication, optical information storage, photoelectronics.Nonlinear optical material all has important application at aspects such as optical signal processing, photoswitch, frequency translation (frequency multiplication, difference frequency, mixing, optical parametric oscillator), light data storage, optical communications.Because have that nonlinear optical coefficients are big, specific inductivity is little, response speed is fast, damage threshold is high, be convenient to characteristics such as molecular designing optimization, organic non linear optical material potential in the electric light sciemtifec and technical sphere is used and is received much attention.
Typical second-order non-linear optical materials is unidimensional, has the organic conjugate system that electronic donor group (Donor)-π grips system-electron acceptor(EA) group (Acceptor) structure altogether, can realize significant molecule hyperpolarizability by the length of optimizing electron donor(ED)/acceptor (D/A) and prolongation conjugated chain though number of research projects shows.But these unidimensional compounds exist tangible problem aspect nonlinear optical property: the first is difficult to solve with traditional D/A system the balance of transparent-efficient, because increase the red shift that conjugate length is accompanied by the transition of electron attitude usually; It two is that molecule most, that one dimension pushes away/draw electronics tends to centrosymmetry and arranges and show as non-SHG activity in crystal; It three is problems of relevant phase matched, and for the symmetric crystal of height, effectively the nonlinear phase coupling is very little, also influences the nonlinear optical response of macro-scale simultaneously.
In view of above problem, that the molecule of two-dirnentional structure then can improve is non-linear/balance between transparent, may form non-centrosymmetrical arrangement in default of permanent dipole moment, and the chromophoric group of two dimension has than the better phase matched of one dimension chromophoric group.Up to the present, the two-dimentional organic non-linear molecule of multiple Λ type occurred, the report of this respect is referring to " JACS " 1996 118 volumes 12950～12955 pages of (Moylan, C.R.; Ermer, S.; Lovejoy, S.M.; McComb, I.-H.; Leung, D.S.; Wortmann, R.; Krdmer, P.; Twieg, R.J., (Dicyanomethylene) pyran Derivativeswith C
2VSymmetry:An Unusual Class of Nonlinear Optical Chromophores, Journal of the American Chemical Society, 1996,118,12950～12955), " JACS " 1997 119 volumes 9550～9557 pages of (Di Bella, S.; Fragala`, I.; Ledoux, I.; Diaz-Garcia, M.A.; Marks, T.J., Synthesis, Characterization, OpticalSpectroscopic, Electronic Structure, and Second-Order Nonlinear Optical (NLO) Properties of a Novel Class of Donor-Acceptor Bis (salicylaldiminato) nickel (II) Schiff Base NLO Chromophores, Journal of the American Chemical Society, 1997,119,9550-9557.), " chemical physics wall bulletin " calendar year 2001 340 volumes 109～115 pages of (Ostroverkhov, V.; Petschek, R.G.; Singer, K.D.; Twieg, R.J. Λ-likechromophores for chiral non-linear optical materials, Chemical Physics Letters, 2001,340,109-115.), 3942～3951 pages of (YangM.-L. of " physical chemistry communication A " 2003 107 volume; Champagne, B.Large Off-Diagonal Contribution to the Second-OrderOptical Nonlinearities of Λ-Shaped Molecules, The Journal of Physical ChemistryA, 2003,107,3942～3951) article.In existing these two-dimentional organic molecules, the report of relevant conjugation organic salt compound is very few.Only report is seen 4845～4859 pages of (Benjamin J.Coe of " JACS " 2005 127 volumes, James A.Harris, Lathe A.Jones, Bruce S.Brunschwig, Kai Song, Koen Clays, Javier Garl ' n, Jesu ' s Orduna, Simon J.Coles, and MichaelB.Hursthouse, Syntheses and Properties of Two-Dimensional Charged NonlinearOptical Chromophores Incorporating Redox-Switchable cis-Tetraammine-ruthenium (II) Centers, Journal of the American Chemical Society, 2005,127,4845～4859), 3284～3285 pages of (Benjamin J.Coe of " JACS " 2005 127 volumes, James A.Harris, Bruce S.Brunschwig, Javier Garl ' n, and Jesu ' s Orduna, Molecular Salts with Diquat-Based Electron Acceptors for Nonlinear Optics, Journal of the American Chemical Society, 2005,127, article 3284-3285).
Two-photon absorption is the process that molecule absorbs two photons simultaneously, square is directly proportional with the light intensity of irradiates light, and be a nonlinear optics behavior.Although the photosensitizers of two-photon polymerized usefulness and initiator are very popular fields of Recent study, in the process of the organic molecule of researching and developing big two photon absorption cross section, many molecules with kind one-dimensional, dendroid and ends of the earth minor structure have appearred.The report of this respect can be referring to 9291～9306 pages of (Stephanie J.K.Pond of " JACS " 2004 126 volumes, Osamu Tsutsumi, Mariacristina Rumi, Ohyun Kwon, Egbert Zojer, Jean-LucBre ' das, Seth R.Marder, and Joseph W.Perry, Metal-Ion Sensing Fluorophoreswith Large Two-Photon Absorption Cross Sections:Aza-Crown Ether SubstitutedDonor-Acceptor-Donor Distyrylbenzenes, Journal of the American ChemicalSociety, 2004,126,9291～9306) article.But in all reports, several examples report relevant with organic salt compound only arranged, see also 820～821 pages of (Han Young Woo of " JACS " 2005 127 volumes in detail, Janice W.Hong, Bin Liu, Alexander Mikhailovsky, Dmitry Korystov, and Guillermo C.Bazan, Water-Soluble[2.2] ParacyclophaneChromophores with Large Two-Photon Action Cross Sections, Journal of theAmerican Chemical Society, 2005,127,820～821) article.Aspect two-photon polymerized photosensitizers and initiator, the report of V-type conjugation organic salt compound is not arranged as yet.
Summary of the invention
One of purpose of the present invention is to provide class ultraviolet/near infrared light-absorbing organic salt compound---V-type conjugation organic salt compound.
The V-type conjugated light-absorbing organic salt compound that two of purpose of the present invention is to provide purpose one carries out the initiator of single two-photon polymerized usefulness as vinyl monomer at visible light/near infrared light, or as the initiator of light solidifying coating material, photoetching material, photoimaging material, optical material, hologram recording material and three-dimensional processing modelling material photocuring etc.
The structure of V-type conjugated light-absorbing organic salt compound of the present invention is as follows:
(1) structure of aromatic nucleus part is:
Z is O, S, Se or NR
1
Ar
+Be selected from
Wherein X is NR
6
R
1, R
6Be selected from hydrogen, C1～C16 alkyl, C1～C16 alkyl that aromatic ring replaces, the alkyl of the C1～C16 of nitrogenous or oxygen containing heterocyclic substituted, nitrogenous or oxygen containing heterocyclic radical, alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group list or polysubstituted phenyl ring, alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group list or polysubstituted naphthalene nucleus contain the fatty chain alkyl of oxygen, sulphur, nitrogen heteroatom;
R
2, R
3, R
4, R
5Be selected from H, C1～C8 alkyl, aryl, alkoxyl group, carboxylic acid ester groups, nitro, alkylamino radical, nitro or sulfonic group etc.
(2) aromatic nucleus and Ar
+Y
-The connection portion, space be selected from: alkene, link to each other by aromatic ring that conjugation is two, polyene hydrocarbon, alkynes links to each other by aromatic ring that conjugation is two, polyine, alkynes that links to each other with alkene by aromatic ring or the alkene that links to each other with alkynes by aromatic ring.
The connection portion is selected from
Wherein: Ar is selected from alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group list or polysubstituted phenyl ring, alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group list or polysubstituted naphthalene, single or polysubstituted anthracene such as alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group; Wherein n is 0～3; M is 0～2;
(3) negative ion partly is:
Y
-Be selected from Cl
-, Br
-, I
-, F
-, SO
3 -, CF
3SO
3 -, BF
4 -, BAr
4 -, NO
3 -, ClO
4 -, PF
6 -, AsF
6 -, SbF
6 -, TsO
-, contain the sour negative ion of chiral centre, the phenylformic acid negative ion that alkoxyl group, C1～C8 alkyl, nitro or alkylamino radical replace; Wherein Ar is selected from alkoxyl group, C1～C8 alkyl, nitro, dialkyl amino, carboxylic acid ester groups or the polysubstituted phenyl ring of sulfonate group, nitrogenous or oxygen containing heterocycle.
V-type conjugated light-absorbing organic salt compound of the present invention has two kinds of synthetic methods:
Method one is corresponding heterocycle dialdehyde and salt by document: " materials chemistry " nineteen nineties 2 synthetic method of 685～690 pages of volumes carry out (Seth R.Marder, Joseph W.Perry, Bruce G.Tiemann, RichardE.Marsh, and William P.Schaefer, Second-order optical nonlinearities andphotostabilities of 2-N-methylstilbazolium salts.Chemisty of Materials, 1990,2,685-690).Step is as follows:
In reaction vessel, add heterocycle dialdehyde and corresponding salt, its molar ratio is 1: 2.The ethanol that adds the weight of 10～50 times of salt then, the organic bases such as the piperidines that can add the weight of 0.00l～0.010 times salt are if necessary made catalyzer, reflux 5～48 hours, reaction finishes, cooling boils off solvent, obtains required V-type conjugation organic salt compound after thick product is purified.
Wherein said heterocycle dialdehyde is by document: " chemistry can will Bai Jin can report I " synthetic method of 41～45 pages in 1999 is carried out (Sumio Maruyama, Yadong Zhang, Tatsuo Wada andHiroyuki Sasabe, Convenient syntheses of cyclic carbazole oligomers by 1-potKnoevenagel reaction.Jounal of the Chemical Society, Perkin Transaction I, 1999,41～45).Its structure is suc as formula shown in (II):
Wherein n is 0～3; Z is O, S, Se or NR
1R
1Be selected from hydrogen, C1～C16 alkyl, C1～C16 alkyl that aromatic ring replaces, the alkyl of the C1～C16 of nitrogenous or oxygen containing heterocyclic substituted, nitrogenous or oxygen containing heterocyclic radical, alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group list or polysubstituted phenyl ring, alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group list or polysubstituted naphthalene nucleus contain the fatty chain alkyl of oxygen, sulphur, nitrogen heteroatom;
The structure of wherein said corresponding salt is suc as formula shown in (III):
Y wherein
-Be selected from Cl
-, Br
-, I
-, F
-, SO
3 -, CF
3SO
3 -, BF
4 -, BAr
4 -, NO
3 -, ClO
4 -, PF
6 -, AsF
6 -, SbF
6 -, TsO
-, contain the sour negative ion of chiral centre, the phenylformic acid negative ion that alkoxyl group, C1～C8 alkyl, nitro or alkylamino radical replace; Wherein Ar is selected from alkoxyl group, C1～C8 alkyl, nitro, dialkyl amino, carboxylic acid ester groups or the polysubstituted phenyl ring of sulfonate group, nitrogenous or oxygen containing heterocycle.Wherein
Ar
+Be selected from
Wherein X is NR
6
R
6Be selected from hydrogen, C1～C16 alkyl, C1～C16 alkyl that aromatic ring replaces, the alkyl of the C1～C16 of nitrogenous or oxygen containing heterocyclic substituted, nitrogenous or oxygen containing heterocyclic radical, alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group list or polysubstituted phenyl ring, alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group list or polysubstituted naphthalene nucleus contain the fatty chain alkyl of oxygen, sulphur, nitrogen heteroatom;
R
2, R
3, R
4, R
5Be selected from H, C1～C8 alkyl, aryl, alkoxyl group, carboxylic acid ester groups, nitro, alkylamino radical, nitro or sulfonic group etc.
Method two be corresponding conjugation organic compound with corresponding halides effect by document: the synthetic method that " Premium Features material " 2003 13 volumes are 347～357 pages is carried out (Coe BJ, Harris JA, AsselberghsI, Wostyn K, Clays K, Persoons A, Brunschwig BS, Coles SJ, Gelbrich T, LightME, Hursthouse MB, Nakatani K, Quadratic optical nonlinearities of N-methyland N-aryl pyridinium salts.Advanced Functional Materials, 2003,13 (5), 347～357).Generally carry out prepared in reaction by 1 mole of corresponding conjugation organic compound and 1 mole of corresponding halides under the condition that catalyzer exists, product is required V-type conjugation organic salt compound.Step is as follows:
In reaction vessel, add conjugation organic compound and corresponding halides, its molar ratio is 1: 2.Add organic solvents such as the benzene of weight of the ethanol of weight of 10～50 times of conjugation organic compound and 5～50 times of conjugation organic compound or toluene then, reflux 5～48 hours, reaction finishes, cooling, boil off solvent, obtain required V-type conjugation organic salt compound after thick product is purified.Other negatively charged ion then obtains by the method for ion-exchange.
Wherein said conjugation organic compound is by document: the synthetic method that " materials chemistry magazine " 2003 13 volumes are 1575～1581 pages is carried out (Iwase Y, Kamada K, Ohta K, Kondo K, Synthesis andphotophysical properties of new two-photon absorption chromophores containing adiacetylene moiety as the central pi-bridge.Journal of Materials Chemistry, 2003,13 (7), 1575～1581).Its structure is suc as formula shown in (IV):
Z is O, S, Se or NR
1
Ar is selected from
Wherein X is a nitrogen-atoms.
R
1Be selected from hydrogen, C1～C16 alkyl, C1～C16 alkyl that aromatic ring replaces, the alkyl of the C1～C16 of nitrogenous or oxygen containing heterocyclic substituted, nitrogenous or oxygen containing heterocyclic radical, single or polysubstituted phenyl ring such as alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group, single or polysubstituted naphthalene nucleus such as alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group contains the fatty chain alkyl of oxygen, sulphur, nitrogen heteroatom.
R
2, R
3, R
4, R
5Be selected from H, C1～C8 alkyl, aryl, alkoxyl group, carboxylic acid ester groups, nitro, alkylamino radical, nitro or sulfonic group etc.
The connection portion is selected from:
Wherein Ar is selected from single or polysubstituted phenyl ring such as alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group, single or polysubstituted naphthalene such as alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group, single or polysubstituted anthracene such as alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group; Wherein n is 0～3; M is 0～2.
Wherein said corresponding halides is R
6Y.R wherein
6Be selected from hydrogen, C
1～C
16C1～C8 alkyl that alkyl, aromatic ring replace, the C of nitrogenous or oxygen containing heterocyclic substituted
1～C
16Alkyl, nitrogenous or oxygen containing heterocyclic radical, single or polysubstituted phenyl ring such as alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group, single or polysubstituted naphthalene nucleus such as alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group contains the fatty chain alkyl of oxygen, sulphur, nitrogen heteroatom; Y is Cl, Br, I or F etc.;
Wherein said other negatively charged ion is SO
3 -, CF
3SO
3 -, BF
4 -, BAr
4 -, NO
3 -, ClO
4 -, PF
6 -, AsF
6 -, SbF
6 -, TsO
-, contain the sour negative ion of chiral centre, the phenylformic acid negative ion that alkoxyl group, C1～C8 alkyl, nitro or alkylamino radical replace.
V-type conjugated light-absorbing organic salt compound of the present invention, can be used as photopolymerisable initiator of vinyl monomer UV-light/visible light/near infrared light and/or photosensitizers, or as photo-curing material, as the photosensitizers and/or the initiator of the UV-light/visible light/near infrared light photocuring of light solidifying coating material, photoetching material, photoimaging material, hologram recording material, optics stored material and three-dimensional modeling material etc.
Consumption and the compound method of V-type conjugated light-absorbing organic salt compound of the present invention during as photopolymerisable photosensitizers of vinyl monomer and/or initiator is as follows:
A.V type conjugation organic salt compound is during as the list of vinyl monomer or double photon photopolymerization initiator, and each component and content thereof are (weight percentage):
Vinyl monomer 25wt%～74.9wt%
Multi-functional acrylate's linking agent 25wt%～74.9wt%
V-type conjugation organic salt compound 0.001wt%～2wt%
Reaction concrete operations step is as follows:
In reactor, add weight percentage and be 25%～74.9% vinyl monomer and weight percentage and be multi-functional acrylate's linking agent of 25%～74.9%, under the condition of lucifuge, the V-type conjugation organic salt compound that adds the 0.001wt%～2wt% that accounts for total reaction liquid weight, to be mixed evenly after, shine with light source under the room temperature, the reaction times stopped illumination at 0.1～1 hour, can obtain the polymkeric substance of vinyl monomer.
B.V type conjugation organic salt compound is during as the list of photo-curing material or double photon photopolymerization initiator, and each component and content thereof are (weight percentage):
Light reactive resin 40wt%～75wt%
Multi-functional acrylate's linking agent 10wt%～50wt%
Simple function group acrylate reactive thinner 5wt%～35wt%
V-type conjugation organic salt compound 0.001wt%～5wt%
Reaction concrete operations step is as follows:
In reactor, add weight percentage and be 40%～75% light reactive resin, simple function group acrylate reactive thinner that weight percentage is 5wt%～35wt% and weight percentage and be multi-functional acrylate's linking agent of 10%～50%, under the condition of lucifuge, the V-type conjugation organic salt compound that adds the 0.001wt%～5wt% that accounts for total reaction liquid weight, to be mixed evenly after, shine with light source under the room temperature, reaction times can obtain the light solidifying coating material at 0.001 second～30 minutes.
Described vinyl monomer is selected from one or more the mixture etc. in vinylformic acid and ester class, acrylic amide, vinyl cyanide, methacrylic acid and ester class thereof, methacryloyl amine, vinylbenzene, vinyl-acetic ester, the vinyl pyrrole ketone.
Described light reactive resin is epoxy acrylate, polyester acrylate, urethane acrylate, unsaturated polyester or their any mixture etc.
Described multi-functional acrylate's linking agent is Viscoat 295, pentaerythritol triacrylate, double pentaerythritol methacrylate or their any mixture etc.
Described simple function group acrylate reactive thinner is ethers simple function group acrylate, hydroxyl simple function group acrylate, acrylic amide, vinyl cyanide, methyl acrylic ester, methacryloyl amine or their any mixture etc.
Described light source can adopt the ultraviolet source mercury lamp, also can adopt LASER Light Source, as argon laser or He-Ne Lasers, titanium precious stone laser lamp.
The mode of V-type conjugation organic salt compound initiated polymerization of the present invention can be carried out in modes such as polymerizations in letex polymerization, solution polymerization or the thick system.
The spectral response range of UV-light/visible light of the present invention/near infrared light photoinitiator---V-type conjugation organic salt compound, photochemical properties, living radical formation efficiency, the solubility property all structure with them are relevant with composition.Table 1 has been listed structure and maximum absorption wavelength, molar extinction coefficient and the emission wavelength of part of compounds.
The maximum absorption wavelength of table 1 part of compounds, molar extinction coefficient and emission wavelength
| Compound number | Ar + | Z | Y - | The connection portion | Ultraviolet maximum absorption wavelength (nm) | Fluorescent emission wavelength (nm) |
| 1 2 3 4 5 6 7 | Py +R 1 Py +R 1 Py +R 1 Py +R 1 Py +R 1 Py +R 1 Py +R 1 | NR 2 NR 2 NR 2 NR 2 NR 2 NR 2 NR 2 | TsO - TsO - TsO - I - I - TsO - Br - | CH＝CH CH＝CH CH＝CH CH＝CH CH＝CH CH＝CH CH＝CH | 456 456 458 458 456 457 460 | 568 567 568 568 567 567 568 |
R wherein
1, R
2Be selected from hydrogen, C1～C16 alkyl, C1～C16 alkyl that aromatic ring replaces, the alkyl of the C1～C16 of nitrogenous or oxygen containing heterocyclic substituted, nitrogenous or oxygen containing heterocyclic radical, single or polysubstituted phenyl ring such as alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group, single or polysubstituted naphthalene nucleus such as alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group contains the fatty chain alkyl of oxygen, sulphur, nitrogen heteroatom; Py+ is the pyridin-4-yl positively charged ion; TsO
-Be the tosic acid negatively charged ion.
V-type conjugation organic salt compound of the present invention can be used as the photosensitizers and/or the light trigger of single or two-photon polymerized usefulness.
V-type conjugation organic salt compound of the present invention can produce and transform fluorescence and as list or two-photon biological fluorescent probe molecule, its working concentration is in μ M magnitude.
V-type conjugation organic salt compound of the present invention can be used as second-order non-linear optical materials, and its crystal can be used as electrooptical material, Terahertz difference frequency generator.
The present invention proposes a kind of suitable V-type organic salt compound as activator, their character has following characteristics: at normal temperatures, solid state is very stable, under the illumination effect, after being subjected to optical excitation, electron-transfer reaction takes place, and produces the free radical fragment of ripple of living, thereby is easy to cause Raolical polymerizable.The mutability of molecule is big in addition, and the length that changes conjugated system can be regulated the extinction scope, and whole extinction scope can cover ultraviolet/near infrared light.In addition, what this organic salt system mainly took place is intramolecular photoinduction electronic transfer process, overcome polymerization reaction system was obstructed, is unfavorable for the bimolecular sensitized reaction because of the high molecular diffusion that causes of viscosity restriction effectively, guaranteed carrying out smoothly of Photoinitiated reactions, has the quick response feature, make and be not vulnerable to the influence of introduced contaminants by free radical formation reaction efficient height.Therefore such organic salt compound is suitable for being used for (list) double photon photopolymerization system in the wide spectrum scope, different viscosity.
Description of drawings
Fig. 1. the photocuring film of the embodiment of the invention 5.
Fig. 2. the photocuring film of the embodiment of the invention 6.
Embodiment
The invention will be further described below by embodiment, but should not limit protection scope of the present invention with this.
Embodiment 1:
3, two [2-(N-picoline-4-base vinyl)]-N-amyl group-9 hydrogen carbazole-two tosilate of 6-synthetic:
The first step: 1,4-lutidine tosilate synthetic:
In reaction vessel, add ethanol 150mL, 4-picoline 4.7g (50mmol) and methyl tosylate 9.3g (50mmol), heating reflux reaction 6 hours, cooling, boil off most of dissolving after, after the ice-water bath cooling, filter, drying obtains white crystal 14.0g, productive rate 93%.
Second step: N-amyl group-9-hydrogen carbazole-3,6-dialdehyde synthetic:
DMF 2.35mL (0.03mol) is placed there-necked flask, and be cooled to below 10 ℃ with water-bath.Again with POCl
32.80mL (0.03mol) slowly be added dropwise among the DMF with constant pressure funnel, controlled temperature is below 10 ℃.N-amyl group carbazole 0.715g (0.003mol) is poured in the reaction system with after the ethylene dichloride dissolving, be warming up to 90 degree.React after 24 hours, slowly pour reaction mixture in water termination reaction, regulate pH value to alkalescence, and with chloroform extraction three times, the merging organic phase is used anhydrous MgSO with the NaOH saturated aqueous solution
4Drying, removing desolvates obtains the thick liquid of black.With volume ratio is that 9: 1 petrol ether/ethyl acetate is that elutriant carries out column chromatography to the product system and separates, and can obtain faint yellow solid 0.495g, productive rate 56%.
The 3rd step: 3, two [2-(N-picoline-4-base vinyl)]-N-amyl group-9 hydrogen carbazole-two tosilate of 6-synthetic:
In reaction vessel, add ethanol 200mL, N-amyl group-9-hydrogen carbazole-3,6-dialdehyde 1.47g (5mmol) and 1,4-lutidine tosilate 2.79g (10mmol) after the heating for dissolving, drips 10 piperidines, refluxes 12 hours.Use acetonitrile and ether recrystallization after boiling off solvent, filter, drying obtains red powder 1.31g, productive rate 32%.
Embodiment 2:
3, two [2-(N-(thiazole-3-methyl)-pyridin-4-yl vinyl)]-N-methyl-9-hydrogen carbazole-dibrominated salt of 6-synthetic:
The first step: 3, two [2-(pyridin-4-yl)-the vinyl]-N-methyl of 6--9-hydrogen carbazole synthetic
In reaction vessel, add 3; 6-two bromo-N-methyl-9-hydrogen carbazole 1.625g (5mmol), palladium 15.5mg (0.06mmol), three (o-tolyl) phosphine 150mg (0.5mmol); 4-vinylpridine 2.10g (20mmol); triethylamine 20mL, nitrogen protection refluxed 24 hours down, cooled and filtered; gained solid water is given a baby a bath on the third day after its birth inferior; use the tetrahydrofuran (THF) dissolved solids then, drying is filtered the back steaming and is desolventized.Get orange solid 1.10g, productive rate 59%.
Second step: 3, two [2-(N-(thiazole-3-methyl)-pyridin-4-yl vinyl)]-N-methyl-9-hydrogen carbazole-dibrominated salt of 6-synthetic
In reaction vessel, add ethanol 150mL, 3, two [2-(pyridin-4-yl)-the vinyl]-N-methyl of 6--9-hydrogen carbazole 3.87g (10mmol) and 3-brooethyl thiazole 3.56g (20mmol), heating reflux reaction 30 hours, the cooling, boil off most of solvent after, after the ice-water bath cooling, filter, drying obtains carmetta powder 6.25g, productive rate 84%.
Embodiment 3:
3, two [2-(N-(2, the 4-dinitrophenyl)-pyridin-4-yl vinyl)]-N-methyl-9-hydrogen carbazole-two iodized salts of 6-synthetic:
In reaction vessel, add ethanol 50mL, 3, two [2-(pyridin-4-yl)-the vinyl]-N-methyl of 6--9-hydrogen carbazole 0.187g (1mmol) and 2,4-dinitrobenzene phenyl-iodide 0.356g (2mmol), heating reflux reaction 40 hours, cooling, after boiling off most of solvent, after the ice-water bath cooling, filter, drying obtains garnet powder 0.152g, productive rate 28%.
Embodiment 4:
3,6-two { 2-[2-(pyridin-4-yl)-vinyl phenyl] ethynyl } N-amyl group-9-hydrogen carbazole-two tosilate synthetic:
The first step: 3,6-diacetylene-N-amyl group-9-hydrogen carbazole synthetic:
In reaction vessel, add 3,6-two bromo-N-amyl groups-9-hydrogen carbazole 3.12g (8mmol), 3-crotonylene-methyl-2-alcohol 2.00g (24mmol), two chloro-be two-(triphenylphosphine) palladium 0.14g (0.2mmol), cupric iodide 0.076g (0.4mmol), triphenylphosphine 0.104g (0.4mmol) and triethylamine 100mL, heating reflux reaction 24 hours, cooling, after boiling off most of solvent, residuum is poured in the water, used chloroform extraction three times, each 50mL.Combined chloroform phase, dry also the steaming desolventize, and residuum gets yellow oil 2.583g (yield 81%) with column chromatography purification.Yellow oil 2.583g, sodium hydroxide 3.10g (78mmol) and the toluene 60mL of gained are added in the reaction vessel, add and refluxed 14 hours.The cooling, boil off most of solvent after, residuum gets faint yellow oily thing 1.140g, productive rate 63% with column chromatography purification.
Second step: 3,6-two [2-(4-carbonyl-phenyl) ethynyl]-N-amyl group-9-hydrogen carbazole synthetic:
In reaction vessel, add 3,6-diacetylene-N-amyl group-9-hydrogen carbazole 0.56g (2mmol), p-bromobenzaldehyde 1.11g (6mmol), two chloro-be two-(triphenylphosphine) palladium 35mg (0.05mmol), cupric iodide 19mg (0.1mmol), triphenylphosphine 26mg (0.1mmol) and triethylamine 30mL, heating reflux reaction 24 hours, cooling, after boiling off most of solvent, residuum is poured in the water, with chloroform extraction three times, boil off most of solvent after the drying, residuum gets faint yellow solid 0.653g with column chromatography purification, productive rate 65%.
The 3rd step: 3,6-two { 2-[2-(pyridin-4-yl)-vinyl phenyl] ethynyl } N-amyl group-9-hydrogen carbazole-two tosilate synthetic:
In reaction vessel, add ethanol 50mL, 3,6-two [2-(4-carbonyl-phenyl) ethynyl]-N-amyl group-9-hydrogen carbazole 0.500g (1mmol) and 1,4-lutidine tosilate 0.580g (2mmol) is after the heating for dissolving, drip 2 piperidines, refluxed 12 hours.Use acetonitrile and ether recrystallization after boiling off solvent, filter, drying obtains red powder 0.376g, productive rate 35%.
Embodiment 5:
The product of embodiment 1 is two-photon polymerized with initiator and photosensitizers as vinyl monomer:
Get in the Glass Containers in that agitator is housed, add methyl-prop diluted acid 0.600g (weight percentage 60%), linking agent DEP-6A 0.396g (weight percentage 39.6%), the product 0.004g of embodiment 1 (weight percentage 0.4%), at room temperature, under the lucifuge condition, the three is mixed.The thick thing for preparing is applied on the washed glass sheet, is the rayed 0.01 second of 300mw with power, can have the photocuring film of three-dimensional microstructures.As shown in Figure 1.
With four beam interferences carry out after two-photon polymerized the electron scanning micrograph of three-dimensional microstructures.(amplifying 14000 times, light source power 300mv, time shutter 1/100s).
Embodiment 6:
The product of embodiment 1 is two-photon polymerized with initiator and photosensitizers as vinyl monomer:
Get in the Glass Containers in that agitator is housed, add methyl-prop diluted acid 0.475g (weight percentage 47.5%), linking agent DEP-6A 0.257g (weight percentage 51.4%), the product 0.005g of embodiment 1 (weight percentage 1%), at room temperature, under the lucifuge condition, the three is mixed.The thick thing for preparing is applied on the washed glass sheet, is the rayed 0.02 second of 300mw with power, the photocuring film that can have two-dimentional microstructure.As shown in Figure 2.
With four beam interferences carry out after two-photon polymerized the electron scanning micrograph of two-dimentional microstructure.(amplifying 5500 times, light source power 300mv, time shutter 1/50s).
Embodiment 7:
The product of embodiment 1 as the polymerization of vinyl monomer single photon with initiator and photosensitizers:
In that being housed, agitator gets in the Glass Containers, add methyl-prop diluted acid 0.338g (weight percentage 65.4%), linking agent DEP-6A 0.177g (weight percentage 34.3%), the product 0.0016g of embodiment 1 (weight percentage 0.31%), at room temperature, under the lucifuge condition, the three is mixed.The thick thing for preparing is applied on the washed glass sheet, is about 10mw/cm with power
2UV-irradiation 5 minutes, can get the photocuring film.
Claims (6)
1. V-type conjugated light-absorbing organic salt compound, it is characterized in that: the structure of described V-type conjugated light-absorbing organic salt compound is:
(1) structure of aromatic nucleus part is:
Z is O, S, Se or NR
1
Ar
+Be selected from
Wherein X is NR
6
R
1, R
6Be selected from hydrogen, C1～C16 alkyl, C1～C16 alkyl that aromatic ring replaces, the alkyl of the C1～C16 of nitrogenous or oxygen containing heterocyclic substituted, nitrogenous or oxygen containing heterocyclic radical, alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group list or polysubstituted phenyl ring, alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group list or polysubstituted naphthalene nucleus contain the fatty chain alkyl of oxygen, sulphur, nitrogen heteroatom;
R
2, R
3, R
4, R
5Be selected from H, C1～C8 alkyl, aryl, alkoxyl group, carboxylic acid ester groups, nitro, alkylamino radical, nitro or sulfonic group;
(2) aromatic nucleus and Ar
+Y
-The connection portion, space be selected from:
HC≡CH、
H
2C＝CH
2、
Wherein: Ar is selected from alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group list or polysubstituted phenyl ring, alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group list or polysubstituted naphthalene, single or polysubstituted anthracene such as alkoxyl group, C1～C8 alkyl, nitro, alkylamino radical, carboxylic acid ester groups or sulfonate group; Wherein n is 0～3; M is 0～2;
(3) negative ion partly is:
Y
-Be selected from Cl
-, Br
-, I
-, F
-, SO
3 -, CF
3SO
3 -, BF
4 -, BAr
4 -, NO
3 -, ClO
4 -, PF
6 -, AsF
6 -, SbF
6 -, TsO
-, contain the sour negative ion of chiral centre, the phenylformic acid negative ion that alkoxyl group, C1～C8 alkyl, nitro or alkylamino radical replace; Wherein Ar is selected from alkoxyl group, C1～C8 alkyl, nitro, dialkyl amino, carboxylic acid ester groups or the polysubstituted phenyl ring of sulfonate group, nitrogenous or oxygen containing heterocycle.
2. the purposes of a V-type conjugated light-absorbing organic salt compound according to claim 1, it is characterized in that: described V-type conjugated light-absorbing organic salt compound is as the initiator and/or the photosensitizers of vinyl monomer UV-light/visible light/near infrared light list or double photon photopolymerization, or as the photosensitizers and/or the initiator of the UV-light/visible light/near infrared light photocuring of light solidifying coating material, photoetching material, photoimaging material, hologram recording material, optics stored material and three-dimensional modeling material.
3. purposes according to claim 2 is characterized in that: described vinyl monomer is selected from one or more the mixture in vinylformic acid and ester class, acrylic amide, vinyl cyanide, methacrylic acid and ester class thereof, methacryloyl amine, vinylbenzene, vinyl-acetic ester, the vinyl pyrrole ketone.
4. the purposes of a V-type conjugated light-absorbing organic salt compound according to claim 1, it is characterized in that: described V-type conjugated light-absorbing organic salt compound is as list or two-photon biological fluorescent probe molecule.
5. the purposes of a V-type conjugated light-absorbing organic salt compound according to claim 1, it is characterized in that: described V-type conjugated light-absorbing organic salt compound is as list or two-photon second-order non-linear optical materials.
6. the purposes of a V-type conjugated light-absorbing organic salt compound according to claim 1, it is characterized in that: the crystal of described V-type conjugated light-absorbing organic salt compound is as electrooptical material, Terahertz difference frequency generator.
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