CN114195660B - Optical chromophore compound and composite material containing same - Google Patents

Optical chromophore compound and composite material containing same Download PDF

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CN114195660B
CN114195660B CN202010907845.4A CN202010907845A CN114195660B CN 114195660 B CN114195660 B CN 114195660B CN 202010907845 A CN202010907845 A CN 202010907845A CN 114195660 B CN114195660 B CN 114195660B
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compound
optical chromophore
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chromophore compound
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CN114195660A (en
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罗敬东
曾世荣
刘泰立
王文
兰柳元
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City University of Hong Kong CityU
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/42—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/03—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on ceramics or electro-optical crystals, e.g. exhibiting Pockels effect or Kerr effect
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Optical Modulation, Optical Deflection, Nonlinear Optics, Optical Demodulation, Optical Logic Elements (AREA)

Abstract

The invention discloses an optical chromophore compound and a composite material containing the same. The optical chromophore compound has a pi-electron donor group and the pi-electron donor group is electronically conjugated to the pi-electron acceptor group via a pi-electron bridge group. The invention also provides a composite material containing the optical chromophore compound. The optical chromophore provided by the invention realizes relatively large electro-optic effect and electro-absorption effect, and the performances of the materials are 10-20 times higher than those of silicon, and the materials are equivalent to semiconductor materials such as InP and GaAs.

Description

Optical chromophore compound and composite material containing same
Technical Field
The invention relates to the technical field of optical materials. And more particularly to an optical chromophore compound and composites containing the same.
Background
The existing optical chromophore compound is limited to the electro-optic effect of a single wavelength, has poor reliability in a simple reflection test, and has no broad spectrum electroabsorption effect test; the molecular design is complex, synthesis is lengthy, and chromophore stability is poor.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide an optical chromophore compound.
The invention also aims to provide a composite material containing the optical chromophore compound.
In order to achieve the above purpose, the invention adopts the following technical scheme: an optical chromophore compound, wherein the optical chromophore compound comprises a pi-electron donor group, and the pi-electron donor group is electronically conjugated to the pi-electron acceptor group via a pi-electron bridge group.
In the above optical chromophore compounds, preferably, the pi-electron donor group is provided by a Mie base, preferably an aromatic Mie base.
In the above optical chromophore compound, preferably, the pi-electron acceptor group is a heterocyclic ring containing a plurality of electron withdrawing groups; more preferably, the compound providing said pi-electron acceptor group is selected from: 1, 3-indenedione, 3- (dicyanomethylene) inden-1-one, tricyanoethylene, tricyanodihydrofuran.
In the above optical chromophore compounds, preferably, the pi-electron bridging group is a single or multiple carbon-carbon double bond.
According to a specific embodiment of the present invention, preferably, the optical chromophore compound has the following structure:
R1-R2-R3
wherein R1 is a pi-electron donor group provided by Mirabilite, preferably an aromatic Mirabilite; more preferably:
or->
R2 is a pi-electron bridging group, preferably an unsaturated alkyl chain or a carbon-carbon double bond; more preferably a single carbon-carbon double bond, =c-c=or=c-c=c-;
r3 is a pi-electron acceptor group; preferably a heterocyclic group containing a plurality of electron withdrawing groups; more preferably 1, 3-indenyldione, 3- (dicyanomethylene) inden-1-one, tricyanovinyl or tricyanobroma.
Wherein when R2 is a single carbon-carbon double bond, R3 is 1, 3-indenodionyl, 3- (dicyanomethylene) inden-1-onyl, tricyanovinyl or tricyanodihydrofuran.
According to a specific embodiment of the present invention, preferably, the optical chromophore compound has the following structure:
the R1 is as follows:
r2 is a single carbon-carbon double bond, =c-c=or=c-c=c-;
r3 is:
or alternatively, the process may be performed,wherein R is CH 3 -or CF 3 -。
According to a specific embodiment of the present invention, preferably, the optical chromophore compound may be a chromophore compound based on an aromatic Mirabilide base and a series of electron withdrawing groups, for example a compound having the structure:
the optical chromophore compound provided by the invention is a nonlinear optical chromophore, and can be used for preparing optical composite materials, optical films or electro-optical devices and the like.
The invention also provides a preparation method of the optical chromophore compound, which comprises the following steps:
wherein A isOr (F)>Wherein R is CH 3 -or CF 3 -。
The invention also provides a composite material comprising the optical chromophore compound. The optical chromophore compound is mixed with polymer to prepare composite material, and the composite material has the advantages of great nonlinear coefficient, high electric absorption effect, etc. and may be prepared into film with excellent optical quality.
According to a specific embodiment of the present invention, preferably, the nonlinear optical chromophore compound is present in an amount of from 10% to 90% by weight based on the total weight of the composite material.
According to a specific embodiment of the present invention, preferably, the composite material further comprises a polymer, and the content of the polymer may be controlled to be 10% -90%. More preferably, the polymer comprises one or a combination of two or more of polymethyl methacrylate, methyl methacrylate styrene copolymer and polycarbonate.
According to a specific embodiment of the invention, the composite material preferably has an electro-optic coefficient r33 in the wavelength range of 400-950nm of 10pm/V to 100pm/V.
According to a specific embodiment of the present invention, it is preferable that the refractive index of the composite material is changed by a certain electric field by a value of 0.00001 to 0.0001.
According to a specific embodiment of the present invention, preferably, the composite material has a light absorption coefficient of 1/cm to 30/cm in a wavelength range of 400-950 nm.
The electro-optic coefficient r33, the refractive index change value and the light absorption coefficient are all obtained by making a composite material into a film and then testing.
The invention also provides a film which is made of the composite material.
The invention also provides an electro-optical device, which is provided with the film.
The invention also provides an electroabsorption modulator which is provided with the film.
The optical chromophore provided by the invention realizes relatively large electro-optic effect and electro-absorption effect, and the performances of the materials are 10-20 times higher than those of silicon, and the materials are equivalent to semiconductor materials such as InP and GaAs.
Electro-optic or electro-absorption modulators are a type of device that modulates the intensity of a laser by a voltage. The high electro-optic and electro-absorption coefficient electro-optic materials currently available also require relatively good thermal stability to achieve modulator fabrication, assembly and end use. The nonlinear electro-optic modulator capable of balancing the driving voltage and the light absorption loss is designed and manufactured based on the waveguide of the electro-optic material, and can realize a relatively high modulation effect through a Pockel effect, an electro-absorption effect or a combination of the two effects, and has the advantages of relatively low optical loss and high-efficiency waveguide manufacture. These highly efficient electro-mechanical optical and electro-absorption materials provide a key technology for high electro-optical bandwidth and low cost, and can be used for hybrid integration with silicon photonics, plasma, conductive oxide, and dielectric photonics platforms. Therefore, the hybrid material method with high electro-optic coefficient/electric absorption coefficient can realize the remarkable energy saving, bandwidth increase, miniaturization and chip-level integration of the nano photon/nano electron system so as to fully exert the potential of the next generation information technology.
Drawings
FIG. 1 shows the H NMR result of compound 4 of example 1.
FIG. 2 shows the C NMR result of compound 4 of example 1.
FIG. 3 shows the H NMR result of compound 5 of example 1.
FIG. 4 shows the C NMR result of compound 5 of example 1.
FIG. 5 shows the H NMR result of compound 2MeOTPA-CNIDO of example 1.
FIG. 6 is the HRMS (ESI) m/z results for compound 2MeOTPA-CNIDO of example 1.
FIG. 7 shows the H NMR result of compound 2MeOTPA-TCF of example 2.
FIG. 8 is the C NMR result of compound 2MeOTPA-TCF of example 2.
FIG. 9 is the HRMS (ESI) m/z results for compound 2MeOTPA-TCF of example 2.
FIG. 10 shows the H NMR result of compound 2MeOTPA-CF3TCF of example 3.
FIG. 11 shows the C NMR result of compound 2MeOTPA-CF3TCF of example 3.
FIG. 12 is the HRMS (ESI) m/z results for compound 2MeOTPA-CF3TCF of example 3.
FIG. 13 is a graph showing the extinction coefficient results for Compound 2MeOTPA-CNIDO of example 1.
FIG. 14 is a graph showing the absorption coefficient of Compound 2MeOTPA-CNIDO of example 1.
Fig. 15 is a schematic diagram of a prism-coupled waveguide reflectivity test.
Fig. 16 is a graph of reflectivity results from a prism-coupled waveguide reflectivity test.
FIG. 17 is a graph showing the results of the waveguide reflection intensity test at voltages of 0V, 50V and 70V using TE mode waves having a wavelength of 830 nm.
FIG. 18 is a graph showing the results of reflection intensity test at 0V, 50V and 70V using a TM wave having a wavelength of 830 nm.
Fig. 19 is a graph of EA spectral absorbance results.
Fig. 20 is a plot of Δα versus electric field intensity obtained by fitting the absorbance of the device.
Fig. 21 is a plot of delta alpha versus electric field strength for a tube and silicon obtained by device absorbance fitting.
FIG. 22 is a graph showing the spectrum of refractive index changes due to the electroabsorption effect.
FIG. 23 is a graph showing the change spectrum of the absorption coefficient obtained by the conversion of FIG. 22.
FIG. 24 is a graph showing the results of the electroabsorption test of compound 2MeOTPA-TCF of example 2.
FIG. 25 is a graph showing the results of the electroabsorption test of compound 2MeOTPA-CNIDO of example 1.
FIG. 26 is a graph of the results of an electro-modulated absorbance spectrum test for compound 2MeOTPA-TCF of example 2.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
The synthetic routes for the optical chromophore compounds of examples 1-3 are as follows:
example 1
This example provides an optical chromophore compound 2MeOTPA-CNIDO, the structure of which is shown below:
the optical chromophore compound is prepared by the steps of:
step i, synthesis of Compound 3: reference "Efficient Hole Transporting Materials with Two or Four N, N-Di (4-methoxyphenyl) aminophenyl Arms on an Ethene Unit for Perovskite Solar cells" (Choi, hyeju, kwangseok Do, sojin Park, jong-Sung Yu, and Jaejung Ko; chemistry-A European Journal, no.45 (2015): 15949-15923).
Step ii, synthesis of Compound 4：
In a two-necked round bottom flask, compound 3 (1 g,1.7 mmol) was added to 20mL anhydrous THF inIn ice bath, in N 2 Slowly dropwise adding CH under atmosphere 3 Li (1.9 mL, 1.6M), then the mixture was stirred at room temperature for 3 hours, quenched with a few drops of water, the THF solvent was removed in vacuo, and the resulting yellow solid was extracted with 100mL of toluene, extracted with anhydrous Na 2 SO 4 Drying and filtering to obtain toluene solution of C; the toluene solution of C was transferred to a two-necked round bottom flask, B (16 mg,0.085 mmol) was added thereto, the mixture was further stirred at 70℃overnight, the crude product was extracted with ethyl acetate and brine, then with anhydrous Na 2 SO 4 Drying, removal of the solvent by rotary evaporation, left a yellow solid (0.9 g,90% yield) which was used directly in the next reaction without further purification.
The H NMR detection result of this compound 4 is as follows, and the specific spectrum is shown in fig. 1:
1 H NMR(400MHz,CDCl 3 )δ7.17(d,J＝8.2Hz,4H),7.07(d,J＝8.1Hz,8H),6.84(dd,J＝14.6,8.4Hz,12H),5.25(s,2H),3.79(s,12H).
the C NMR detection result of this compound 4 is as follows, and the specific spectrum is shown in FIG. 2:
13 C NMR(101MHz,CDCl 3 )δ155.83,149.18,148.26,140.92,133.64,128.90,126.62,119.86,114.67,110.85,55.51.
step iii, synthesis of Compound 5：
A (0.63 g,0.99 mmol) was added to a two-necked round bottom flask in 8mL DCM and 4mL anhydrous DMF in an ice bath in N 2 Slowly dropwise adding POCl under atmosphere 3 (0.14 mL,1.49 mmol) and after the mixture was heated at 50deg.C overnight, ice water (60 mL) and sodium acetate solution (aqueous solution) were poured into the mixture; after general work-up, the crude product was purified over silica gel using hexane/ethyl acetate (2:1, v/v) as eluent to give a red solid (0.52 g, 79%).
The H NMR detection result of this compound 5 is as follows, and the specific spectrum is shown in fig. 3:
1 H NMR(400MHz,CDCl 3 )δ9.50(d,J＝8.0Hz,1H),7.20(d,J＝7.9Hz,2H),7.10(d,J＝3.6Hz,10H),6.84(dd,J＝18.5,8.1Hz,12H),6.43(d,J＝7.8Hz,1H),3.80(s,12H).
the C NMR detection result of this compound 5 is as follows, and the specific spectrum is shown in FIG. 4:
13 C NMR(101MHz,CDCl 3 )δ193.86,162.77,156.71,156.47,150.99,150.06,140.06,139.65,132.16,130.48,130.17,127.95,127.55,127.32,123.93,118.14,117.96,114.89,114.87,55.51.
step iv, synthesis of 2MeOTPA-CNIDO：
In a two-necked round bottom flask, compound 5 (300 mg,0.45 mmol), compound 1' (106 mg,0.55 mmol) and 3mL N-methylmorpholine were mixed in 40mL CHCl 3 And a catalytic amount of pyridine (pyridine); the mixture was stirred and heated at 70 ℃ under nitrogen for 24h; the crude product was extracted with ethyl acetate and brine, then purified by silica gel chromatography (hexane/ethyl acetate, 2:1) to give a green solid (80%, 303 mg).
The H NMR detection result of the compound 2MeOTPA-CNIDO is as follows, and the specific spectrum is shown in figure 5:
1 H NMR(400MHz,CDCl 3 )δ8.63(t,J＝11.2Hz,2H),8.46(d,J＝12.0Hz,1H),7.83(d,J＝5.8Hz,1H),7.67(s,2H),7.38(d,J＝8.4Hz,2H),7.21–7.08(m,10H),6.96(d,J＝8.1Hz,2H),6.86(dd,J＝19.1,8.1Hz,10H),3.82(s,12H).
the compound 2MeOTPA-CNIDO (C 55 H 42 N 4 O 5 + (M) + ) HRMS (ESI) m/z calculated for 838.31497 and found 838.31433. The specific results are shown in FIG. 6.
The compound 2MeOTPA-CNIDO has HOMO (Highest Occupied Molecular Orbital ) = -5.07eV, lumo (Lowest Unoccupied Molecular Orbital, lowest occupied molecular orbital) = -3.71eV.
Example 2
This example provides an optical chromophore compound 2MeOTPA-TCF having the structure shown below:
the optical chromophore compound 2MeOTPA-TCF was prepared by the following steps:
in a two-necked round bottom flask, compound 5 (0.2 g,0.3 mmol) and compound 2' (0.072 g,0.36 mmol) were added to 1.5 ml of DCM and 6 ml of absolute ethanol; the mixture was stirred and heated at 80 ℃ for 24 hours under nitrogen blanket; the crude product was collected by filtration through a porous filter and then purified by silica gel chromatography (hexane/ethyl acetate, 2:1) to give a green solid (81%, 206 mg). Wherein the synthesis of compound 5 is referred to in example 1.
The H NMR detection result of the compound 2MeOTPA-TCF is as follows, and the specific spectrogram is shown in FIG. 7:
1 H NMR(400MHz,CDCl 3 )δ7.67-7.58(m,1H),7.25(s,1H),7.23(s,1H),7.15-7.08(m,8H),7.05-7.00(m,2H),6.93(d,J＝8.8Hz,2H),6.91-6.85(m,8H),6.81(dd,J＝10.4,4.7Hz,3H),6.41(d,J＝15.1Hz,1H),3.81(s,12H),1.58(s,6H).
the C NMR detection result of the compound 2MeOTPA-TCF is as follows, and the specific spectrum is shown in FIG. 8:
13 C NMR(101MHz,CDCl 3 )δ176.26,173.65,159.89,157.03,156.67,151.32,150.69,148.95,139.79,139.21,132.22,130.92,130.76,128.93,127.71,127.32,123.33,118.58,117.79,115.20,114.97,114.90,112.83,111.88,96.56,55.55,55.53,26.50.
the compound 2MeOTPA-TCF (C 54 H 45 N 5 O 5 + (M) + ) HRMS (ESI) m/z calculated for 843.34152 and found 843.34155. The specific results are shown in FIG. 9.
The compound 2MeOTPA-TCF has HOMO= -5.16eV, LUMO= -3.82eV.
Example 3
This example provides an optical chromophore compound 2MeOTPA-CF3TCF having the structure shown below:
the optical chromophore compound 2MeOTPA-CF3TCF was prepared by the following steps:
in a two-necked round bottom flask, compound 5 (0.186 g,0.28 mmol) and compound 3' (0.075 g,0.30 mmol) were added to 4mL anhydrous ethanol; the mixture was stirred and heated at 80 ℃ for 24 hours under nitrogen blanket; the crude product was collected by filtration through a porous filter and then purified by silica gel chromatography (hexane/ethyl acetate, 3:1) to give a green solid (83%, 210 mg). Wherein the synthesis of compound 5 is referred to in example 1.
The H NMR detection result of the compound 2MeOTPA-CF3TCF is as follows, and the specific spectrogram is shown in FIG. 10:
1 H NMR(400MHz,CDCl 3 )δ8.11(s,1H),7.30(s,1H),7.28(s,1H),7.16-7.11(m,8H),7.06(d,J＝8.7Hz,2H),6.94(d,J＝8.7Hz,2H),6.88(dd,J＝8.9,1.8Hz,8H),6.86-6.78(m,3H),6.31(d,J＝14.6Hz,1H),3.81(d,J＝2.3Hz,12H),1.78(s,3H).
the C NMR detection result of the compound 2MeOTPA-CF3TCF is as follows, and the specific spectrogram is shown in FIG. 11:
13 C NMR(101MHz,CDCl 3 )δ163.51,157.29,156.84,151.63,139.52,138.84,132.92,131.95,130.60,127.84,127.52,124.37,118.63,117.54,115.03,114.91,55.54,19.31.
the compound 2MeOTPA-CF3TCF (C 54 H 42 F 3 N 5 O 5 + (M) + ) HRMS (ESI) m/z calculated for 897.31326 and found 897.31311. The concrete results are shown in the figureShown at 12.
The compound 2MeOTPA-TCF has homo= -4.98eV and lumo= -3.83eV.
Example 4
This example provides an optical chromophore compound 2MeOTPA-IDO having the structure shown below:
the optical chromophore compound 2MeOTPA-IDO is prepared by the method of reference example 1 by taking 1, 3-indendione as a raw material.
The optical chromophore compound 2MeOTPA-IDO had = -5.01eV, lumo = -3.56eV.
Example 5
This example provides an optical chromophore compound 2MeOTPA-TCN having the structure shown below:
the optical chromophore compound 2MeOTPA-TCN is prepared by the method of reference example 1 by taking tricyanoethylene as a raw material.
The optical chromophore compound 2MeOTPA-TCN has HOMO= -5.14eV, LUMO= -3.79eV.
Test example 1
Absorption Spectrometry test for Compound 2MeOTPA-CNIDO of example 1 the Compound of example 1 was diluted to a concentration of 1X 10 using an infrared visible absorption Spectrometry test -4 M is a solution of dioxane (1, 4-dioxane), chloroform (chloroform), dichloromethane (dichlorometane), acetone (acetone), acetonitrile (acetonic), and dimethyl sulfoxide (DMSO), respectively; the test was performed using a 1cm glass cuvette at room temperature. Wherein the extinction coefficient (ε) of the material is defined by the formula: a=epsilon cb, a being the absorbance of the maximum absorption peak; c is the mass concentration of the material; b is the thickness of the cuvette used. FIG. 13 is a graph of extinction coefficient (Exctinction Coefficient) results (wherein, alongThe line A-A is chloroform, methylene dichloride, dimethyl sulfoxide, acetonitrile, acetone and dioxane in sequence from top to bottom, and FIG. 14 is a graph showing the absorption coefficient. As can be seen from fig. 13 and 14, the material shows Strong near infrared absorption and solvent discoloration results (Strong vis-NIR Absorption and Solvatochromism).
Test example 2
The compound 2MeOTPA-TCF of example 2 was subjected to prism-coupled waveguide reflectivity test, specifically in the manner shown in fig. 15, with incident wavelengths of 0.5 μm, 1.0 μm, 1.5 μm.
The test results are shown in fig. 15, 16, 17 and 18. Fig. 15 is a schematic diagram of a test method, fig. 16 is a reflectance (reflectance) result diagram, fig. 17 is a graph of a waveguide reflection intensity test result at voltages of 0V, 50V, and 70V using TE mode waves having a wavelength of 830nm, and fig. 18 is a graph of a reflection intensity test result at voltages of 0V, 50V, and 70V using TM waves having a wavelength of 830nm, respectively. As can be seen from fig. 16, the refractive index and thickness of the thin film material can be measured by waveguide coupling in both the SPR mode (surface plasmon resonance mode) and the PWR mode (core mode).
As can be seen from fig. 17 and 18: under the condition of applying a certain voltage, the refractive index of the compound is greatly reduced, which indicates that the compound 2MeOTPA-TCF of the example 2 has good electro-optic effect; the magnitude of the change at refractive indices of 1.58, 1.56, 1.535, etc. is large.
Test example 3
EA spectroscopic testing of compound 2MeOTPA-TCF of example 2 was performed in the manner described in Ageneralized Stark effect electromodulation model for extracting excitonic properties in organic semiconductors (Liu, taili, YISHU Foo, juan Antonio Zapien, menglin Li, and Sai-Wing Tsang; nature communications, no.1 (2019): 1-11).
The test results are shown in fig. 19 and 20. FIG. 19 is a graph showing the results of the absorption rate of the EA spectrum (wherein the curves In the In-Phase (In Phase) state are 6Vpp, 5Vpp, 4Vpp, 3Vpp, 2Vpp, and the curves In the quadrature (Out of Phase) state are all around the line A-A from top to bottom)Δt/t=0.0 vicinity), fig. 20 is a graph of Δα versus electric field intensity obtained by fitting device absorbance, fig. 21 is a graph of Δα versus electric field intensity of tube and silicon obtained by fitting device absorbance, wherein in fig. 20, voltage is divided by film thickness, converted into electric field intensity, for example, 2Vpp/549 nm=1.82×10 4 V/cm. As can be seen from fig. 19, 20, with reference to fig. 21: the EA effect in 2MeOTPA-TCF/PMMA-PS is 10 times stronger than that of the band-like edge, and 20 times higher in the strongly absorbing region (about 1.75 eV); no red or blue shift in the EA spectrum was observed.
Test example 4
ER effect test was performed on the compound 2MeOTPA-TCF of example 2, and the test results are shown in FIG. 22 and FIG. 23. Fig. 22 is a graph of the variation spectrum of refractive index due to the electro-absorption effect (wherein the curves are 2Vpp, 3Vpp, 4Vpp, 5Vpp, 6Vpp in order from top to bottom along the line A-A), and fig. 23 is a graph of the variation spectrum of absorption coefficient measured by the conversion of fig. 22. The ER effect in 2MeOTPA-TCF/PMMA-PS is approximately 5 times higher at the 800nm band edge and 20 times higher at the 675nm strong absorption range compared to the silicon of FIG. 23.
The results of all electroabsorption tests in the present invention can be calculated by the variation of the real (real) and imaginary (im) refractive index of the following organic nonlinear optical materials (for specific reference, heldmann, C., brombacher, L., neher, D.and Graf, M.,1995.Dispersion of the electro-optical response in poled polymer Films determined by Stark spectrum. Thin Solid Films,261 (1-2), pp.241-247). Wherein, the liquid crystal display device comprises a liquid crystal display device,
fig. 24 is a graph showing the results of the electroabsorption test of compound 2MeOTPA-TCF of example 2, and fig. 25 is a graph showing the results of the electroabsorption test of compound 2MeOTPA-CNIDO of example 1, converted into a graph of the real and imaginary parts of the nonlinear coefficient. As can be seen from fig. 24 and 25: the NLO coefficient at non-resonant wavelengths is consistent with PWR EO measurements made by prism coupling techniques.
The electro-modulated (EM) absorption spectrum test for all the film embodiments of the present invention was specifically performed as follows:
an EM spectrum test system built by self is adopted to test the EM signal of the sample;
for reflection mode EM testing, a monochromatic beam is incident at an angle of incidence of about 7 ° from the ITO side of the sample; for transmission mode EM testing, monochromatic light is incident at an angle perpendicular to the sample surface. In the EM test in reflection mode, the sample is packaged in a glove box filled with nitrogen; in the transmission mode EM test, the sample is placed in a small vacuum chamber for testing. A small 1kHz sinusoidal voltage is applied to the positive and negative electrodes of the sample by a function generator (Stanford Research Systems, DS 360), the voltage corresponding to an electric field strength of 10 4 -10 5 In the V/cm range to ensure that the EM signal is subject to the second order Stark effect.
Silicon and germanium photodetectors (Thorlabs) are used to detect the intensity of light passing through the device under test and the ac signal in the intensity of light after a sinusoidal voltage is applied. The photodetector is linked to a current amplifier (Stanford Research Systems, SR 570) and a lock-in amplifier (Stanford Research Systems, SR 830) whose probing frequency is a sinusoidal modulated signal frequency of a function generator under test.
Wherein:
FIG. 26 is a graph of the results of an electro-modulated (EM) absorption spectrum test of compound 2MeOTPA-TCF of example 2. As can be seen from fig. 26: the absence of dc offset dependence means Δp=0 and Δu z Small, and therefore, deltau can be ignored z 2 . This shows that the compound has good thermal stability, large nonlinear coefficient, excellent electric absorption effect and good compatibility with polymer.
It should be understood that the foregoing examples of the present invention are provided for the purpose of illustration only and are not intended to limit the embodiments of the present invention, and that various other changes and modifications can be made by those skilled in the art based on the foregoing description, and it is not intended to be exhaustive of all the embodiments, and all obvious changes and modifications that come within the scope of the invention are defined by the following claims.

Claims (18)

1. An optical chromophore compound, wherein the optical chromophore compound comprises a pi-electron donor group, and the pi-electron donor group is electronically conjugated to the pi-electron acceptor group via a pi-electron bridge group;
the optical chromophore compound has the following structure:
R1-R2-R3
wherein, R1 is:
r2 is a single carbon-carbon double bond, =c-c=or=c-c=c-;
r3 is:
or alternatively, the process may be performed,wherein R is CH 3 -or CF 3 -。
2. The optical chromophore compound of claim 1, wherein the optical chromophore compound has the structure:
3. a composite material comprising the optical chromophore compound of claim 1 or 2.
4. A composite material according to claim 3, wherein the optical chromophore compound is present in an amount of 10% to 90% by total weight of the composite material.
5. A composite according to claim 3, wherein the composite further comprises a polymer.
6. The composite of claim 5, wherein the polymer comprises one or a combination of two or more of polymethyl methacrylate, methyl methacrylate styrene copolymer, and polycarbonate.
7. The composite of claim 4, wherein the composite further comprises a polymer.
8. The composite of claim 7, wherein the polymer comprises one or a combination of two or more of polymethyl methacrylate, methyl methacrylate styrene copolymer, and polycarbonate.
9. The composite material according to any one of claims 4-8, wherein the composite material has an electro-optic coefficient r33 of 10pm/V to 100pm/V in the wavelength range of 400-950 nm.
10. The composite material according to any one of claims 4-8, wherein the refractive index of the composite material changes by a certain electric field by a value of 0.00001 to 0.0001.
11. The composite of claim 9, wherein the refractive index of the composite changes by a value of 0.00001 to 0.0001 under the influence of an electric field.
12. The composite material according to any one of claims 4-8, wherein the composite material has a light absorption coefficient of 1/cm to 30/cm in the wavelength range of 400-950 nm.
13. The composite of claim 9, wherein the composite has a light absorption coefficient of 1/cm to 30/cm in the wavelength range of 400-950 nm.
14. The composite of claim 10, wherein the composite has a light absorption coefficient of 1/cm to 30/cm in the wavelength range of 400-950 nm.
15. The composite of claim 11, wherein the composite has a light absorption coefficient of 1/cm to 30/cm in the wavelength range of 400-950 nm.
16. A film made from the composite of any one of claims 3-15.
17. An electro-optic device having the film of claim 16.
18. An electro-absorption modulator having the film of claim 16.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104558004A (en) * 2013-10-11 2015-04-29 中国科学院理化技术研究所 Organic second-order nonlinear optical chromophore with D-pi-A structure and its synthesis method and use
CN106905169A (en) * 2017-01-13 2017-06-30 中山大学 A kind of vinyl conjugation tri-arylamine group charge transport materials and preparation method thereof
JP2018186188A (en) * 2017-04-26 2018-11-22 三菱製紙株式会社 All-solid-state power generation element
CN110624509A (en) * 2018-06-25 2019-12-31 香港城市大学深圳研究院 Preparation method of porous composite material based on graphene oxide and chitosan
CN110776434A (en) * 2019-09-29 2020-02-11 中山大学 Hole transport material based on tetraaryl butadiene and preparation method and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7019453B2 (en) * 2000-08-17 2006-03-28 Lumera Corporation Polymers having pendant nonlinear optical chromophores and electro-optic devices therefrom

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104558004A (en) * 2013-10-11 2015-04-29 中国科学院理化技术研究所 Organic second-order nonlinear optical chromophore with D-pi-A structure and its synthesis method and use
CN106905169A (en) * 2017-01-13 2017-06-30 中山大学 A kind of vinyl conjugation tri-arylamine group charge transport materials and preparation method thereof
JP2018186188A (en) * 2017-04-26 2018-11-22 三菱製紙株式会社 All-solid-state power generation element
CN110624509A (en) * 2018-06-25 2019-12-31 香港城市大学深圳研究院 Preparation method of porous composite material based on graphene oxide and chitosan
CN110776434A (en) * 2019-09-29 2020-02-11 中山大学 Hole transport material based on tetraaryl butadiene and preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Can hydrogen bonds improve the hole-mobility in amorphous organic semiconductors? Experimental and theoretical insights;Mimaite, Viktorija，等;《Journal of Materials Chemistry C: Materials for Optical and Electronic Devices》;第3卷(第44期);第11660-11674页 *
Optical and electrical properties of triphenylamine derivatives for dye-sensitized solar cells and designing of novel molecule;Chen, Jun，等;《Chemical Research in Chinese Universities 》;第29卷(第3期);第584-588页 *
Photochemical Synthesis of Nonplanar Small Molecules with Ultrafast Nonradiative Decay for Highly Efficient Phototheranostics;Li, Xiaozhen，等;《Advanced Materials》;第33卷(第38期);第1-10页 *

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