CN115141193A - 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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- CN115141193A CN115141193A CN202110345549.4A CN202110345549A CN115141193A CN 115141193 A CN115141193 A CN 115141193A CN 202110345549 A CN202110345549 A CN 202110345549A CN 115141193 A CN115141193 A CN 115141193A
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- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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- 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
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- C07D405/08—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing alicyclic rings
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Abstract
The invention discloses an optical chromophore compound, a composite material containing the same, a film and a photoelectric integratorAnd (3) a component. The optical chromophore compound takes a Fischer base or a Michelle base compound as a pi-electron donor, tricyanofuran (TCF) and derivatives thereof as pi-electron acceptors, and the donors are connected with the acceptors through conjugate bridges with different side chain modifications. Compared with the chromophore compound without modification, the order parameter (phi) of the chromophore compound is increased from almost zero to more than 0.1, and the hyperpolarizability (beta) and the electro-optic coefficient (r) of the chromophore compound are increased 33 ) The maximum increase is more than 3 times. At 1304nm, a large linear electro-optic coefficient (r) is shown 33 ) Number concentration of 1.3X 10 20 mL ‑1 In the case of M2-SO2Ph, the electro-optic coefficient is 73.3pm/V, which is more than two times of 30pm// V of the 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, ultrafast response time, small dielectric constant and the like, can manufacture a complex photoelectric integrated device by processes of spin coating, photoetching or coining and the like, and can be produced in a large scale. However, chromophore compounds are often limited to low electrooptical coefficients, and how to simply and efficiently modify the chromophore compounds has great significance for the development of electrooptical 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 represented by formula 1:
R 1 ＝R 2 -R 3 formula 1;
in the formula 1, R 1 Is a pi-electron donor group which is a fischer base, a michael base or an aromatic michael base compound; the structure is as shown in formula 2 or formula 3The following steps:
r in formula 2 or 3 4 Selected from C1-12 alkyl;
R 2 is a conjugate bridge selected from cyclopentene and derivatives thereof or cyclohexene and derivatives thereof, and has a structure represented by formula 4 or formula 5:
r in formula 4 or 5 5 Selected from C1-12 alkyl; r is 6 Selected from thioethers or a sulfoxide group;
R 3 is a pi-electron acceptor group, is Tricyanofuran (TCF) and derivatives thereof, and has a structure shown in formula 6:
r in formula 6 7 、R 8 Independently selected from C1-C6 alkyl or halogen substituted C1-C6 alkyl.
The optical chromophore compounds according to the invention, preferably R 6 Selected from aromatic thioether or aromatic sulfoxide groups, more particularly, R 6 A substituent selected from the group consisting of:
In the optical chromophore compound provided by the invention, a pi-electron donor group is conjugated and connected with a pi-electron acceptor group through a conjugate bridge modified by different groups, and R 6 The substituent modifies the cyclopentene or cyclohexene conjugate bridge. By structural modification, steric hindrance, alternate bond length andgiving the push-pull strength to the receptor. Mercapto group and sodium benzene sulfinate are easy to generate substitution reaction with Cl atom under alkalescent condition, and the reaction yield is high. The rigid structure of the conjugated bridge of cyclopentene and cyclohexene leads to the generation of chromophore with large steric hindrance and chemical stability, and R with multiple electronegative atoms 6 The substituent has stronger electron-withdrawing ability compared with Cl atom, thereby influencing the D-pi-A main chain electron cloud distribution.
The optical chromophore compounds according to the invention, when conjugated to a bridge R 2 When cyclohexene is used, the structure is shown as formula 4, preferably, R in formula 4 5 Is selected from C1-6 alkyl; for example, in particular embodiments of the present invention, R 5 May be a tert-butyl group. Chromophores need to be formed into films and then further applied in electro-optic waveguide processing. The main chain structure is an aromatic conjugated structure, the rigidity is high, the solubility is poor, the solubility of the chromophore can be obviously improved by alkyl groups such as tertiary butyl and the like, the processing of a solvent is easy, and the optical quality of a film is improved.
According to the optical chromophore compounds of the present invention, the pi-electron donor group is a fischer base, a michael base or an aromatic michael base compound, preferably a fischer base or a michael base compound; the structure is shown as formula 2 or formula 3, preferably, R 4 Selected from C2-8 alkyl; for example, R 4 Can be ethyl, -CH 2 CH(C 2 H 5 )C 4 H 9 And so on. In a particular embodiment of the invention, R 4 May be ethyl or-CH 2 CH(C 2 H 5 )C 4 H 9 。
According to the optical chromophore compound of the present invention, the pi-electron acceptor group is Tricyanofuran (TCF) and its derivatives, the structure of which is shown in formula 6, preferably, R 7 、R 8 Are all methyl.
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:
wherein R is 4 、R 5 、R 6 、R 7 And R 8 As defined hereinbefore.
Compounds F3 and M2 by reaction with R 6 The corresponding raw materials react to modify the conjugate bridge, and the optical chromophore compound is obtained.
Synthetic references Zhang, d., zou, j., wang, w.et al. Systematic study of the structure-property correlation of a series of near-involved absorbing push-pull-peptide chromophores for electro-optics, sci. China chem. (2020).
Synthetic references to compound M2 are Luo J, lin F, li M, et al, new push-pull polyethylene phosphorescens condensation a Michler's base donor and a tricarbon acquisition: multicomponent condensation, allopolar isomerous and large optical NONLINEARITY [ J ]. Journal of Materials Chemistry C,2017,5 (9): 2230-2234.
In a second aspect, the 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, easiness in 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 80pm/V; more preferably 46pm/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 10-40V/. Mu.m.
The composite material according to the present invention preferably has an optical absorption coefficient of 5000 to 30000/cm in the wavelength range of 400nm to 1300 nm.
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 integrated device is an electro-optical device. The optical chromophore provided by the invention realizes a relatively large electro-optic effect.
Electro-optic 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, the structure of the conjugate bridge of the chromophore compound is modified, so that the solubility, the processability and the stability of the material are obviously improved, and the electro-optic coefficient is obviously increased. The method is 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 scheme showing the preparation of the compound F3-SNS of example 1 1 H NMR results.
FIG. 2 is a scheme showing the preparation of the compound F3-SNS of example 1 13 C NMR results.
FIG. 3 shows HRMS (ESI) m/z results for compound F3-SNS of example 1.
FIG. 4 is a scheme showing the preparation of compound F3-ONS of example 2 1 H NMR results.
FIG. 5 is a diagram of the compound F3-ONS of example 2 13 C NMR results.
FIG. 6 is the HRMS (ESI) m/z results for compound F3-ONS of example 2.
FIG. 7 shows the compound F3-SO2Ph of example 3 1 H NMR results.
FIG. 8 is a representation of the compound F3-SO2Ph of example 3 13 C NMR results.
FIG. 9 is the HRMS (ESI) m/z results for the compound F3-SO2Ph of example 3.
FIG. 10 shows the preparation of the compound M2-SNS of example 4 1 H NMR results.
FIG. 11 is a drawing of the compound M2-ONS of example 5 1 H NMR results.
FIG. 12 is a drawing of the compound M2-ONS of example 5 13 C NMR results.
FIG. 13 shows the reaction scheme for the compound M2-SO2Ph of example 6 1 H NMR results.
FIG. 14 is a photograph of compound M2-PhN S of example 7 1 H NMR results.
FIG. 15 is a drawing of compound M2-PhN S of example 7 13 C NMR results.
FIG. 16 is a cyclic voltammogram of the compounds of examples 1-7 in a tetra-n-butylammonium hexafluorophosphate/methylene chloride solution.
FIG. 17 is a molar extinction coefficient spectrum of the compound F3-SNS of example 1 in a solution.
FIG. 18 is a plot of the molar extinction coefficient spectrum of compound F3-ONS of example 2 in solution.
FIG. 19 is a plot of the molar extinction coefficient in solution for the compound F3-SO2Ph of example 3.
FIG. 20 is a molar extinction coefficient spectrum chart of the compound M2-SNS of example 4 in a solution.
FIG. 21 is a plot of the molar extinction coefficient spectrum in solution of the compound M2-ONS of example 5.
FIG. 22 is a plot of the molar extinction coefficient in solution for the compound M2-SO2Ph of example 6.
FIG. 23 is a plot of the molar extinction coefficient in solution for compound M2-PhN S of example 7.
FIG. 24 is a pure film absorption coefficient spectrum of the compounds of examples 1-7.
FIG. 25 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 the compound F3-SNS of example 1 with a polymer at a wavelength of 1304nm.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
All numerical designations herein (e.g., temperature, time, concentration, and weight, etc., including ranges for each) may generally be approximated as varied (+) or (-) in increments of 0.1 or 1.0, as appropriate. All numerical designations should be understood as preceded by the term "about".
The synthetic routes for the optical chromophore compounds of examples 1-7 are as follows:
wherein R is 6 Is composed of
Example 1
This example prepares an optical chromophore compound (compound F3-SNS) having the structure shown below:
the optical chromophore compound is prepared by the following steps:
step i, synthesis of F3：
Reference is made to the method described in Zhang, D.D., zou, J., wang, W.et al.systematic study of the structure-property correlation of a series of near-concerned adsorbed push-pull-push-peptide conjugates (2020). Https:// doi.org/10.1007/s 11426-020-9860-5.
Step ii, synthesis of Compound F3-SNS：
In a flask, compound F3 (0.18g, 0.27mmol), 2-mercaptobenzothiazole (89.7mg, 0.54mmol), triethylamine (54.3mg, 0.54mmol), acetonitrile 10mL, chloroform 5mL, and refluxed for 2 days. After the reaction was complete, silica gel was added, the solvent was evaporated to dryness, and the mixture was purified with DCM: EA (50% by volume.
The compound F3-SNS 1 The detection result of H NMR is as follows, and the specific spectrogram is shown in figure 1:
1 H NMR(300MHz,Chloroform-d)δ8.69(d,J＝13.0Hz,1H),8.39(d,J＝15.6Hz,1H),8.08(d,J＝7.4Hz,1H),7.95–7.88(m,1H),7.81(d,J＝8.1Hz,1H),7.74–7.60(m,2H),7.49–7.39(m,2H),7.39–7.30(m,2H),6.77(d,J＝7.1Hz,1H),6.68(d,J＝15.6Hz,1H),6.29(d,J＝13.0Hz,1H),3.86(d,J＝7.2Hz,2H),3.14(d,J＝14.8Hz,1H),2.94(d,J＝16.4Hz,1H),2.28(dt,J＝28.3,13.6Hz,2H),1.96(d,J＝5.7Hz,1H),1.68(d,J＝4.6Hz,7H),1.52–1.28(m,8H),1.13(s,9H),1.00(td,J＝7.3,5.7Hz,3H),0.91(td,J＝7.1,3.0Hz,3H).
the compound F3-SNS 13 The C NMR detection result is as follows, and the specific spectrogram is shown in figure 2:
13 C NMR(101MHz,CDCl 3 )δ175.69,173.33,166.84,153.35,148.49,144.88,143.42,143.39,139.05,135.78,134.92,134.85,130.94,130.52,129.32,128.93,127.71,126.56,126.23,125.03,124.25,122.14,121.09,118.59,113.78,112.73,112.02,110.97,104.07,103.33,97.03,96.72,54.91,47.55,42.34,42.30,39.25,39.17,32.53,31.36,31.03,29.22,29.07,28.40,27.83,27.39,26.98,26.94,24.53,24.36,23.13,23.07,14.08,11.20.
the compound F3-SNS (C) 50 H 52 N 5 OS 2 + (M+H) + ) HRMS (ESI) m/z of (A) calculated 802.36078, found 802.36041. The specific results are shown in FIG. 3.
Example 2
This example prepares an optical chromophore compound (compound F3-ONS) having the structure shown below:
the procedure is as in example 1, except that the starting material, 2-mercaptobenzothiazole, is replaced by 2-mercaptobenzoxazole.
In a flask, compound F3 (0.18g, 0.27mmol), 2-mercaptobenzoxazole (81.1mg, 0.54mmol), triethylamine (54.3mg, 0.54mmol), acetonitrile 10mL, chloroform 5mL was added, and the mixture was refluxed overnight. After the reaction was complete, silica gel was added, the solvent was evaporated to dryness, and the mixture was purified with DCM: EA (50% by volume.
Process for preparing the compound F3-ONS 1 The H NMR detection result is as follows, and the specific spectrogram is shown in figure 4:
1 H NMR(300MHz,Chloroform-d)δ8.61(d,J＝12.9Hz,1H),8.42(d,J＝15.6Hz,1H),8.14(d,J＝7.4Hz,1H),7.82(d,J＝8.1Hz,1H),7.71–7.57(m,2H),7.49–7.33(m,3H),7.30(s,1H),7.27(s,1H),6.77(d,J＝7.1Hz,1H),6.65(d,J＝15.5Hz,1H),6.28(d,J＝13.0Hz,1H),3.85(d,J＝7.3Hz,2H),3.12(d,J＝14.8Hz,1H),2.93(d,J＝16.0Hz,1H),2.30(dt,J＝27.6,13.4Hz,2H),1.96(d,J＝5.5Hz,1H),1.73(d,J＝3.9Hz,7H),1.40(dp,J＝23.6,8.1,6.5Hz,8H),1.11(s,9H),1.00(q,J＝7.2Hz,3H),0.91(td,J＝7.1,3.2Hz,3H).
preparation of the compound F3-ONS 13 The C NMR detection result is as follows, and the specific spectrogram is shown in figure 5:
13 C NMR(101MHz,CDCl 3 )δ175.73,173.28,161.11,151.88,148.17,145.10,143.53,143.50,141.72,140.53,139.29,135.41,134.84,131.03,130.58,129.21,128.93,127.55,126.32,125.04,124.80,124.04,119.39,118.37,113.72,112.70,111.95,110.98,110.25,103.79,103.36,96.99,96.66,55.03,47.55,42.23,39.22,39.14,32.53,31.37,31.03,29.21,29.07,28.49,27.88,27.37,26.92,26.90,24.53,24.34,23.12,23.05,14.05,11.20,11.17.
the compound F3-ONS (C) 50 H 52 N 5 O 2 S + (M+H) + ) HRMS (ESI) m/z of (D) calculated 786.38362, found 786.38330. The specific results are shown in FIG. 6.
Example 3
This example provides an optical chromophore compound (compound F3 — SO2 Ph) having the structure shown below:
the procedure is as in example 1, except that the starting material, 2-mercaptobenzothiazole, is replaced by sodium benzenesulfinate.
Of this compound F3-SO2Ph 1 The detection result of H NMR is as follows, and the specific spectrogram is shown in figure 7:
1 H NMR(400MHz,Chloroform-d)δ9.00(d,J＝15.7Hz,1H),8.66(d,J＝12.7Hz,1H),8.18(d,J＝7.4Hz,1H),7.90–7.81(m,3H),7.69(t,J＝7.7Hz,1H),7.60–7.53(m,1H),7.49(dd,J＝8.4,6.7Hz,2H),7.43(dd,J＝8.3,7.2Hz,1H),7.36(d,J＝8.3Hz,1H),6.83(d,J＝15.7Hz,1H),6.75(d,J＝7.2Hz,1H),6.10(d,J＝12.7Hz,1H),3.80(d,J＝7.4Hz,2H),2.95(td,J＝15.2,4.9Hz,2H),2.31–2.16(m,1H),2.05(td,J＝13.7,7.7Hz,1H),1.98–1.88(m,1H),1.83(s,3H),1.75(s,3H),1.55–1.23(m,9H),1.05(s,9H),0.97(q,J＝7.2Hz,3H),0.89(td,J＝7.2,3.6Hz,3H).
of this compound F3-SO2Ph 13 The C NMR detection result is as follows, and the specific spectrogram is shown in FIG. 8:
13 C NMR(101MHz,CDCl 3 )δ175.35,173.89,148.30,145.30,143.55,143.34,141.79,138.70,138.65,133.80,133.25,130.94,130.58,129.49,129.45,129.31,128.94,127.57,126.30,125.54,123.86,118.37,116.20,112.35,111.67,110.48,103.70,102.69,99.33,97.79,56.12,47.53,42.45,42.42,39.09,39.02,32.44,31.24,30.99,29.61,29.07,29.02,28.54,28.50,27.20,26.67,26.62,24.48,24.27,23.09,23.04,14.05,11.20,11.15.
this compound F3-SO2Ph (C) 49 H 53 N 4 O 3 S + (M+H) + ) HRMS (ESI) m/z of (A) calculated 777.38329, found 777.38287. The specific results are shown in FIG. 9.
Example 4
This example prepares an optical chromophore compound (compound M2-SNS), whose structure is shown below:
the optical chromophore compound is prepared by the following steps:
step i, synthesis of M2：
Reference is made to the method described in Luo J, lin F, li M, et al, new push-pull polyethylene phosphorescene conjugation a Michler's base donor and a tricyclic organic receptor, multicomponent condensation, allopolar isometrism and large optical informality [ J ]. Journal of Materials Chemistry C,2017,5 (9): 2230-2234.
Step ii, step iiiCompound M2-SNS formation：
The same preparation as that of the compound F3-SNS of example 1 was conducted, except that the compound F3 was replaced with a compound M2.
The compound M2-SNS 1 The detection result of H NMR is as follows, and the specific spectrogram is shown in figure 10:
1 H NMR(300MHz,Chloroform-d)δ7.93(d,J＝8.1Hz,1H),7.86–7.70(m,2H),7.55–7.43(m,1H),7.43–7.34(m,1H),7.23(dd,J＝15.2,10.5Hz,3H),6.93(d,J＝8.5Hz,2H),6.72–6.51(m,4H),6.24(d,J＝8.6Hz,2H),3.42(q,J＝7.0Hz,4H),3.30(q,J＝7.1Hz,4H),3.12(d,J＝7.4Hz,2H),3.03(d,J＝7.7Hz,2H),1.66(s,6H),1.18(dt,J＝17.5,7.0Hz,12H).
example 5
This example prepares an optical chromophore compound (compound M2-ONS) having the structure shown below:
the same preparation as that of the compound F3-ONS in example 2 was carried out, except that the compound F3 was replaced with a compound M2.
The method for preparing the compound M2-ONS 1 The H NMR detection result is as follows, and the specific spectrogram is shown in FIG. 11:
1 H NMR(300MHz,Chloroform-d)δ7.79(d,J＝15.6Hz,1H),7.73–7.66(m,1H),7.57–7.47(m,1H),7.44–7.32(m,2H),7.28–7.20(m,2H),7.10(d,J＝12.4Hz,1H),6.95–6.86(m,2H),6.63(dd,J＝10.6,6.3Hz,3H),6.53(d,J＝15.6Hz,1H),6.20–6.08(m,2H),3.42(q,J＝7.0Hz,4H),3.28(q,J＝7.0Hz,4H),3.09(dd,J＝31.7,5.6Hz,4H),1.69(s,6H),1.21(t,J＝7.0Hz,6H),1.14(t,J＝7.0Hz,6H).
of the compound M2-ONS 13 The C NMR detection result is as follows, and the specific spectrogram is shown in FIG. 12:
13 C NMR(101MHz,CDCl 3 )δ175.49,172.39,160.53,152.03,151.88,149.01,148.46,148.15,145.52,142.61,141.90,137.93,132.86,131.50,130.88,129.49,125.56,124.82,124.76,120.99,119.14,115.75,112.45,111.68,110.96,110.80,110.22,110.17,97.67,96.95,55.76,44.48,44.20,29.30,27.16,26.85,12.70.
example 6
This example prepares an optical chromophore compound (compound M2 — SO2 Ph) having the structure shown below:
the same preparation as for the compound F3-SO2Ph in example 3 was carried out, except that the compound F3 was replaced with the compound M2.
Of this compound M2-SO2Ph 1 The detection result of H NMR is as follows, and the specific spectrogram is shown in figure 13:
1 H NMR(300MHz,Chloroform-d)δ8.77(d,J＝15.9Hz,1H),7.70–7.53(m,3H),7.43(t,J＝7.7Hz,2H),7.31(d,J＝2.5Hz,1H),7.26(d,J＝8.6Hz,2H),7.10(d,J＝8.5Hz,2H),6.79(d,J＝8.5Hz,2H),6.74–6.49(m,4H),3.51(q,J＝7.0Hz,4H),3.41(q,J＝7.0Hz,4H),3.06–2.81(m,4H),1.87(s,6H),1.29(t,J＝6.9Hz,6H),1.20(t,J＝7.0Hz,6H).
example 7
This example prepared an optical chromophore compound (compound M2-PhN S) having the structure shown below:
the same preparation method as that of the compound F3-SNS in the example 1 is adopted, the compound M2 is adopted instead of the compound F3, and 5-mercapto-1-phenyl-tetrazole is adopted instead of 2-mercaptobenzothiazole.
Preparation of the Compound M2-PhN S 1 The detection result of H NMR is as follows, and the specific spectrogram is shown in figure 14:
1 H NMR(400MHz,Chloroform-d)δ7.95(d,J＝15.5Hz,1H),7.59–7.50(m,1H),7.47(dd,J＝8.6,6.7Hz,2H),7.34–7.18(m,4H),6.90(d,J＝8.6Hz,2H),6.76–6.51(m,6H),6.37(d,J＝15.5Hz,1H),3.42(q,J＝7.0Hz,4H),3.33(q,J＝7.0Hz,4H),3.06–2.96(m,2H),2.96–2.85(m,2H),1.71(s,6H),1.19(dt,J＝16.5,7.0Hz,12H).
preparation of the Compound M2-PhN S 13 The C NMR detection result is as follows, and the specific spectrogram is shown in FIG. 15:
13 C NMR(101MHz,CDCl 3 )δ175.66,172.16,152.48,151.38,149.41,148.54,148.20,144.39,141.94,138.01,133.09,132.65,131.18,130.78,130.65,129.71,129.09,125.73,124.99,120.57,115.63,112.42,111.61,111.13,110.99,110.45,97.06,96.95,55.95,44.51,44.13,29.22,26.89,26.66,12.70.
test example 1
Cyclic voltammetry tests were performed on the compounds of examples 1-7 using 0.1M tetra-n-butylammonium hexafluorophosphate/dichloromethane as the electrolyte, a platinum wire electrode as the working electrode, a platinum sheet electrode as the counter electrode, and Ag/AgCl as the reference electrode, and calibrated with ferrocene. FIG. 16 is a cyclic voltammogram of a chromophore compound. As can be seen from fig. 16, the material has reversible redox peaks, showing reversible redox processes.
Test example 2
The compounds of examples 1 to 7 were subjected to absorption spectroscopy, and UV-vis-NIR absorption spectroscopy was used to dilute the compounds of examples 1 to 7 to a concentration of 1X 10 -5 M in the solvent of dioxane (1,4-dioxane), chloroform (chloroform), dichloromethane (dichloromethane), acetone (acetone), acetonitrile (acetonitrile), methanol (methanol), dimethyl sulfoxide (DMSO); 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. 17 to 23 are graphs showing the results of Extinction Coefficient (Extinction Coefficient) measurement. The compound was dissolved in chloroform and spin coated on glass to form a thin film, referred to as a neat film. The thickness of the film was measured by a step meter, and the absorption coefficient was calculated by measuring the absorbance of the maximum absorption peak. The absorption coefficient is according to the formula: a = lgT = Kbc, a is the absorbance of the maximum absorption peak, T is the transmittance, K is the absorption coefficient, b is the thickness, c is the concentration. FIG. 24 is a graph of normalized absorption coefficient results for pure membranes. ByAs can be seen in FIGS. 17-23, the material shows Strong near infrared Absorption and lyotropic discoloration results (Strong vis-NIR absorbance and Solvatochromism).
Test example 3
The prism-coupled waveguide refractive index test was performed on the compound F3-SNS of example 1, wherein the incident wavelength was 1304nm.
Test methods reference Wang, w.; wu, j.; chen, k.; huang, q.; luo, j.; chiang, K.S., graphene electrodes for electro-polar polymers films, optics Letters,2020,45,2383-2386.Kuzyk, M.G.and C.W.Dirk, characterisation Techniques and tabs for Organic Nonlinear Optical materials, 1998, markel Dekker.
Mixing chromophore compound with polymer methyl methacrylate-styrene copolymer according to a certain proportion (chromophore compound accounts for 10-20 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 a positive electrode and ITO as a negative electrode, and an electric field (100V/. Mu.m) was applied. And (3) increasing the temperature, wherein after the temperature is increased to the glass transition temperature range of 108-113 ℃, the leakage current is obviously increased, which indicates that the polarization is successful, and cooling is carried out. 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. 25 and tables 1 and 2. FIG. 25 shows that the F3-SNS polarizing film contains 15.75% of chromophore, which corresponds to a number density N of 1.30X 10 in the polymer 20 cm -1 And at the wavelength of 1304nm laser, the TE and TM waves are respectively shown in the test result of the reflection intensity of the unpolarized film and the polarized film. As can be seen from fig. 25: 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 at 1304nm for the compound F3-SNS polarized film. Under the condition of applying a certain voltage, the refractive index of the compound is obviously changed, which shows that the compound F3-SNS of the example 1 has good electro-optic effect. The compounds of examples 2-7 exhibited similar electro-optic effects as shown in table 2 below.
TABLE 1 test results of prism-coupled waveguide refractive index at 1304nm for F3-SNS polarizing film of Compound
TABLE 2 number Density N of different chromophore compounds is 1.30X 10 20 cm -1 Maximum absorption wavelength λ of time max (film blended with polymer), electro-optic coefficient (r) 33 ) Sequence parameter (. PHI.) and hyperpolarizability (. Beta.) μ )
The electrooptical coefficients of compound F3 and compound M2 without conjugate bridge modification are described in the references Zhang, D., zou, J., wang, W.et al, systematic study of the structure-property correlation of a series of near-isolated adsorbed pure-pull peptide for electro-optical, sci.China chem.2021,64,263-273.
Compared with the chromophore compound without modification, the order parameter (phi) of the chromophore compound provided by the invention is increased to more than 0.1 from almost zero, and the hyperpolarizability (beta) and the electro-optic coefficient (r) are increased 33 ) The maximum increase is more than 3 times. At 1304nm, a large linear electro-optic coefficient (r) is shown 33 ) Number concentration of 1.3X 10 20 mL -1 In the case of M2-SO2Ph, the electro-optic coefficient is 73.3pm/V, which is more than two times of 30pm// V of the 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 Selected from C1-12 alkyl;
R 2 the structure of (A) is shown in formula 5 or formula 6:
r in the formulae 4 and 5 5 Selected from C1-12 alkyl; r 6 Selected from thioether or sulfoxide groups;
R 3 the structure of (D) is shown in formula 6:
r in formula 6 7 、R 8 Independently selected from C1-C6 alkyl or halogen substituted C1-C6 alkyl.
2. The optical chromophore compound of claim 1, wherein R 6 A substituent selected from the group consisting of:
3. the optical chromophore compound of claim 1, wherein R 4 Is ethyl or-CH 2 CH(C 2 H 5 )C 4 H 9 (ii) a Preferably, R 5 Is tert-butyl; preferably, R 7 、R 8 Are all methyl.
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 electro-optic coefficient r of the composite material is within the wavelength range of 1000nm-1600nm 33 Is 40pm/V to 80pm/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;
preferably, the optical absorption coefficient of the composite material is-5000 to 30000/cm in the wavelength range of 400nm to 1300 nm.
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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Non-Patent Citations (1)
| Title |
|---|
| DI ZHANG 等: "Systematic study of the structure-property relationship of a series of near-infrared absorbing push-pull heptamethine chromophores for electro-optics", SCIENCE CHINA-CHEMISTRY, vol. 64, no. 2, pages 263 - 273, XP037351322, DOI: 10.1007/s11426-020-9860-5 * |
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