CN109438459A - A kind of organic second order non-linear optical chromophore and its synthetic method and application - Google Patents
A kind of organic second order non-linear optical chromophore and its synthetic method and application Download PDFInfo
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Abstract
The present invention relates to a kind of organic second order non-linear optical chromophore and its synthetic method and application, the chromophore has structure shown in formula I:, formula I wherein,For conjugated electrons bridge, R1、R2Separately it is selected from substituted or unsubstituted following radicals: C1‑6Alkyl, C1‑6Alkoxy, C4‑12Aryl or any one of heteroaryl.Chromophore of the invention selects julolidine derivative as electron donor, and tricyano furans are electron acceptor, has suitable construction, intermolecular force, First-order Molecular Hyperpolarizability (β value) with higher can be effectively reduced.Meanwhile the chromophore has conjugate length appropriate, has preferable stability, thermal decomposition temperature can achieve 250 DEG C or more, also, chromophore of the invention has excellent optical property, and electro-optic coefficient can achieve 76pm/V or more.
Description
Technical field
The present invention relates to organic second-order non-linear optical Material Fields, include julolidine derivative more particularly to one kind
Electron donor, tricyano furans electron acceptor, novel organic second-order non-linear chromophore and its synthesis with D- π-A structure
Methods and applications.
Background technique
Nonlinear optical material is able to carry out frequency of light wave conversion and optical signal prosessing, such as utilizes mixing phenomenon realization pair
The amplification of low light signals realizes optical recording and calculation function etc. using nonlinear response, therefore in laser, communication, electronic instrument
And there is important application value in the fields such as medical devices.Nonlinear optical material can be divided into inorganic nonlinear optics according to composition
Material, organic low molecular nonlinear optical material, macromolecule nonlinear optical material, inorganic/organic composite nonlinear optics material
Material, five major class of review of Organometal Nonlinear Optical Materials.Wherein compared with inorganic material, organic low molecular nonlinear optical material
With following distinguishing feature: (1) biggish nonlinear optical coefficients；(2) very high optical damage threshold values density, can be by required
Physical characteristic think design synthesis organic crystal；(3) very wide transmission wave-length coverage；(4) low-k optic response is fast
Speed.Therefore, organic non linear optical material has been a hot spot of research.
The response performance of organic non linear optical material and the structure of its chromophore are closely related.Theoretical research shows have
The performance of machine nonlinear optical material and the height of electronics are delocalized related.Chromophoric Electrons height with D- π-A structure from
Domain is easily polarized, and has biggish nonlinear optical coefficients.This conjugated molecule with charge transfer property is organic non-thread
Most effective ingredient in property optical material.On the one hand, the intensity of electron donor and receptor in chromophore's structure is regulated and controled,
The non-linear optical property of chromophore can effectively be optimized；On the other hand, between chromophore there are dipole-dipole interaction power,
This will affect the orientations processing (and then influencing macro property) of non-linear optical chromophore, and isolation base is introduced in chromophore
Rolling into a ball or reasonably adjust chromophore's structure helps to inhibit the dipole-dipole interaction of chromophore.Therefore, development structure is novel
Electron donor material has important influence to material macro property is promoted.
Summary of the invention
Problems to be solved by the invention
In order to overcome the above technical problems, relatively easy, cheap, atom economy that the object of the present invention is to provide a kind of structures
Property it is good, while having both that stability is good and the organic second-order non-linear chromophore of the novel D- π-A structure of one kind of excellent in optical properties.
The solution to the problem
The technical scheme adopted by the invention is as follows:
Firstly, the present invention provides a kind of organic second-order non-linear chromophories with D- π-A structure, which is characterized in that described
Chromophore has structure shown in formula I:
,
Formula I
Wherein,For conjugated electrons bridge, R1、R2Separately it is selected from substituted or unsubstituted following radicals: C1-6's
Alkyl, C1-6Alkoxy, C4-12Aryl or any one of heteroaryl.
Preferably, the conjugated electrons bridge can be the linking group with a conjugated structure of this field routine, preferably
Selected from any one in flowering structure:
。
Preferably, the substitution is by halogen atom, cyano, nitro, C1-3Alkyl or any one of alkoxy or more
Kind replaces, the C4-12Aryl or heteroaryl be selected from phenyl, thienyl, pyridyl group, pyrimidine radicals, pyrazinyl, pyridazinyl, pyrrole
Cough up one of base, pyrazolyl, thiazolyl or a variety of.
Preferably, above-mentioned halogen atom is fluorine, chlorine, bromine, iodine, preferably fluorine.
It is furthermore preferred that above-mentioned R1、R2Separately it is selected from hydrogen, methyl, trifluoromethyl and phenyl.
Preferably, the structure of the chromophore are as follows:
, or,
More preferably
。
Secondly, preparing any of the above-described kind of organic second-order non-linear hair with D- π-A structure the present invention also provides a kind of
The method of color group, the described method comprises the following steps:
Method one:
Julolidine derivative and tricyano furans electron acceptor are dissolved in ethanol solution, in the effect of organic alkali catalyst
Under, reaction temperature is 50 ~ 80 DEG C, and reaction obtains the novel organic second-order non-linear chromophore with D- π-A structure,
Wherein, the structure of the julolidine derivative are as follows:
,
The tricyano furans electron acceptor has following arbitrary structures:
,
The molar ratio of the julolidine derivative and tricyano furans electron acceptor is 1:1.1 ~ 1:1.2；
Or method two:
1) julolidine derivative and phosphonium salt and sodium hydride are mixed in 1,2- dichloroethane solvent, reaction temperature is 20 ~ 50
DEG C, reaction terminates the post-treated intermediate compound for obtaining structure as formula II,
Formula II
Wherein julolidine derivative: the molar ratio of phosphonium salt is 0.8:1 ~ 1.2:1,
The wherein structure of the julolidine derivative are as follows:
The structure of the phosphonium salt are as follows:
2) it after mixing II intermediate compound of formula in organic solvent with phosphorus oxychloride, is stirred at reflux at 70 ~ 90 DEG C of temperature, instead
It is post-treated to obtain the intermediate compound that structure is formula III after answering,
Formula III
Wherein II intermediate compound of formula: the molar ratio of phosphorus oxychloride is 1:1 ~ 1.2；
3) III compound of formula and tricyano furans electron acceptor are dissolved in ethyl alcohol, react, reacts at being 50 ~ 80 DEG C in temperature
After, the post-treated novel organic second order non-linear optical chromophore for obtaining that there is D- π-A structure,
Wherein, the tricyano furans electron acceptor has following arbitrary structures:
,
The molar ratio of III intermediate compound of formula and tricyano furans electron acceptor is 1:1.1 ~ 1:1.5.
Preferably, the organic alkali catalyst can be the condensation catalyst of this field any conventional, more preferably select
From triethylamine, one of pyridine and piperidines or a variety of.
Again, the present invention also provides a kind of any of the above-described organic second-order non-linear hairs with D- π-A structure
The application of color group, the organic second order non-linear optical chromophore and amorphous polymer doping prepare film.
Finally, the present invention also provides a kind of according to a kind of any of the above-described organic second with D- π-A structure
Application of the non-linear chromophore in photoelectric field.
The effect of invention
1. julolidine derivative fragment structure is introduced into organic second-order non-linear chromophore by the present invention for the first time, long Lip river Buddhist nun
Stator segment structure can be attached with simple conjugated electrons bridge, such as, and then available structure is new
Grain husk, Atom economy is good, cheap, the simple organic second-order non-linear chromophore of structure.
2. the cumarin of the long Luo Niding of tetramethyl has in structure there are four methyl, can be used as steric group effectively every
From non-linear optical chromophore, thus inhibiting dipole-dipole interaction to a certain degree, meanwhile, preferable electron energy
Power also contributes to being promoted the microcosmic non-linear optical property of chromophore, and the present invention selects julolidine derivative to give as electronics
Intermolecular force, First-order Molecular Hyperpolarizability (β with higher can be effectively reduced as electron acceptor in body, tricyano furans
Value).Meanwhile the chromophore has conjugate length appropriate, has preferable stability, thermal decomposition temperature can achieve 250
DEG C or more.
3. chromophore of the invention has excellent optical property, electro-optic coefficient can achieve 76pm/V or more.
4. present invention preparation has the method for the novel organic second-order non-linear chromophore of D- π-A structure simple, raw material is just
Preferably it is easy to get, easy to operate, the yield of product is high, and it is easily processed into type, it is convenient for device, keeps its application more convenient.
Specific embodiment
Firstly, the present invention provides a kind of organic second-order non-linear chromophories with D- π-A structure, which is characterized in that
The chromophore has structure shown in formula I:
,
Formula I
Wherein,For conjugated electrons bridge, R1、R2Separately it is selected from substituted or unsubstituted following radicals: C1-6's
Alkyl, C1-6Alkoxy, C4-12Aryl or any one of heteroaryl.
In a preferred embodiment, the conjugated electrons bridge can be the with a conjugated structure of this field routine
Linking group is preferably selected from any one in flowering structure:
。
In a preferred embodiment, the substitution is by halogen atom, cyano, nitro, C1-3Alkyl or alcoxyl
Any one or more of substitution of base, the C4-12Aryl or heteroaryl be selected from phenyl, thienyl, pyridyl group, pyrimidine radicals,
One of pyrazinyl, pyridazinyl, pyrrole radicals, pyrazolyl, thiazolyl are a variety of.
In a further preferred embodiment, above-mentioned halogen atom is fluorine, chlorine, bromine, iodine, preferably fluorine.
In a further preferred embodiment, above-mentioned R1、R2Separately it is selected from hydrogen, methyl, trifluoromethyl and benzene
Base.
In a further preferred embodiment, the structure of the chromophore are as follows:
, or,
More preferably
。
Secondly, preparing any of the above-described kind of organic second-order non-linear hair with D- π-A structure the present invention also provides a kind of
The method of color group, the described method comprises the following steps:
Method one:
Julolidine derivative and tricyano furans electron acceptor are dissolved in ethanol solution, in the effect of organic alkali catalyst
Under, reaction temperature is 50 ~ 80 DEG C, and reaction obtains the novel organic second-order non-linear chromophore with D- π-A structure,
Wherein, the structure of the julolidine derivative are as follows:
,
The tricyano furans electron acceptor has following arbitrary structures:
,
The molar ratio of the julolidine derivative and tricyano furans electron acceptor is 1:1.1 ~ 1:1.2；
Or method two:
1) julolidine derivative and phosphonium salt and sodium hydride are mixed in 1,2- dichloroethane solvent, reaction temperature is 20 ~ 50
DEG C, reaction terminates the post-treated intermediate compound for obtaining structure as formula II,
Formula II
Wherein julolidine derivative: the molar ratio of phosphonium salt is 0.8:1 ~ 1.2:1,
The wherein structure of the julolidine derivative are as follows:
The structure of the phosphonium salt are as follows:
2) it after mixing II intermediate compound of formula in organic solvent with phosphorus oxychloride, is stirred at reflux at 70 ~ 90 DEG C of temperature, instead
It is post-treated to obtain the intermediate compound that structure is formula III after answering,
Formula III
Wherein II intermediate compound of formula: the molar ratio of phosphorus oxychloride is 1:1 ~ 1.2；
3) III compound of formula and tricyano furans electron acceptor are dissolved in ethyl alcohol, react, reacts at being 50 ~ 80 DEG C in temperature
After, the post-treated novel organic second order non-linear optical chromophore for obtaining that there is D- π-A structure,
Wherein, the tricyano furans electron acceptor has following arbitrary structures:
,
The molar ratio of III intermediate compound of formula and tricyano furans electron acceptor is 1:1.1 ~ 1:1.5.
In a preferred embodiment, the organic alkali catalyst can urge for the condensation of this field any conventional
Agent is more preferably selected from triethylamine, one of pyridine and piperidines or a variety of.
Again, the present invention also provides a kind of any of the above-described organic second-order non-linear hairs with D- π-A structure
The application of color group, the organic second order non-linear optical chromophore and amorphous polymer doping prepare film.
Finally, the present invention also provides a kind of according to a kind of any of the above-described organic second with D- π-A structure
Application of the non-linear chromophore in photoelectric field.
In order to make the objectives, technical solutions, and advantages of the present invention clearer, right below in conjunction with specific embodiment
The present invention is further elaborated.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
Embodiment 1
The synthesis novel organic second-order non-linear chromophore with D- π-A structure as follows:
Synthetic route is as follows:
Synthetic method:
Julolidine derivative 0.5g(1.60mmol is added in round-bottomed flask) and tricyano furans 0.35g(1.76mmol) be dissolved in
2 drop triethylamines are added into solution for 20 ~ 25ml ethyl alcohol, are stirred at reflux at being 60 DEG C in temperature, react complete revolving and remove ethyl alcohol,
Obtain crude product.(stationary phase is the silica gel of 200 ~ 300 mesh to pillar layer separation, and mobile phase is the mixing of petroleum ether and ethyl acetate
Liquid), obtain product 0.66g, yield 81%.1H NMR (300 MHz, CDCl3) δ 10.11 (s, 1H), 8.17 (s,
1H), 7.20 (s, 1H), 3.50 – 3.38 (m, 2H), 3.37 – 3.25 (m, 2H), 1.88 – 1.69 (m,
4H), 1.55 (s, 6H), 1.29 (s, 6H). 13C NMR (126 MHz, CDCl3) δ 187.95, 161.86,
155.17, 148.93, 145.60, 129.38, 126.39, 114.78, 112.75, 108.67, 47.76, 47.17,
38.62, 34.91, 32.11, 32.02, 29.74, 28.47. MS (ESI) (M+, C31H32N4O3): calcd:
508.25; found: 508.55。
Embodiment 2
The synthesis novel organic second-order non-linear chromophore with D- π-A structure as follows:
Synthetic route is as follows:
Synthetic method:
Julolidine derivative 0.5g(1.60mmol is added in round-bottomed flask) and trifluoromethyl tricyano furans 0.55g
(1.75mmol) is dissolved in 20 ~ 25ml ethyl alcohol, and 2 drop triethylamines are added into solution, is stirred at reflux at being 60 DEG C in temperature, reaction is finished
Revolving removes ethyl alcohol, obtains crude product.(stationary phase is the silica gel of 200 ~ 300 mesh to pillar layer separation, and mobile phase is petroleum ether and second
The mixed liquor of acetoacetic ester), obtain product 0.79g, yield 79%.1H NMR (500 MHz, CDCl3) δ 8.02 (d, J =
15.4 Hz, 1H), 7.77 (d, J = 15.5 Hz, 1H), 7.74 (s, 1H), 7.58 (s, 2H), 7.54 (s,
3H), 7.18 (s, 1H), 3.52 (t, J = 5.9 Hz, 2H), 3.42 (d, J = 5.1 Hz, 2H), 1.88 –
1.82 (m, 2H), 1.80 (m, 2H), 1.56 (s, 3H), 1.55 (s, 3H), 1.33 (s, 6H). 13C NMR
(126 MHz, CDCl3) δ 176.07, 164.12, 159.13, 153.94, 150.10, 146.77, 131.24,
130.47, 129.73, 129.67, 126.41, 125.87, 114.86, 111.98, 111.58, 111.23,
110.81, 110.74, 60.41, 57.91, 48.26, 47.60, 38.27, 34.60, 32.07, 30.94,
29.56, 28.27, 21.10, 14.19. MS (ESI) (M+, C36H31F3N4O3): calcd: 624.23; found:
624.60。
Embodiment 3
The synthesis novel organic second-order non-linear chromophore with D- π-A structure as follows:
Synthetic route is as follows:
Synthetic method
1) synthesis of compound 2
0.5g (1.60mmol) julolidine derivative and 0.84g (1.9mmol) thiophene phosphonium salt are added in round-bottomed flask, is dissolved in
In 20 ~ 25ml1,2- dichloroethane solvent, appropriate sodium hydride is added, is stirred at room temperature.Reaction, which is finished, is poured into water reaction solution,
Liquid separation, methylene chloride aqueous phase extracted merge organic phase, the dry organic phase of anhydrous magnesium sulfate, filtering, revolving removing solvent, column color
Spectrum separation (stationary phase is the silica gel of 200 ~ 300 mesh, and mobile phase is the mixed liquor of petroleum ether and ethyl acetate), obtains 0.55gization
Close object 2, yield 85%.1H NMR (400 MHz, CDCl3) δ 7.70 (d, J = 16.2 Hz , 1H), 7.53 (s,
1H), 7.17 (d, J = 5.0 Hz, 1H), 7.09 (s, 1H), 7.06 (d, J = 3.4 Hz, 1H), 6.99
(dd, J = 5.0, 3.6 Hz, 1H), 6.85 (d, J = 16.0 Hz, 1H), 3.32 – 3.28 (m, 2H),
3.24 – 3.20 (m, 2H), 1.84 – 1.79 (m, 2H), 1.78 – 1.74 (m, 2H), 1.57 (s, 6H),
1.30 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 160.78, 151.71, 145.21, 143.67,
139.27, 128.42, 127.63, 126.04, 124.17, 123.29, 116.30, 115.01, 109.72,
47.35, 46.91, 39.42, 35.82, 32.24, 32.19, 30.75, 29.70, 28.96。
2) synthesis of compound 3
By 0.25g(1.65mmol) phosphorus oxychloride and 5mlN, dinethylformamide mixes at 0 DEG C, nitrogen protection, at 0 DEG C
The dichloromethane solution of 0.55g (1.35mmol) compound 2 is added after reaction 2h, is stirred at reflux at 70 ~ 90 DEG C of temperature, reacts
Bi Jiangwen is poured into aqueous sodium carbonate, and water phase is extracted with dichloromethane, and liquid separation merges organic phase, and anhydrous magnesium sulfate drying has
Machine phase, filtering, revolving remove solvent, and (stationary phase is the silica gel of 200 ~ 300 mesh to pillar layer separation, and mobile phase is petroleum ether and second
The mixed liquor of acetoacetic ester), obtain 0.42g compound 3, yield 72%.1H NMR (400 MHz, CDCl3) δ 9.83 (s,
1H), 7.79 (d, J = 15.8, 1H), 7.65 (d, J = 3.9, 1H), 7.58 (s, 1H), 7.13 (d, J
= 3.7, 1H), 7.12 (s, 1H), 7.01 (d, J = 15.8 Hz, 1H), 3.36-3.30 (m, 3H), 3.27-
3.23 (m, 2H), 1.85 – 1.79 (m, 2H), 1.78-1.74 (m, 2H), 1.56 (s, 6H), 1.31 (s,
6H). 13C NMR (100 MHz, CDCl3) δ 182.38, 160.39, 153.82, 152.11, 146.00,
142.02, 140.99, 137.49, 128.68, 128.38, 126.44, 123.69, 122.12, 114.53,
109.48, 47.39, 46.91, 39.19, 35.55, 32.17, 32.14, 30.49, 28.83。
3) synthesis of compound 4
0.42g (1.0mmol) compound 3 and 0.21g (1.1mmol) tricyano furans are added in round-bottomed flask, it is dissolved in 20 ~
In 25ml ethyl alcohol, 2 drop triethylamines are added into solution, are stirred at reflux at being 60 DEG C in temperature, reacts complete revolving and removes ethyl alcohol, obtain
To crude product.(stationary phase is the silica gel of 200 ~ 300 mesh to pillar layer separation, and mobile phase is the mixing of petroleum ether and ethyl acetate
Liquid), obtain 0.49g compound 4, yield 79%.1H NMR (400 MHz, CDCl3) δ 7.79 (d, J = 15.8 Hz,
1H), 7.78 (d,J=15.7 Hz, 1H), 7.59 (s, 1H), 7.38 (d,J = 3.3 Hz, 1H), 7.12
(s, 1H), 7.11 (d, J = 3.4 Hz, 1H), 7.01 (d, J = 15.8 Hz, 1H), 6.61 (d, J =
15.7 Hz, 1H), 3.40 – 3.18 (m, 4H), 1.90-1.7 (m, 10H), 1.57 (s, 6H), 1.30 (s,
10H). 13C NMR (100 MHz, CDCl3) δ 175.67, 172.98, 160.36, 153.70, 152.29,
150.22, 146.38, 142.33, 139.34, 138.36, 137.27, 129.47, 128.92, 128.16,
123.86, 121.82, 118.07, 114.83, 114.52, 112.34, 109.65, 97.16, 56.30, 47.50,
47.00, 39.14, 35.50, 32.20, 32.18, 30.39, 28.81, 26.54。
Embodiment 4
The synthesis novel organic second-order non-linear chromophore with D- π-A structure as follows:
Synthetic route is as follows:
Synthetic method
1) synthesis of compound 2
Julolidine derivative 0.5g (1.60mmol) and 0.81g (1.9mmol) furans phosphonium salt are added in round-bottomed flask, is dissolved in
In 20 ~ 25ml1,2- dichloroethane solvent, appropriate sodium hydride is added, is stirred at room temperature.Reaction, which is finished, is poured into water reaction solution,
Liquid separation, methylene chloride aqueous phase extracted merge organic phase, the dry organic phase of anhydrous magnesium sulfate, filtering, revolving removing solvent, column color
Spectrum separation (stationary phase is the silica gel of 200 ~ 300 mesh, and mobile phase is the mixed liquor of petroleum ether and ethyl acetate), obtains 0.54gization
Close object 2, yield 87%.1H NMR (400 MHz, CDCl3) δ 7.51 (s, 1H), 7.44 (d, J = 16.0 Hz,
1H), 7.39 (d, J = 1.5 Hz, 1H), 6.92 (d, J = 16.1 Hz, 1H), 6.41 (dd, J = 3.3,
1.8 Hz, 1H), 6.34 (d, J = 3.3 Hz, 1H), 3.32 – 3.27 (m, 2H), 3.24 – 3.19 (m,
2H), 1.82 – 1.79 (m, 2H), 1.77 – 1.73 (m, 2H), 1.56 (s, 6H), 1.30 (s, 6H). 13C
NMR (100 MHz, CDCl3) δ 160.83, 153.86, 151.68, 145.18, 142.02, 139.75,
128.40, 123.30, 122.22, 118.10, 116.37, 114.99, 111.79, 109.76, 108.73,
47.34, 46.90, 39.43, 35.84, 32.23, 32.19, 30.75, 28.97。
2) synthesis of compound 3
By 0.26g (1.7mmol) phosphorus oxychloride and 5mlN, dinethylformamide mixes at 0 DEG C, nitrogen protection, anti-at 0 DEG C
0.54g(1.4mmol is added after answering 2h) dichloromethane solution of compound 2, it is stirred at reflux at 70 ~ 90 DEG C of temperature, reaction is finished
Cooling, is poured into aqueous sodium carbonate, and water phase is extracted with dichloromethane, and liquid separation merges organic phase, and anhydrous magnesium sulfate drying is organic
Phase, filtering, revolving remove solvent, and (stationary phase is the silica gel of 200 ~ 300 mesh to pillar layer separation, and mobile phase is petroleum ether and acetic acid
The mixed liquor of ethyl ester), obtain 0.41g compound 3, yield 70%.1H NMR (400 MHz, CDCl3) δ 9.56 (s,
1H), 7.58 (d, J = 15 Hz, 1H), 7.57 (s, 1H), 7.26 (d, J = 3.7 Hz, 1H), 7.22
(d, J = 15 Hz, 1H), 7.11 (s, 1H), 6.50 (d, J = 3.7 Hz, 1H), 3.39 – 3.30 (m,
2H), 3.29 – 3.14 (m, 2H), 1.86 – 1.70 (m, 4H), 1.56 (s,6H), 1.31 (s, 6H). 13C
NMR (100 MHz, CDCl3) δ 160.30, 159.72, 152.15, 151.57, 146.03, 142.95,
128.86, 128.70, 123.76, 116.29, 114.78, 110.90, 109.55, 47.42, 46.93, 39.21,
35.59, 32.18, 32.16, 30.49, 28.84。
3) synthesis of compound 4
0.41g (1.0mmol) compound 3 and 0.38g (1.2mmol) trifluoromethyl tricyano furan are added in round-bottomed flask
It mutters, is dissolved in 20 ~ 25ml ethyl alcohol, 2 drop triethylamines are added into solution, be stirred at reflux at being 60 DEG C in temperature, react and finish revolving
Ethyl alcohol is removed, crude product is obtained.(stationary phase is the silica gel of 200 ~ 300 mesh to pillar layer separation, and mobile phase is petroleum ether and acetic acid second
The mixed liquor of ester), obtain 0.54g compound 4, yield 76%.1H NMR (500 MHz, CDCl3) δ 7.62 (s, 1H),
7.53 (d, J = 15.8 Hz, 1H), 7.50 – 7.42 (m, 5H), 7.20 – 7.12 (m, 1H), 7.15 (d,J = 15.8 Hz, 1H), 7.10 (s, 1H), 6.90 (s,1H), 6.88 (d, J = 15.1 Hz, 1H), 6.53
(d, J = 3.5 Hz, 1H), 3.30 (t, J = 5.8 Hz, 2H), 3.21 (d, J = 5.0 Hz, 2H), 1.75
(d, J = 5.0 Hz, 2H), 1.70 (t, J = 5.8 Hz, 2H), 1.49 (s, 6H), 1.24 (s, 6H)。
Embodiment 5
5 milligrams of embodiments, 1 gained non-linear optical chromophore is taken, is analyzed on thermogravimetric analyzer, test condition: nitrogen protection,
Heating rate is 10 DEG C per minute, and the thermal decomposition temperature for measuring 1 gained non-linear optical chromophore of embodiment is 228 DEG C.
Embodiment 6
5 milligrams of embodiments, 2 gained non-linear optical chromophore is taken, is analyzed on thermogravimetric analyzer, test condition: nitrogen protection,
Heating rate is 10 DEG C per minute, and the thermal decomposition temperature for measuring 2 gained non-linear optical chromophore of embodiment is 203 DEG C.
Embodiment 7
5 milligrams of embodiments, 3 gained non-linear optical chromophore is taken, is analyzed on thermogravimetric analyzer, test condition: nitrogen protection,
Heating rate is 10 DEG C per minute, and the thermal decomposition temperature for measuring 3 gained non-linear optical chromophore of embodiment is 250 DEG C.
Embodiment 8
5 milligrams of embodiments, 4 gained non-linear optical chromophore is taken, is analyzed on thermogravimetric analyzer, test condition: nitrogen protection,
Heating rate is 10 DEG C per minute, and the thermal decomposition temperature for measuring 4 gained non-linear optical chromophore of embodiment is 256 DEG C.
Performance test
Organic second-order non-linear chromophore prepared by embodiment is tested below.
1,0.08 gram of polymethyl methacrylate (PMMA) is added in 1.00ml methylene bromide, stirring 3~5 is small
After PMMA is completely dissolved, non-linear optical chromophore synthesized by 0.02 gram of embodiment 1 is added, obtains mixed solution, mistake
Spin-coating method film is used in filter on ito glass substrate.Controlling revolving speed is 500~1000 revs/min, and obtained film is at 60 DEG C
It is 24 hours dry in vacuum oven.Film thickness is between 1~5 μm.By 1 gained film using contact polarization method polarization, pole
Change 108 DEG C of temperature, the polarization time is 5-20 minutes, and polarizing voltage is 60-130V/ μm, electro-optic coefficient (r33) pass through simple reflex
Method (Simple Reflection Method, also known as Teng-Man method, referring to Teng C. C., Man H. T.,
Simple reflection technique for measuring the electro-optic coefficient of
Poled polymers, Applied Physics Letters, 1990,56 (18), 1734-1736.) measurement.It measures
Electro-optic coefficient peak is 40pm/V.
2,0.08 gram of polymethyl methacrylate (PMMA) is added in 1.00ml methylene bromide, is stirred 3~5 hours
After being completely dissolved to PMMA, non-linear optical chromophore synthesized by 0.02 gram of embodiment 2 is added, obtains mixed solution, filters,
Spin-coating method film is used on ito glass substrate.Controlling revolving speed is 500~1000 revs/min, vacuum of the obtained film at 60 DEG C
It is 24 hours dry in drying box.Film thickness is between 1~5 μm.By 1 gained film using contact polarization method polarization, polarization temperature
110 DEG C of degree, polarization time are 5-20 minutes, and polarizing voltage is 60-130V/ μm, electro-optic coefficient (r33) pass through simple reflex method
(Simple Reflection Method, also known as Teng-Man method, referring to Teng C. C., Man H. T., Simple
reflection technique for measuring the electro-optic coefficient of poled
Polymers, Applied Physics Letters, 1990,56 (18), 1734-1736.) measurement.Measure electric light system
Number peak is 76pm/V.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to restrict the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent substitution, improvement and etc. done be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of organic second-order non-linear chromophore with D- π-A structure, which is characterized in that the chromophore has I institute of formula
Show structure:
,
Formula I
Wherein,For conjugated electrons bridge, R1、R2Separately it is selected from substituted or unsubstituted following radicals: C1-6's
Alkyl, C1-6Alkoxy, C4-12Aryl or any one of heteroaryl.
2. a kind of organic second-order non-linear chromophore with D- π-A structure according to claim 1, which is characterized in that
The conjugated electrons bridge is with any one in flowering structure:
。
3. a kind of organic second-order non-linear chromophore with D- π-A structure according to claim 1, which is characterized in that
The substitution is by halogen atom, cyano, nitro, C1-3Alkyl or any one or more of substitution of alkoxy, it is described
C4-12Aryl or heteroaryl be selected from phenyl, thienyl, pyridyl group, pyrimidine radicals, pyrazinyl, pyridazinyl, pyrrole radicals, pyrazolyl,
One of thiazolyl is a variety of.
4. a kind of organic second-order non-linear chromophore with D- π-A structure according to claim 3, which is characterized in that
The halogen atom is fluorine, chlorine, bromine, iodine, preferably fluorine.
5. a kind of organic second-order non-linear chromophore with D- π-A structure according to claim 3, which is characterized in that
R1、R2Separately it is selected from hydrogen, methyl, trifluoromethyl and phenyl.
6. a kind of organic second-order non-linear chromophore with D- π-A structure stated according to claim 1, which is characterized in that described
The structure of chromophore are as follows:
, or。
7. a kind of method for preparing any organic second-order non-linear chromophore with D- π-A structure of claim 1-6, special
Sign is, the described method comprises the following steps:
Method one:
Julolidine derivative and tricyano furans electron acceptor are dissolved in ethanol solution, in the effect of organic alkali catalyst
Under, reaction temperature is 50 ~ 80 DEG C, and reaction obtains the novel organic second-order non-linear chromophore with D- π-A structure,
Wherein, the structure of the julolidine derivative are as follows:
,
The tricyano furans electron acceptor has following arbitrary structures:
,
The molar ratio of the julolidine derivative and tricyano furans electron acceptor is 1:1.1 ~ 1:1.2；
Or method two:
1) julolidine derivative and phosphonium salt and sodium hydride are mixed in 1,2- dichloroethane solvent, reaction temperature is 20 ~ 50
DEG C, reaction terminates the post-treated intermediate compound for obtaining structure as formula II,
Formula II
Wherein julolidine derivative: the molar ratio of phosphonium salt is 0.8:1 ~ 1.2:1,
The wherein structure of the julolidine derivative are as follows:
The structure of the phosphonium salt are as follows:
2) it after mixing II intermediate compound of formula in organic solvent with phosphorus oxychloride, is stirred at reflux at 70 ~ 90 DEG C of temperature, instead
It is post-treated to obtain the intermediate compound that structure is formula III after answering,
Formula III
Wherein II intermediate compound of formula: the molar ratio of phosphorus oxychloride is 1:1 ~ 1.2；
3) III compound of formula and tricyano furans electron acceptor are dissolved in ethyl alcohol, react, reacts at being 50 ~ 80 DEG C in temperature
After, the post-treated organic second order non-linear optical chromophore for obtaining that there is D- π-A structure,
Wherein, the tricyano furans electron acceptor has following arbitrary structures:
,
The molar ratio of III intermediate compound of formula and tricyano furans electron acceptor is 1:1.1 ~ 1:1.5.
8. the method for claim 7, which is characterized in that the organic alkali catalyst is selected from triethylamine, pyridine and piperazine
One of pyridine is a variety of.
9. a kind of organic second-order non-linear chromophore according to claim 1-6 with D- π-A structure is answered
With it is characterized in that: the organic second order non-linear optical chromophore and amorphous polymer doping prepare film.
10. a kind of a kind of organic second-order non-linear chromophore with D- π-A structure according to claim 1-6
In the application of photoelectric field.
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