CN115960093A - Optical chromophore compound, composite material containing optical chromophore compound, thin film and photoelectric integrated device - Google Patents
Optical chromophore compound, composite material containing optical chromophore compound, thin film and photoelectric integrated device Download PDFInfo
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- CN115960093A CN115960093A CN202111176852.2A CN202111176852A CN115960093A CN 115960093 A CN115960093 A CN 115960093A CN 202111176852 A CN202111176852 A CN 202111176852A CN 115960093 A CN115960093 A CN 115960093A
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 4
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- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
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- 230000008033 biological extinction Effects 0.000 description 7
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- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
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- UKTDFYOZPFNQOQ-UHFFFAOYSA-N tributyl(thiophen-2-yl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=CS1 UKTDFYOZPFNQOQ-UHFFFAOYSA-N 0.000 description 4
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Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an optical chromophore compound, and a composite material, a thin film and a photoelectric integrated device containing the optical chromophore compound. The optical chromophore compound uses alkyl aniline thiophene compound as a pi-electron donor, tricyano furan(TCF) and its derivatives are pi-electron acceptors, coupled by conjugated bridges with different side chain modifications. The chromophore compounds of the present invention exhibit a large linear electro-optic coefficient (r) at 1304nm as compared to the unmodified chromophore compound 33 ) And good optical transparency at a number concentration of 2.16X 10 20 mL ‑1 In the case of the ZJL-8 polarized polymer film, the electro-optic coefficient is 75pm/V, which is more than two times of 30 pm/V of commercial inorganic electro-optic crystal lithium niobate.
Description
Technical Field
The invention relates to the technical field of optical materials, in particular to an optical chromophore compound, a composite material containing the optical chromophore compound, a thin film and a photoelectric integrated device.
Background
The organic polymer optical waveguide material has the advantages of simple manufacturing process, ultra-fast response time, small dielectric constant and the like, can manufacture a complex photoelectric integrated device by spin coating, photoetching or impressing and other processes, and can be produced in a large scale. However, the chromophore compound is often limited by a low electro-optic coefficient, and how to simply and efficiently modify the chromophore compound and improve the electro-optic coefficient and maintain the optical transparency at the working wavelength is of great significance to the development of electro-optic materials.
Disclosure of Invention
In order to solve the above technical problems, a first object of the present invention is to provide an optical chromophore compound.
It is a second object of the present invention to provide a composite material containing the above optical chromophore compound.
A third object of the present invention is to provide a thin film made of the above composite material, and a photovoltaic integrated device having the thin film.
In order to achieve the purpose, the invention adopts the following technical scheme:
the first aspect of the present invention provides an optical chromophore compound, wherein the structural formula of the optical chromophore compound is shown as formula 1:
R 1 ＝R 2 -R 3 formula 1;
in the formula 1, R 1 Is a pi-electron donor group and is an alkyl aniline thiophene compound; the structure is shown in formula 2 or formula 3:
r in formula 2 or 3 4 、R 4 ' is independently selected from C1-12 alkyl or siloxy substituted C1-12 alkyl;
R 2 is a conjugate bridge, and the structure of the conjugate bridge is shown as formula 4:
R 3 is a pi-electron acceptor group, is tricyano furan (TCF) and derivatives thereof, and has a structure shown in a formula 5:
r in the formula 5 5 、R 6 Independently selected from C1-C6 alkyl, halogen substituted C1-C6 alkyl or aryl; the aryl group is preferably a phenyl group or a substituted phenyl group.
In the optical chromophore compound provided by the invention, a pi-electron donor group is conjugated with a pi-electron acceptor group through a diene conjugated bridge. Through structural modification, steric hindrance, bond length alternation and receptor push-pull strength are changed.
According to the optical chromophore compound, the pi-electron donor group is an alkyl aniline thiophene compound; the structure is shown as formula 2 or formula 3, preferably, R 4 、R 4 ' is independently selected from C2-8 alkyl or substituted C2-8 alkyl; for example, R 4 、R 4 ' may be independently n-butyl, -CH 2 CH 2 OSiPh 2 (t-C 4 H 9 ) And so on.
According to the bookThe inventive optical chromophore compound has a pi-electron acceptor group of Tricyanofuran (TCF) and derivatives thereof, and has a structure shown in formula 5, preferably, R 5 、R 6 Independently selected from trifluoromethyl or phenyl, e.g. R 5 Is phenyl, R 6 Is trifluoromethyl.
The optical chromophore compound according to the present invention, preferably, the structural formula of the optical chromophore compound is one of the following formulae:
the optical chromophore compound provided by the invention is a nonlinear optical material and can be used for preparing optical composite materials, optical films, electro-optical devices and the like.
The invention also provides a synthetic route of more than one optical chromophore compound:
route one:
and a second route:
wherein R is 4 、R 4 ’、R 5 And R 6 As defined hereinabove.
The aniline compound reacts with corresponding raw materials through four steps of NBS bromination, stille coupling, allenylation and condensation to obtain the optical chromophore compound.
In a second aspect, the present invention provides a composite material comprising the above-described optical chromophore compound.
According to the composite material of the present invention, preferably, the content of the optical chromophore compound is 10% to 90% based on the total weight of the composite material.
According to the composite material of the present invention, preferably, the composite material further comprises a polymer. The optical chromophore compound is mixed with the polymer to prepare the composite material, and the composite material has the advantages of large nonlinear coefficient, easy processing and the like, and can be prepared into a film with good optical quality.
According to the composite material of the present invention, preferably, the polymer includes one or a combination of two or more of polymethyl methacrylate, methyl methacrylate-styrene copolymer, and polycarbonate.
The composite material according to the invention preferably has an electro-optical coefficient r in the wavelength range of 1000nm to 1600nm 33 Is 40pm/V to 90pm/V; more preferably from 41pm/V to 75pm/V.
According to the composite material of the present invention, preferably, the refractive index of the composite material changes by 0.0005 to 0.005 under the action of an electric field of 0 to 40V/. Mu.m.
The above-mentioned electro-optic coefficient r 33 The refractive index change was measured by forming the composite material into a film and then testing the film.
In a third aspect, the present invention provides a film made from the above composite material.
The invention also provides a photoelectric integrated device which is provided with the film. Preferably, the optoelectronic integration device is an electro-optical device. The optical chromophore provided by the invention realizes a relatively large electro-optic effect.
Electro-optical or electro-absorption modulators are a class of devices that modulate the intensity of laser light by means of a voltage. Organic electro-optic materials are of great significance for modulating electrical signals. The prior electro-optical material has the problems of low electro-optical coefficient, poor solubility, low thermal stability, poor film-forming quality and the like. According to the invention, through carrying out structural modification on the donor of the chromophore compound, the solubility, the processability and the stability of the material are obviously improved, the electro-optic coefficient is obviously increased, and the transparency at the working wavelength of 1300nm is good. And the synthesis method of the invention directly condenses with the receptor after one-step allenation to obtain the required chromophore compound, compared with the related documents, the synthesis method is relatively simple and efficient, has high synthesis efficiency, and greatly simplifies the synthesis time and cost. The method has wide potential for realizing large-area preparation, assembly and application of the modulator and the application of the next generation information technology.
Drawings
FIG. 1 is a diagram of compound N-2 of example 1 1 H NMR spectrum.
FIG. 2 shows Compound N-3 of example 1 1 H NMR spectrum.
FIG. 3 is a drawing of compound N-3 of example 1 1 H NMR spectrum.
FIG. 4 is a drawing of compound N-4 of example 1 13 C NMR spectrum.
FIG. 5 is a scheme of ZJL-7, a compound of example 1 1 H NMR spectrum.
FIG. 6 is a scheme of ZJL-7, a compound of example 1 13 C NMR spectrum.
FIG. 7 is a photograph of Compound A-2 of example 2 1 H NMR spectrum.
FIG. 8 is a photograph of Compound A-2 of example 2 13 C NMR spectrum.
FIG. 9 is a drawing of Compound A-3 of example 2 1 H NMR spectrum.
FIG. 10 is a drawing of Compound A-3 of example 2 13 C NMR spectrum.
FIG. 11 is a drawing of Compound A-4 of example 2 1 H NMR spectrum.
FIG. 12 is a photograph of Compound A-4 of example 2 13 C NMR spectrum.
FIG. 13 shows ZJL-8, a compound of example 2 1 H NMR spectrum.
FIG. 14 shows ZJL-8, a compound of example 2 13 C NMR spectrum.
FIG. 15 is a drawing of the compound AT-2 of example 3 1 H NMR spectrum.
FIG. 16 is a drawing of the compound AT-2 of example 3 13 C NMR spectrum.
FIG. 17 is a drawing of compound AT-3 of example 3 1 H NMR spectrum.
FIG. 18 is a drawing of the compound AT-3 of example 3 13 C NMR spectrum.
FIG. 19 is a drawing of the compound AT-4 of example 3 1 H NMR spectrum.
FIG. 20 is a drawing of the Compound AT-4 of example 3 13 C NMR spectrum.
FIG. 21 is of compound ZJL-9 of example 3 1 H NMR spectrum.
FIG. 22 shows ZJL-9 Compound of example 3 13 C NMR spectrum.
FIG. 23 is a depiction of compound TQ-8 from example 4 1 H NMR spectrum.
FIG. 24 is a scheme showing the preparation of compound TQ-8 of example 4 13 C NMR spectrum.
FIG. 25 is a scheme showing that compound TQ-9 of example 4 1 H NMR spectrum.
FIG. 26 is a sample of Compound TQ-9 of example 4 13 C NMR spectrum.
FIG. 27 is a schematic representation of compound TQ-10 of example 4 1 H NMR spectrum.
FIG. 28 is a sample of compound TQ-10 of example 4 13 C NMR spectrum.
FIG. 29 is a scheme showing that compound TQ-11 of example 4 1 H NMR spectrum.
FIG. 30 is a sample of Compound TQ-12 of example 4 1 H NMR spectrum.
FIG. 31 is a scheme showing that compound TQ-12 of example 4 13 C NMR spectrum.
FIG. 32 shows ZJL-10, a compound of example 4 1 H NMR spectrum.
FIG. 33 is of compound ZJL-10 of example 4 13 C NMR spectrum.
FIG. 34 is a plot of molar extinction coefficient spectra in solution of compound ZJL-7 of example 1.
FIG. 35 is a molar extinction coefficient spectrum of compound ZJL-8 of example 2 in solution.
FIG. 36 is a molar extinction coefficient spectrum of compound ZJL-9 of example 3 in solution.
FIG. 37 is a molar extinction coefficient spectrum of the compound ZJL-10 of example 4 in a solution.
FIG. 38 is a graph showing the results of the test of the reflection intensity of TE and TM waves of an unpolarized film, a polarized film and a film made by mixing ZJL-8 of example 2 with a polymer at a wavelength of 1304nm.
Detailed Description
In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is intended to be illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
All numerical designations of the invention (e.g., temperature, time, concentration, weight, and the like, including ranges for each) may generally be approximations that vary (+) or (-) in increments of 0.1 or 1.0 as appropriate. All numerical designations should be understood as preceded by the term "about".
Example 1
This example prepares an optical chromophore compound (compound ZJL-7) having the structure shown below:
the optical chromophore compound is prepared by the following steps:
step i Synthesis of Compound N-2：
5.0g of Compound N-1 is dissolved in 20mL of DMF and cooled to 0 ℃; 4.55g of NBS in DMF (dissolved in 5mL of DMF) was added dropwise thereto; after the dropwise addition is finished, heating the solution to room temperature, and stirring overnight to obtain a reaction solution; the reaction solution was poured into water toExtracting with hexane; the obtained solution was treated with anhydrous Na 2 SO 4 Drying, concentrating, evaporating to dryness, and separating by column chromatography (adsorbent is silica gel, n-hexane: ethyl acetate =10 =1 (V/V)); compound N-2 (6.6g, 95%) was obtained.
Of the compound N-1 1 The H NMR detection result is as follows, and the specific spectrogram is shown in figure 1:
1 H NMR(CDCl 3 ,400MHz,ppm):δ7.25(d,J＝9.2Hz,2H),6.50(d,J＝8.4Hz, 2H),3.22(t,J＝7.7Hz,4H),1.58-1.52(m,4H),1.37-1.31(m,4H),0.95(t,J＝7.4 Hz,6H).
step ii, synthesis of Compound N-3：
4.0g of the compound N-2,0.25g Pd obtained in step i 2 (dba) 3 0.34g of tri (o-tolyl) phosphine and 5.8g of 2-tributylstannyl thiophene were reacted in 30mL of a toluene solution at 115 ℃ for 24 hours; after the reaction, the solvent was evaporated to dryness, and separated by column chromatography (adsorbent was silica gel, n-hexane: ethyl acetate =10:1 (V/V)); compound N-3 (4.1 g, equiv.) is obtained.
Of the compound N-3 1 The H NMR detection result is as follows, and the specific spectrogram is shown in figure 2:
1 H NMR(CDCl 3 ,400MHz,ppm):δ7.45(d,J＝8.8Hz,2H),7.13-7.11(m,2H), 7.02(dd,J＝3.6Hz,5.0Hz,1H),6.63(d,J＝8.9Hz,2H),3.28(t,J＝7.9Hz,3H), 1.66-1.59(m,4H),1.39-1.31(m,4H),0.96(t,J＝7.3Hz,6H).
step iii Synthesis of Compound N-4：
Dissolving 0.5g of the compound N-3 obtained in step ii in 5mL of anhydrous tetrahydrofuran and cooling to-20 ℃; 1.2mL of a 1.6M n-butyllithium solution was added dropwise thereto, and the resulting reaction solution was reacted at-20 ℃ for 2 hours; 0.2g of 3- (dimethylamino) acrolein was added dropwise to the reaction solution at-20 ℃ above; after the dropwise addition is finished, heating the solution to room temperature, and stirring overnight to obtain a reaction solution; pouring the reaction solution into water, and extracting with dichloromethane; the obtained solution was treated with anhydrous Na 2 SO 4 Drying, concentrating, evaporating to dryness, and separating by column chromatography (adsorbent is silica gel, eluting agent is dichloromethane); compound N-4 (0.31g, 52%) was obtained.
Of the compound N-4 1 The H NMR detection result is as follows, and the specific spectrogram is shown in figure 3:
1 H NMR(CDCl 3 ,300MHz,ppm):δ9.57(d,J＝7.8Hz,1H),7.53-7.46(m,3H), 7.25(d,J＝3.8Hz,1H),7.11(d,J＝3.9Hz,1H),6.62(d,J＝8.9Hz,2H),6.41(dd,J ＝7.8Hz,15.4Hz,1H),3.30(t,J＝7.6Hz,4H),1.63-1.53(m,4H),1.43-1.30(m, 4H),0.97(t,J＝7.3Hz,6H).
of this compound N-4 13 The C NMR detection result is as follows, and the specific spectrogram is shown in figure 4:
13 C NMR(CDCl 3 ,75MHz,ppm):δ192.91,151.63,148.61,145.12,135.65, 134.45,127.34,125.38,121.47,120.06,111.55,50.79,29.42,20.35,14.04.
step iv, synthesis of Compound ZJL-7：
0.25g of the compound N-4,0.23g of CF obtained in step iii 3 Ph-TCF is refluxed and reacted for 1h in 2mL ethanol; ethanol was distilled off, and the product was separated by column chromatography (adsorbent: silica gel, n-hexane: ethyl acetate =4 (V/V)); compound ZJL-7 (0.32g, 68%) was obtained.
Of this compound ZJL-7 1 The H NMR detection result is as follows, and the specific spectrogram is shown in figure 5:
1 H NMR(CDCl 3 ,300MHz,ppm):δ7.70(dd,J＝14.4,11.8Hz,1H),7.60-7.43(m, 7H),7.26(s,1H),7.25-7.12(m,2H),6.66(dd,J＝15.9,10.3Hz,3H),6.41(d,J＝14.9Hz, 1H),3.39-3.23(m,4H),1.66-1.58(m,3H),1.54-1.50(m,1H),1.37(dd,J＝14.9,7.4Hz, 4H),0.97(t,J＝7.3Hz,6H).
of this compound ZJL-7 13 The C NMR detection result is as follows, and the specific spectrogram is shown in FIG. 6:
13 C NMR(150MHz,CDCl 3 )δ175.55,162.04,155.00,151.19,149.36,142.05,137.96, 136.68,131.46,129.74(d,J＝8.3Hz),128.41,127.77,126.80,125.61,122.74,119.83, 115.94,111.76(d,J＝11.8Hz),111.22,110.70,96.04,58.08,50.85,31.60,29.46,22.66, 20.31,14.13,13.97.
example 2
This example provides an optical chromophore compound (compound ZJL-8) having the structure shown below:
the optical chromophore compound is prepared by the following steps:
step i, synthesis of Compound A-2：
6.0g of Compound A-1 is dissolved in 20mL of DMF and cooled to 0 ℃; to this was added dropwise a solution of 2.7g NBS in DMF (dissolved in 5mL DMF); after the dropwise addition is finished, heating the solution to room temperature, and stirring overnight to obtain a reaction solution; pouring the reaction solution into water, and extracting by using n-hexane; the obtained solution is treated with anhydrous Na 2 SO 4 Concentrating and evaporating after drying, and separating by column chromatography (the adsorbent is silica gel, normal hexane: ethyl acetate =10 =1 (V/V)); compound A-2 (7.2 g, equiv.) was obtained.
Of the Compound A-2 1 The detection result of H NMR is as follows, and the specific spectrogram is shown in figure 7:
1 H NMR(CDCl 3 ,300MHz,ppm):δ7.83(dt,J＝5.9,1.9Hz,4H),7.58-7.49(m,6H), 7.30(d,J＝9.1Hz,2H),6.48(d,J＝9.2Hz,2H),3.92(t,J＝6.7Hz,2H),3.52(t,J＝6.7 Hz,2H),3.42(d,J＝7.1Hz,2H),1.20(dd,J＝9.0,5.3Hz,12H).
of the Compound A-2 13 The C NMR detection result is as follows, and the specific spectrogram is shown in FIG. 8:
13 C NMR(CDCl 3 ,75MHz,ppm):δ146.90,135.79(d,J＝2.8Hz),133.55(s), 131.95,129.94(d,J＝9.5Hz),127.93(d,J＝6.3Hz),113.35,107.32,61.14,52.26, 45.53,27.06(d,J＝3.9Hz),19.30,12.18.
step ii, synthesis of Compound A-3：
1.0g of Compound A-2 from step i, 80mg of Pd 2 (dba) 3 0.1g of tri (o-tolyl) phosphine and 0.9g of 2-tributylstannyl thiophene were reacted in 10mL of toluene solution at 115 ℃ for 24h; after the reaction is finished, the solvent is evaporated to dryness, and the mixture is separated by column chromatography (the adsorbent is silica gel, normal hexane: ethyl acetate =10 =1 (V/V)); compound A-3 (0.63g, 81%) was obtained.
Of the Compound A-3 1 The detection result of H NMR is as follows, and the specific spectrogram is shown in figure 9:
1 H NMR(CDCl 3 ,300MHz,ppm):δ7.82(d,J＝2.2Hz,1H),7.70(dd,J＝7.8, 1.6Hz,4H),7.50-7.41(m,7H),7.36-7.27(m,3H),7.11(ddd,J＝8.8,6.7,3.9Hz, 3H),3.82(t,J＝6.3Hz,2H),3.20(dt,J＝14.1,6.7Hz,4H),1.14-1.02(m,12H).
of the Compound A-3 13 The C NMR result is as follows, and the specific spectrogram is shown in FIG. 10:
13 C NMR(CDCl 3 ,75MHz,ppm):δ147.33,144.31,141.24,135.68,133.73, 130.99,129.68(d,J＝3.9Hz),128.06,127.75,127.21,126.29(d,J＝13.6Hz), 125.36,124.33,123.62,122.64,61.94,54.22,48.16,26.93,19.20,11.89.
step iii Synthesis of Compound A-4：
Dissolving 0.6g of Compound A-3 from step ii in 5mL of anhydrous tetrahydrofuran and cooling to-20 ℃; 1.2mL of 1.6M n-butyllithium solution was added dropwise thereto, and the obtained reaction solution was reacted at-20 ℃ for 2 hours; 0.2g of 3- (dimethylamino) acrolein was added dropwise to the reaction solution at-20 ℃ above; after the dropwise addition is finished, heating the temperature of the solution to room temperature, and stirring overnight to obtain a reaction solution; pouring the reaction solution into water, and extracting with dichloromethane; the obtained solution was treated with anhydrous Na 2 SO 4 Drying, concentrating, evaporating to dryness, and separating by column chromatography (adsorbent is silica gel, eluting agent is dichloromethane); compound N-4 (0.41g, 62%) was obtained.
Of the Compound A-4 1 The H NMR detection result is as follows, and the specific spectrogram is shown in FIG. 11:
1 H NMR(CDCl 3 ,300MHz,ppm):δ9.60(d,J＝7.8Hz,1H),7.73-7.66(m,4H), 7.57-7.34(m,9H),7.27(d,J＝3.9Hz,1H),7.12(d,J＝3.9Hz,1H),6.56-6.39(m, 3H),3.83(t,J＝6.5Hz,2H),3.49(dd,J＝8.4,4.7Hz,2H),3.39(q,J＝7.0Hz,2H), 1.15(t,J＝7.0Hz,3H),1.09(s,9H).
of the Compound A-4 13 The C NMR detection result is as follows, and the specific spectrogram is shown in FIG. 12:
13 C NMR(CDCl 3 ,75MHz,ppm):δ192.89,151.49,148.37,145.07,135.74(d, J＝10.5Hz),134.42,133.39,129.87,127.84,127.34,125.50,121.63,120.52,111.60, 61.08,51.98,45.46,26.91,19.17,12.20.
step iv, synthesis of Compound ZJL-8：
0.4g of Compound A-4,0.24g CF obtained in step iii 3 Ph-TCF is refluxed and reacted for 1h in 2mL ethanol; distilling off ethanol, and separating by column chromatography (adsorbent is silica gel, n-hexane: ethyl acetate =4 =1 (V/V)); compound ZJL-8 (0.47g, 77%) was obtained.
Of this compound ZJL-8 1 The detection result of H NMR is as follows, and the specific spectrogram is shown in figure 13:
1 H NMR(CDCl 3 ,300MHz,ppm):δ7.76-7.61(m,5H),7.59-7.32(m,13H),7.27(s, 1H),7.25-7.13(m,2H),6.67(dd,J＝14.4,11.5Hz,1H),6.46(dd,J＝24.4,11.9Hz,3H), 3.80(t,J＝6.4Hz,2H),3.47(t,J＝6.4Hz,2H),3.38(q,J＝7.0Hz,2H),1.13(t,J＝7.0 Hz,3H),1.05(s,9H).
of this compound ZJL-8 13 The C NMR detection result is as follows, and the specific spectrogram is shown in FIG. 14:
13 C NMR(CDCl 3 ,150MHz,ppm):δ175.59,162.11,154.88,151.26,149.19,142.11, 138.10,136.71,135.65,133.33,131.52,129.96-129.60(m),127.78(d,J＝12.7Hz),126.82, 125.74,123.07,122.90,121.17,120.25,116.05,111.79,111.24(d,J＝2.3Hz),110.76, 96.45-96.00(m),61.09,58.45,58.08,51.99,45.56,26.89,19.14,18.47,12.19.
example 3
This example prepares an optical chromophore compound (compound ZJL-9) having the structure shown below:
the optical chromophore compound is prepared by the following steps:
step i Synthesis of Compound AT-2：
1.75g of the compound AT-1 are dissolved in 10mL of DMF and cooled to 0 ℃; 1.73g of NBS in DMF (dissolved in 5mL of DMF) was added dropwise thereto; after the dropwise addition is finished, heating the solution to room temperature, and stirring overnight to obtain a reaction solution; pouring the reaction liquid into water, and extracting by using normal hexane; the obtained solution was treated with anhydrous Na 2 SO 4 Drying, concentrating, evaporating to dryness, and separating by column chromatography (adsorbent is silica gel, n-hexane: ethyl acetate =10 =1 (V/V)); compound AT-2 (1.71g, 69%) was obtained.
Of the Compound AT-2 1 The detection result of H NMR is as follows, and the specific spectrogram is shown in figure 15:
1 H NMR(CDCl 3 ,300MHz,ppm):δ7.14(dd,J＝8.8,2.5Hz,1H),7.09-7.02(m,1H), 6.46(d,J＝8.8Hz,1H),3.34-3.18(m,4H),2.75(t,J＝6.4Hz,2H),2.03-1.88(m,2H),1.60 (ddd,J＝11.9,9.3,7.2Hz,2H),1.41(dq,J＝14.4,7.2Hz,2H),1.01(t,J＝7.3Hz,3H).
of the Compound AT-2 13 The results of the C NMR measurements are as follows, and the specific spectrum is shown in FIG. 16:
13 C NMR(CDCl 3 ,75MHz,ppm):δ144.37,131.45,129.60,124.34,112.01, 106.61,51.26,49.37,28.21(d,J＝6.3Hz),22.05,20.51,14.16.
step ii, synthesis of Compound AT-3：
1.5g of the compound AT-2,0.1g Pd obtained in step i 2 (dba) 3 0.14g of tri (o-tolyl) phosphine and 2.5g of 2-tributylstannyl thiophene were reacted in 20mL of toluene solution at 115 ℃ for 24h; after the reaction is finished, the solvent is evaporated to dryness, and the mixture is separated by column chromatography (the adsorbent is silica gel, normal hexane: ethyl acetate =10 =1 (V/V)); the compound AT-3 (1) is obtained.50g，92％)。
Of the compound AT-3 1 The detection result of H NMR is as follows, and the specific spectrogram is shown in figure 17:
1 H NMR(CDCl 3 ,300MHz,ppm)δ7.28(d,J＝8.5Hz,1H),7.18(s,1H),7.08(dd,J ＝4.5,1.4Hz,2H),7.02-6.95(m,1H),6.53(d,J＝8.6Hz,1H),3.35-3.11(m,4H),2.75(t, J＝6.2Hz,2H),1.99-1.85(m,2H),1.68-1.49(m,4H),1.39-1.26(m,6H),1.00-0.86(m, 7H).
of the Compound AT-3 13 The C NMR detection result is as follows, and the specific spectrogram is shown in FIG. 18:
13 C NMR(CDCl 3 ,75MHz,ppm):145.72,144.99,127.80,126.98,125.03, 122.31(d,J＝2.9Hz),121.75,120.43,110.56,51.26,49.55,28.76–28.10(m),26.88, 22.25,20.53,17.38,14.15,13.72.
step iii Synthesis of Compound AT-4：
0.5g of the compound AT-3 obtained in step ii and 0.25g of 3- (dimethylamino) acrolein are dissolved in 5mL of chloroform and cooled to 0 ℃; dropwise adding 0.25mL of phosphorus oxychloride, and after dropwise adding, heating the solution to 70 ℃ for reacting for 3h; pouring the reaction solution into water, and extracting with dichloromethane; the obtained solution is treated with anhydrous Na 2 SO 4 Drying, concentrating, evaporating to dryness, and separating by column chromatography (adsorbent is silica gel, eluting agent is dichloromethane); compound AT-4 (0.31 g, 52%) was obtained.
Of the Compound AT-4 1 The detection result of H NMR is as follows, and the specific spectrogram is shown in figure 19:
1 H NMR(CDCl 3 ,30 0MHz,ppm):δ9.56(d,J＝7.8Hz,1H),7.54-7.46(m,1H), 7.32(dd,J＝8.6,2.3Hz,1H),7.25(d,J＝3.9Hz,1H),7.20(d,J＝2.2Hz,1H),7.09 (d,J＝3.9Hz,1H),6.54(d,J＝8.7Hz,1H),6.40(dd,J＝15.4,7.8Hz,1H),3.36– 3.22(m,4H),2.77(t,J＝6.3Hz,2H),1.94(dd,J＝11.5,6.1Hz,2H),1.63-1.54(m, 2H),1.40-1.32(m,2H),0.95(d,J＝7.3Hz,3H).
of the Compound AT-4 13 The C NMR detection result is as follows, and the specific spectrogram is shown in FIG. 20: 13 C NMR(CDCl 3 ,75MHz,ppm):δ192.94,151.87,146.10,145.21,135.49,134.49, 126.89,125.27(d,J＝5.8Hz),122.32,121.36,120.08,110.33,51.13,49.55,28.32 (d,J＝19.9Hz),21.94,20.41,14.04.
step iv Synthesis of Compound ZJL-9：
0.2g of the compound AT-4,0.19g CF obtained in step iii 3 Ph-TCF is subjected to reflux reaction in 2mL of ethanol for 1h; distilling off ethanol, and separating by column chromatography (adsorbent is silica gel, n-hexane: ethyl acetate =4 =1 (V/V)); compound ZJL-9 (0.25g, 65%) was obtained.
Of the compound ZJL-9 1 The detection result of H NMR is as follows, and the specific spectrogram is shown in figure 21:
1 H NMR(CDCl 3 ,300MHz,ppm):δ7.73(dd,J＝14.6,11.7Hz,1H),7.58-7.49(m, 5H),7.37(dd,J＝8.7,2.3Hz,1H),7.29(s,1H),7.24(s,2H),7.19(d,J＝4.1Hz,1H),6.67 (dd,J＝14.4,11.5Hz,1H),6.57(d,J＝8.8Hz,1H),6.41(d,J＝14.8Hz,1H),3.42-3.29 (m,4H),2.79(t,J＝6.2Hz,2H),1.99(dd,J＝11.8,5.8Hz,2H),1.66(d,J＝7.2Hz,1H), 1.57(s,2H),1.40(dd,J＝15.0,7.4Hz,2H),0.99(t,J＝7.3Hz,3H).
process for preparation of ZJL-9 13 The result of the C NMR is as follows, and the specific spectrogram is shown in FIG. 22:
13 C NMR(CDCl 3 ,150MHz,ppm):δ175.58,161.89,155.43,151.15,147.02,142.09, 137.88,136.80,131.42,129.74(d,J＝14.8Hz),129.52,127.15,126.79,125.94,125.53, 122.67,122.54,119.83,115.80,111.27(d,J＝8.2Hz),110.75,110.46,95.79,57.87,51.19, 49.70,28.58,28.15,21.78,20.37,13.98.
example 4
This example prepares an optical chromophore compound (compound ZJL-10) having the structure shown below:
the optical chromophore compound is prepared by the following steps:
step i, synthesis of Compound TQ-8：
5.0g of Compound TQ-7 was dissolved in 20mL DMF and cooled to 0 ℃; 4.1g of NBS in DMF (dissolved in 5mL of DMF) was added dropwise thereto; after the dropwise addition is finished, heating the solution to room temperature, and stirring overnight to obtain a reaction solution; pouring the reaction solution into water, and extracting by using n-hexane; the obtained solution is treated with anhydrous Na 2 SO 4 Drying, concentrating, evaporating to dryness, and separating by column chromatography (adsorbent is silica gel, n-hexane: ethyl acetate =10 =1 (V/V)); compound TQ-8 (4.0 g, 58%) was obtained.
Process for preparing this compound TQ-8 1 The detection result of H NMR is as follows, and the specific spectrogram is shown in figure 23:
1 H NMR(CDCl 3 ,300MHz,ppm):δ7.13-7.06(m,1H),7.06-7.00(m,1H),6.48(d,J ＝8.8Hz,1H),4.23(t,J＝6.2Hz,2H),3.49(t,J＝6.2Hz,2H),3.34-3.27(m,2H),2.71(t, J＝6.3Hz,2H),2.03(s,3H),1.91(dq,J＝8.8,6.2Hz,2H).
process for preparing this compound TQ-8 13 The results of the C NMR measurements are as follows, and the specific spectrum is shown in FIG. 24:
13 C NMR(CDCl 3 ,75MHz,ppm):δ171.03,143.89,131.63,129.65,124.52,112.10, 107.56,60.96,49.90(d,J＝2.4Hz),27.95,21.86,20.95.
step ii, synthesis of Compound TQ-9：
2.5g of the compound TQ-8,0.15g Pd obtained in step i 2 (dba) 3 0.2g of tri (o-tolyl) phosphine and 3.7g of 2-tributylstannyl thiophene were reacted in 20mL of a toluene solution at 115 ℃ for 24h; after the reaction is finished, evaporating the solvent, and separating by column chromatography (the adsorbent is silica gel, normal hexane: ethyl acetate =10 =1 (V/V)); compound TQ-9 (1.50g, 59%) was obtained.
Preparation of this compound TQ-9 1 The detection result of H NMR is as follows, and the specific spectrogram is shown in figure 25:
1 H NMR(CDCl 3 ,400MHz,ppm):δ7.32(dd,J＝8.5,2.3Hz,1H),7.24-7.20 (m,1H),7.16-7.10(m,2H),7.02(dd,J＝5.0,3.7Hz,1H),6.63(d,J＝8.6Hz,1H), 4.28(t,J＝6.2Hz,2H),3.56(t,J＝6.2Hz,2H),3.40-3.33(m,2H),2.80(t,J＝6.4 Hz,2H),2.05(s,3H),1.97(dd,J＝6.3,5.3Hz,2H).
process for preparing this compound TQ-9 13 The C NMR result is as follows, and the specific spectrogram is shown in FIG. 26:
13 C NMR(CDCl 3 ,75MHz,ppm):δ171.07,145.35,144.49,127.81,127.10,125.03, 122.58,120.71,110.69,61.17,50.00(d,J＝19.6Hz),28.12,22.14,20.99.
step iii Synthesis of Compound TQ-10：
0.7g of the compound TQ-9 obtained in step ii and 0.3g of 3- (dimethylamino) acrolein are dissolved in 5mL of chloroform and cooled to 0 ℃; dropwise adding 0.3mL of phosphorus oxychloride, and after dropwise adding, heating the solution to 70 ℃ for reaction for 3h; pouring the reaction solution into water, and extracting with dichloromethane; the obtained solution was treated with anhydrous Na 2 SO 4 Drying, concentrating, evaporating to dryness, and separating by column chromatography (adsorbent is silica gel, eluting agent is dichloromethane); compound TQ-10 (0.60 g, 73%) was obtained.
Process for preparing this compound TQ-10 1 The detection result of H NMR is as follows, and the specific spectrogram is shown in figure 27:
1 H NMR(CDCl 3 ,300MHz,ppm):δ9.56(d,J＝7.8Hz,1H),7.49(d,J＝15.4 Hz,1H),7.32(dd,J＝8.6,2.3Hz,1H),7.24(d,J＝3.9Hz,1H),7.21(d,J＝2.2Hz, 1H),7.10(d,J＝3.9Hz,1H),6.62(d,J＝8.7Hz,1H),6.40(dd,J＝15.4,7.8Hz, 1H),4.26(t,J＝6.2Hz,2H),3.56(t,J＝6.2Hz,2H),3.44-3.31(m,2H),2.77(t,J＝ 6.3Hz,2H),2.03(s,3H),2.00-1.90(m,2H).
process for preparing this compound TQ-10 13 The results of the C NMR measurements are as follows, and the specific spectrum is shown in FIG. 28:
13 C NMR(CDCl 3 ,75MHz,ppm):δ192.87,171.00,151.37,145.66,145.05, 135.83,134.36,127.07,125.37(d,J＝12.0Hz),122.66,121.70,121.03,110.56, 60.98,50.13,49.72,28.07,21.89,20.95.
step iv Synthesis of Compound TQ-11：
0.6gDissolving the compound TQ-10 obtained in the step iii in 3mL of methanol containing 1M KOH, and stirring overnight at room temperature to obtain a reaction solution; pouring the reaction solution into water, and extracting with dichloromethane; the obtained solution was treated with anhydrous Na 2 SO 4 Drying, concentrating, evaporating to dryness, and separating by column chromatography (adsorbent is silica gel, n-hexane: ethyl acetate =2 =1 (V/V)); compound TQ-11 (0.43g, 81%) was obtained.
Preparation of this Compound TQ-11 1 The detection result of H NMR is as follows, and the specific spectrogram is shown in figure 29:
1 H NMR(CDCl 3 ,300MHz,ppm):δ9.59(d,J＝7.8Hz,1H),7.53(d,J＝15.4 Hz,1H),7.34(dd,J＝8.6,2.3Hz,1H),7.29(d,J＝3.6Hz,1H),7.28-7.21(m,2H), 7.14(d,J＝3.9Hz,1H),6.69(d,J＝8.6Hz,1H),6.43(dd,J＝15.4,7.8Hz,1H), 3.88(t,J＝5.7Hz,2H),3.53(t,J＝5.8Hz,2H),3.47-3.36(m,2H),2.83(t,J＝6.2 Hz,2H),2.01(dt,J＝12.4,6.3Hz,2H),1.80(s,1H).
step v, synthesis of Compound TQ-12：
Dissolving 0.4g of the compound TQ-11 obtained in the step iv and 0.17g of imidazole in 5mL of DMF, dropwise adding 0.53g of tert-butyldiphenylchlorosilane into the solution, and stirring the obtained reaction solution at room temperature overnight to obtain a reaction solution; pouring the reaction solution into water, and extracting with dichloromethane; the obtained solution is treated with anhydrous Na 2 SO 4 Drying, concentrating, evaporating to dryness, and separating by column chromatography (adsorbent is silica gel, n-hexane: ethyl acetate =10 =1 (V/V)); compound TQ-12 (0.52 g, 74%) was obtained.
Preparation of this Compound TQ-12 1 The detection result of H NMR is as follows, and the specific spectrogram is shown in figure 30:
1 H NMR(CDCl 3 ,300MHz,ppm):δ9.61(d,J＝7.8Hz,1H),7.69(dd,J＝7.9, 1.5Hz,4H),7.54(d,J＝15.4Hz,1H),7.50-7.35(m,7H),7.30-7.26(m,1H),7.25- 7.17(m,2H),7.13(d,J＝3.9Hz,1H),6.45(dd,J＝15.4,7.8Hz,1H),6.35(d,J＝ 9.2Hz,1H),3.86(t,J＝6.2Hz,2H),3.49(t,J＝6.2Hz,2H),3.45-3.31(m,2H),2.78 (t,J＝6.2Hz,2H),2.00-1.85(m,2H),1.09(s,10H).
process for preparing this compound TQ-12 13 The C NMR result is as follows, and the specific spectrogram is shown in FIG. 31:
13 C NMR(CDCl 3 ,75MHz,ppm):δ192.90,151.79,146.02,145.13,135.62, 134.42,133.37,129.80,127.78,126.87,125.32(d,J＝4.4Hz),122.28,121.44, 120.41,110.59,60.62,53.26,50.57,28.16,26.86,21.95,19.14.
step vi Synthesis of Compound ZJL-10：
0.3g of the compound TQ-12 from step v, 0.17g of CF 3 Ph-TCF is refluxed and reacted for 1h in 2mL ethanol; distilling off ethanol, and separating by column chromatography (adsorbent is silica gel, n-hexane: ethyl acetate =4 =1 (V/V)); compound ZJL-10 (0.32g, 68%) was obtained.
Of the compound ZJL-10 1 The detection result of H NMR is as follows, and the specific spectrogram is shown in figure 32:
1 H NMR(CDCl 3 ,300MHz,ppm):δ7.77-7.61(m,5H),7.56-7.32(m,11H),7.26(s, 1H),7.26-7.13(m,5H),6.66(dd,J＝14.4,11.5Hz,1H),6.36(dd,J＝20.2,12.1Hz,2H), 3.83(t,J＝6.1Hz,2H),3.44(dt,J＝11.1,5.8Hz,4H),2.74(t,J＝6.1Hz,2H),2.00-1.84 (m,2H),1.04(s,9H).
the compound ZJL-10 13 The results of the C NMR measurements are as follows, and the specific spectrum is shown in FIG. 33:
13 C NMR(CDCl 3 ,150MHz,ppm):δ175.59,161.95,155.26,151.17,146.99,142.08, 137.95,136.74,135.60,133.28,131.45,129.91-129.62(m),127.78,127.09,126.80,125.86, 125.60,122.74,122.51,120.14,115.88,111.26(d,J＝7.3Hz),110.78,96.22,60.66,57.97, 53.27,50.67,28.12,26.84,21.78,19.12.
test example 1
Absorption spectrum tests were carried out on the compounds of examples 1 to 4 using UV-vis-NIR absorption spectrum tests in solvents of toluene (tolumen), trichloroethylene (trichloroethylene), chloroform (chloroform), methylene chloride (dichloromethane), cyclohexanone (cyclohexoxanone), acetone (acetone), acetonitrile (acetonitrile); the test was carried out at room temperature using a 1cm quartz cuvette. Wherein the extinction coefficient (ε) of the material is determined using the formula: a = ∈ cb, where a is the absorbance of the maximum absorption peak; c is the mass concentration of the material; b is the thickness of the cuvette used. FIGS. 34 to 37 are graphs showing the results of Extinction Coefficient (Extinction Coefficient) measurement. As can be seen from FIGS. 34-37, the material shows Strong near infrared Absorption and lyotropic discoloration results (Strong vis-NIR absorbance and Solvatochromism).
Test example 2
The compound ZJL-8 of example 2 was subjected to a prism coupled waveguide refractive index test, wherein the incident wavelength was 1304nm.
Test methods reference Wang, w.; wu, j.; chen, k.; huang, q.; luo, j.; chiang, K.S., graphene electronics for electronic polarity of electronic-Optical polymer files, 2020, 45,2383-2386.Kuzyk, M.G.and C.W.Dirk, characterization Techniques and protocols for Organic Nonlinear materials 1998 Markel Dekker.
Mixing chromophore compound with polymer polycarbonate according to a certain proportion (chromophore compound accounts for 20-30 wt%), adding dibromomethane, fully dissolving and uniformly mixing, and spin-coating on ITO glass. And processing and testing after vacuum drying. And testing the thickness of the film by using a step meter. Gold was plated as the positive electrode and ITO as the negative electrode, and an electric field (100V/. Mu.m) was applied. Raising the temperature, when the temperature is raised to a glass transition temperature range of 125-135 ℃, the leakage current is obviously increased, which indicates that the polarization is successful, and cooling. The prism coupling used was a commercially available prism coupling tester, model 2010/M, manufactured by Metricon corporation, USA.
The test results are shown in fig. 38 and tables 1 and 2. FIG. 38 shows that the ratio of chromophore contained in the polarizing film of ZJL-8 is 25%, which corresponds to a number density N of 2.16X 10 in the polymer 20 cm -1 And at the wavelength of 1304nm laser, the reflection intensity test results of TE and TM waves in the unpolarized film and the polarized film respectively are shown. As can be seen from fig. 38: after polarization, the TE and TM refractive indexes of the polarized film are changed, and the TM after polarization is obviously larger than the TE. Table 1 shows the refractive index test results of the prism coupled waveguide of the compound ZJL-8 polarized film at 1304nm. Under the condition of applying a certain voltage, the refractive index of the compound is obviously changed, which indicates that the compound ZJL-8 of the example 2 has good electro-optic effect.
The compounds of examples 1-4 exhibited similar electro-optic effects as shown in table 2 below.
TABLE 1 test result of prism coupling waveguide refractive index at 1304nm for ZJL-8 polarized film of compound
TABLE 2 maximum absorption wavelength λ of different chromophore compounds max (film blended with polymer), the electro-optic coefficient (r) 33 ) Sequence parameter (. PHI.) and hyperpolarizability (. Beta.) μ )
The chromophore compound provided by the invention shows a large linear electro-optic coefficient (r) at 1304nm 33 ) Number concentration of 2.16X 10 20 mL -1 In the case of the ZJL-8 polarized polymer film, the electro-optic coefficient is 74.9pm/V, which is more than two times of 30 pm/V of commercial inorganic electro-optic crystal lithium niobate.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. An optical chromophore compound, wherein the structural formula of the optical chromophore compound is shown as formula 1:
R 1 ＝R 2 -R 3 formula 1;
in the formula 1, R 1 The structure of (1) is shown as formula 2 or formula 3:
r in formula 2 or 3 4 、R 4 ' is independently selected from C1-12 alkyl or siloxy substituted C1-12 alkyl;
R 2 the structure of (D) is shown in formula 4:
R 3 the structure of (A) is shown in formula 5:
r in formula 5 5 、R 6 Independently selected from C1-C6 alkyl, halogen substituted C1-C6 alkyl or aryl.
2. The optical chromophore compound of claim 1, wherein R 4 、R 4 ' independently selected from n-butyl or-CH 2 CH 2 OSiPh 2 (t-C 4 H 9 )。
3. The optical chromophore compound of claim 1, wherein R 5 、R 6 Independently selected from trifluoromethyl or phenyl.
4. The optical chromophore compound of claim 1, wherein the structural formula of the optical chromophore compound is one of the following formulas:
5. a composite material comprising the optical chromophore compound of any one of claims 1-4;
preferably, the optical chromophore compound is present in an amount of 10% to 90% based on the total weight of the composite material.
6. The composite of claim 5, wherein the composite further comprises a polymer;
preferably, the polymer comprises one or a combination of two or more of polymethyl methacrylate, methyl methacrylate-styrene copolymer and polycarbonate.
7. The composite material of claim 6, wherein the composite material has an electro-optic coefficient r in the wavelength range of 1000nm-1600nm 33 Is 40pm/V to 90pm/V.
8. The composite material of claim 6, wherein the refractive index of the composite material changes by a value of 0.0005 to 0.005 under the influence of an electric field of 0V-40V/μm.
9. A film made from the composite material of any one of claims 5-8.
10. A photovoltaic integrated device having the thin film of claim 9;
preferably, the optoelectronic integrated device is an electro-optical device.
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