Push-pull type heptamethine chromophore compounds containing silicon-asymmetric Michaelis base derivatives, composite materials, thin films and optoelectronic integrated devices

Abstract

This invention discloses a push-pull type silicon-containing asymmetric Michaelis base derivative heptamethrin chromophore compound, composite material, thin film, and optoelectronic integrated device. The chromophore compound uses a silicon-modified asymmetric Michaelis base derivative as the π-electron donor, six-membered rings modified with different groups as conjugated bridges, and a fluorophenylmethyl-substituted tricyanofuran (TCF) derivative as the π-electron acceptor. The chromophore doping concentration is increased by adjusting the asymmetry of the electron donor. When p-fluorobenzene-substituted tricyanofuran (FP-TCF) is used as the π-electron acceptor and the side chain is modified with diphenyloxazolyl thio, the electro-optic coefficient is the highest. At a working wavelength of 1304 nm, M3FPPhON exhibits the optimal electro-optic coefficient at a number concentration of 1.6 × 10⁻⁶. 20 mL ‑1 At that time, the electro-optic coefficient was 135.6 pm / V.

Description

Technical Field

[0001] This invention relates to the field of optical materials technology, specifically to a push-pull type heptamethrin chromophore compound containing silicon-containing asymmetric Michaelis base derivatives, and composite materials, thin films, and optoelectronic integrated devices containing it. Background Technology

[0002] Organic electro-optic materials possess advantages such as solution processing and easily tunable structure, making them crucial for modulating electrical signals. Traditional tetraene dipole molecules exhibit high electro-optic coefficients and high doping concentrations, but their complex synthesis, poor chemical and thermal stability hinders large-area thin-film fabrication and device stability. Heptamethrin chromophore molecules, on the other hand, offer advantages such as fewer synthesis steps and high chemical stability. When using a Michaelis base as a donor, they exhibit relatively good electro-optic performance, but the highest doping concentration is 1.3 × 10⁻⁶. 20 mL -1 Further increasing the number concentration leads to a decrease in the electro-optic coefficient due to the accumulation of dipole molecules. Therefore, heptamethrin chromophore molecules, which possess advantages such as high synthesis efficiency, good stability, and high number concentration, are of great significance for the development of electro-optic materials. They have broad potential for the large-area fabrication, assembly, and application of modulators, as well as for applications in next-generation information technologies. Summary of the Invention

[0003] To solve the above-mentioned technical problems, the first objective of this invention is to provide a push-pull type silicon-containing asymmetric Michaelis base derivative heptamethrin chromophore compound.

[0004] A second objective of the present invention is to provide a composite material containing the above-mentioned chromophore compound.

[0005] A third objective of the present invention is to provide a thin film made of the above-described composite material, and an optoelectronic integrated device having the thin film.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] This invention provides a push-pull type heptamethrin chromophore compound containing a silicon-containing asymmetric Michaelis base derivative, wherein the chromophore compound comprises a π-electron donor group, a conjugated bridging group, and a π-electron acceptor group; the general structural formula of the chromophore compound is shown in Formula 1:

[0008] R1-R2=R3 Equation 1;

[0009] In Formula 1, R1 is a π-electron donor group, the structure of which is shown in Formula 2:

[0010]

[0011] In Formula 2, R4, R5, and R6 are independently selected from C1-12 alkyl groups and silicon-containing groups.

[0012] R2 is a conjugate bridge, and its structure is shown in Equation 3:

[0013]

[0014] In Formula 3, R7 is selected from Cl atoms, Benzenesulfonyl and its derivatives, wherein X is O or S, R 11 R 12 Independently selected from phenyl, substituted phenyl, or R 11 and R 12 The fused group is an aromatic group. The substituted phenyl group includes, for example, common alkyl-substituted phenyl groups, halogen-substituted phenyl groups, etc.

[0015] R3 is a π-electron acceptor group selected from tricyanofuran (TCF) derivatives, and its structure is shown in Formula 4:

[0016]

[0017] In Formula 4, R8 and R9 are independently selected from methyl and fluorophenyl, and preferably, the fluorophenyl is p-fluorophenyl or trifluorophenyl.

[0018] According to the chromophore compounds of the present invention, Formula 4 is preferably composed of the following structure:

[0019]

[0020] As understood by those skilled in the art, in the above structural formula The chemical bonds involved are the connecting bonds between the various groups.

[0021] In the chromophore compounds provided by this invention, the π-electron donor group is conjugated with π-electron acceptor groups of different structures through cyclohexene groups modified with different side chains. By changing the asymmetry of the π-electron donor, the doping concentration is increased, thereby improving the nonlinear optical properties of the chromophore.

[0022] According to the chromophore compound of the present invention, the π-electron donor is an asymmetric Michaelis base derivative, the structure of which is shown in Formula 2. Preferably, R4 and R5 in Formula 2 are selected from C1-12 alkyl groups, and R6 is selected from the following silicon-containing group:

[0023] Among them, R 10 The alkyl group is selected from C1-12, and n is an integer from 1 to 5, preferably 2. After adding the silicon-containing group R6 in the above formula, the asymmetry of the π-electron donor is improved, the number concentration is increased, the solubility is improved, and it has stronger compatibility with polymers, which is beneficial for solution processing and improving electro-optic properties.

[0024] For example, in a specific embodiment of the present invention, R4 is butyl, R5 is ethyl, and R6 is 2-((tert-butyldiphenylsilyl)oxy)ethyl.

[0025] According to the chromophore compound of the present invention, the conjugated bridge is a cyclohexene derivative modified with different groups; its structure is shown in Formula 3. Preferably, R7 is selected from Cl atom, benzenesulfonyl group and its derivatives; for example, in a specific embodiment of the present invention, R7 can be Cl atom, (4,5-diphenyloxazol-2-yl)thio, (phenyloxazol-2-yl)thio, (phenylthiazol-2-yl)thio, or benzenesulfonyl group.

[0026]

[0027] R7 is Cl,

[0028] According to the chromophore compound of the present invention, the π-electron acceptor group is a tricyanofuran (TCF) derivative, and its structure is shown in Formula 4:

[0029]

[0030] According to the chromophore compounds of the present invention, preferably, Formula 4 is selected from the following structures:

[0031]

[0032] According to the chromophore compound of the present invention, preferably, the chromophore compound has one of the following structural formulas:

[0033]

[0034]

[0035] The chromophore compounds provided by this invention are nonlinear optical materials that can be used to prepare optical composite materials, optical thin films, and electro-optic devices.

[0036] This invention also provides a synthetic route for the above chromophore compounds:

[0037]

[0038] R4, R5, R6, R7, R8, and R9 are defined as above.

[0039] A second aspect of the present invention provides a composite material comprising the above-mentioned chromophore compound.

[0040] According to the composite material of the present invention, preferably, the chromophore compound accounts for 10%-40% of the total weight of the composite material.

[0041] The composite material according to the present invention preferably further comprises a polymer. The composite material prepared by mixing the chromophore compound of the present invention with the polymer has advantages such as easy processing into films and a large nonlinear coefficient.

[0042] According to the composite material of the present invention, preferably, the polymer includes one or more of polymethyl methacrylate, methyl methacrylate-styrene copolymer and polycarbonate, and more preferably, the present invention uses methyl methacrylate-styrene copolymer.

[0043] According to the composite material of the present invention, preferably, the electro-optic coefficient r of the composite material is within the wavelength range of 1000nm-1600nm. 33 The time ranges from 50 pm / V to 160 pm / V.

[0044] According to the present invention, the composite material preferably exhibits a refractive index change of 0.0005 to 0.02 within a wavelength range of 1000 nm to 1600 nm under an electric field of 0-40 V / μm.

[0045] According to the composite material of the present invention, preferably, the hyperpolarizability β of the composite material is... μ (4000-8000)×10 -30 esu.

[0046] The above electro-optic coefficient r 33 Hyperpolarizability β μ The changes in refractive index were obtained by making the composite material into a thin film and then testing it.

[0047] A third aspect of the present invention provides a thin film made of the above-described composite material.

[0048] The present invention also provides an optoelectronic integrated device having the aforementioned thin film. Preferably, the optoelectronic integrated device is an electro-optic device, specifically an electro-optic modulator. The chromophore provided by the present invention achieves a relatively large electro-optic effect.

[0049] Electro-optic modulators are devices that modulate laser intensity using voltage. Organic electro-optic materials play a crucial role in electro-optic signal modulation. Existing electro-optic materials suffer from problems such as low electro-optic coefficients, low thermal stability, and poor film quality. This invention utilizes silicon-containing asymmetric Michaelis base derivatives as donors, cyclohexene derivatives with different side chain modifications as conjugated bridges, and p-fluorobenzene TCF (FP-TCF) and trifluorobenzenemethyl TCF (F3P-TCF) as acceptors, resulting in significant improvements in the electro-optic properties, stability, and processability of the materials. This has broad potential for the large-area fabrication, assembly, and application of modulators, as well as for applications in next-generation information technologies.

[0050] The chromophore compound of this invention uses an asymmetric Michaelis base derivative modified with tert-butyldiphenylsiloxy as the π-electron donor, a six-membered ring modified with different groups as a conjugated bridge, and a fluorophenylmethyl-substituted tricyanofuran (TCF) derivative as the π-electron acceptor. The chromophore doping concentration is increased by adjusting the asymmetry of the electron donor. When p-fluorobenzene-substituted tricyanofuran (FP-TCF) is used as the π-electron acceptor and the side chain is modified with diphenyloxazolyl thio, the electro-optic coefficient is the highest. At a working wavelength of 1304 nm, M3FPPhON exhibits the optimal electro-optic coefficient at a number concentration of 1.6 × 10⁻⁶. 20 mL -1 At that time, the electro-optic coefficient was 135.6 pm / V. Attached Figure Description

[0051] Figure 1 Compound 1 of Example 1 1 H NMR results.

[0052] Figure 2 Compound 1 of Example 1 13 C NMR results.

[0053] Figure 3 Compound 2 of Example 1 1 H NMR results.

[0054] Figure 4 Compound 2 of Example 1 13 C NMR results.

[0055] Figure 5 Compound 3 of Example 1 1 H NMR results.

[0056] Figure 6 Compound 3 of Example 1 13 C NMR results.

[0057] Figure 7 Compound 4 of Example 1 1 H NMR results.

[0058] Figure 8 Compound 4 of Example 1 13 C NMR results.

[0059] Figure 9 The compound M3FPCl of Example 1 1 H NMR results.

[0060] Figure 10 The compound M3FPCl of Example 1 13 C NMR results.

[0061] Figure 11 The compound M3FPPhON of Example 2 1 H NMR results.

[0062] Figure 12 The compound M3FPPhON of Example 2 13 C NMR results.

[0063] Figure 13 The compound M3FPSN of Example 3 1 H NMR results.

[0064] Figure 14 The compound M3FPSN of Example 3 13 C NMR results.

[0065] Figure 15 The compound M3FPON of Example 4 1 H NMR results.

[0066] Figure 16 The compound M3FPON of Example 4 13 C NMR results.

[0067] Figure 17 For compound M3FPSO2 in Example 5 1 H NMR results.

[0068] Figure 18 For compound M3FPSO2 in Example 5 13 C NMR results.

[0069] Figure 19 The compound M3F3PCl of Example 6 1 H NMR results.

[0070] Figure 20 The compound M3F3PPhON of Example 7 1 H NMR results.

[0071] Figure 21 The compound M3F3PPhON of Example 7 13 C NMR results.

[0072] Figure 22 The graphs show the cyclic voltammetry of the compounds in Examples 1-7 in tetra-n-butylammonium hexafluorophosphate / dichloromethane solution.

[0073] Figure 23 The image shows the molar extinction coefficient spectrum of compound M3FPCl in solution from Example 1.

[0074] Figure 24 The image shows the molar extinction coefficient spectrum of compound M3FPPhON in solution in Example 2.

[0075] Figure 25 The image shows the molar extinction coefficient spectrum of compound M3FPSN in solution in Example 3.

[0076] Figure 26 The image shows the molar extinction coefficient spectrum of compound M3FPON in solution in Example 4.

[0077] Figure 27 The image shows the molar extinction coefficient spectrum of compound M3FPSO2 in solution in Example 5.

[0078] Figure 28 The image shows the molar extinction coefficient spectrum of compound M3F3PCl in solution in Example 6.

[0079] Figure 29 The image shows the molar extinction coefficient spectrum of compound M3F3PPhON in solution in Example 7.

[0080] Figure 30 The images show the pure membrane absorption spectra of the compounds in Examples 1-7.

[0081] Figure 31 The graph shows the test results of the reflection intensity of the unpolarized film and the polarized film using a wavelength of 1304 nm, when the thin film prepared by mixing compound M3FPPhON with a polymer in Example 2 is mixed. Detailed Implementation

[0082] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments, further clarifies the invention. Those skilled in the art should understand that the specific descriptions below are illustrative rather than restrictive, and should not be construed as limiting the scope of protection of the present invention.

[0083] All numerical specifications in this invention (e.g., temperature, time, concentration, and weight, including ranges for each) are generally approximate values ​​that may be changed (+) or (-) in increments of 0.1 or 1.0. All numerical specifications are to be understood as being preceded by the term "about".

[0084] Example 1

[0085] In this embodiment, a chromophore compound (compound M3FPCl) was prepared, the structure of which is shown below:

[0086]

[0087] This optical chromophore compound was prepared by the following steps:

[0088] Step i, Synthesize compound 1 :

[0089]

[0090] In a flask, add p-aminoacetophenone (5 g, 37 mmol), bromobutane (60 g, 438 mmol), potassium carbonate (12.3 g, 88.8 mmol), and KI (1.2 g, 7.4 mmol), and reflux for 10 days. Add silica gel, evaporate the solvent to dryness, and pass the solution through a column chromatography using n-hexane:ethyl acetate (v / v 10:1) (8.7 g, 95.1%).

[0091] Compound 1 1 The H NMR detection results are as follows, and the specific spectra are shown below. Figure 1 As shown:

[0092] 1 H NMR(300MHz,Chloroform-d)δ7.96–7.79(m,2H),6.73–6.48(m,2H),3.51–3.19( m,4H),2.51(s,3H),1.68–1.52(m,4H),1.52–1.31(m,4H),0.99(t,J=7.3Hz,6H).

[0093] Compound 1 13 The C NMR detection results are as follows, and the specific spectra are shown below. Figure 2 As shown:

[0094] 13 C NMR (75MHz, CDCl3) δ195.00,151.28,130.50,124.42,110.02,50.43,29.17,25.54,20.06,13.79.

[0095] Step ii, Synthesize compound 2:

[0096]

[0097] At room temperature, N-ethyl-N-hydroxyethylaniline (2 g, 12.1 mmol), imidazole (1.24 g, 18.2 mmol), 20 ml DMF, and 15 ml tetrahydrofuran were added to a flask. Tert-butyldiphenylchlorosilane (3.7 g, 13.3 mmol) was added dropwise. The mixture was reacted at room temperature for 24 h. Dichloromethane and water were added for extraction. The mixture was dried over anhydrous sodium sulfate and passed through a column (4.6 g, 95%) using hexane:ethyl acetate (v / v 20:1).

[0098] Compound 2 1The H NMR detection results are as follows, and the specific spectra are shown below. Figure 3 As shown:

[0099] 1 H NMR(300MHz,Chloroform-d)δ7.73(dq,J=8.0,1.8Hz,4H),7.46(dtdd,J=15.9,8.4,3.4,1.7Hz,6H),7.16(tt,J=7.1,1.8Hz,2H),6.64(td ,J=7.4,6.4,3.0Hz,1H),6.58–6.48(m,2H),3.98–3.75(m,2H),3.48(ddt,J=8.9,3.8,1.9Hz,2H),3.44–3.32(m,2H),1.20–1.07(m,12H).

[0100] Compound 2 13 The C NMR detection results are as follows, and the specific spectra are shown below. Figure 4 As shown:

[0101] 13 C NMR (75MHz, CDCl3) δ147.96,135.89,133.78,129.99,129.47,128.01,115.71,111.73,61.45,52.30,45.49,27.17,19.39,12.44.

[0102] Step iii: Synthesize compound 3 :

[0103]

[0104] In a flask, compound 2 (4.9 g, 12.1 mmol) and 20 mL of DMF were added. The mixture was kept in an ice bath. N-bromosuccinimide (NBS, 2.26 g, 12.7 mmol) was dissolved in 15 mL of DMF and added dropwise to the flask. The reaction was carried out in the dark for 18 h. DCM was added, and the mixture was washed three times with water and dried over anhydrous sodium sulfate. The solution was packed into a column in hexane, and then purified using a hexane:ethyl acetate (v / v) mixture (4.5 g, 77.7%).

[0105] Compound 3 1 The H NMR detection results are as follows, and the specific spectra are shown below. Figure 5 As shown:

[0106] 1H NMR(300MHz,Chloroform-d)δ7.78–7.68(m,4H),7.54–7.38(m,6H),7.26–7.17(m,2H),6.46–6.34( m,2H),3.82(t,J=6.7Hz,2H),3.44(t,J=6.7Hz,2H),3.35(q,J=7.0Hz,2H),1.13(d,J=4.1Hz,12H).

[0107] Compound 3 13 The C NMR detection results are as follows, and the specific spectra are shown below. Figure 6 As shown:

[0108] 13 C NMR (75MHz, CDCl3) δ146.80,135.67,133.44,131.80,129.84,127.81,113.21,107.16,60.99,52.13,45.40,26.91,19.16,12.00.

[0109] Step iv, Synthesize compound 4:

[0110]

[0111] Compound 3 (0.745 g, 1.54 mmol) and 20 mL of THF were added to a flask and placed in a cryogenic reactor (-78 °C). Compound 1 was dissolved in 20 mL of THF and added to the reaction flask using a syringe. The reaction was carried out at low temperature for 1 h, then at room temperature overnight. Water was added, and the mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate. The product was used directly without column chromatography.

[0112] Compound 4 1 The H NMR detection results are as follows, and the specific spectra are shown below. Figure 7 As shown:

[0113] 1H NMR(300MHz,Chloroform-d)δ7.75–7.68(m,4H),7.50–7.37(m,6H),7.29–7.24(m,2H),7 .24–7.14(m,2H),6.67–6.59(m,2H),6.55–6.46(m,2H),5.17(dd,J=12.5,1.7Hz,2H),3.8 4(t,J=6.7Hz,2H),3.49(t,J=6.7Hz,2H),3.36(dt,J=24.4,7.4Hz,6H),1.63(ddd,J=15. 0,8.9,6.3Hz,4H),1.40(h,J=7.3Hz,4H),1.13(d,J=14.1Hz,12H),1.00(t,J=7.3Hz,6H).

[0114] Compound 4 13 The C NMR detection results are as follows, and the specific spectra are shown below. Figure 8 As shown:

[0115] 13 C NMR (75MHz, CDCl3) δ149.61,147.73,147.28,135.66,133.55,129.74,129.42,129.31,129.29,128.76, 127.75,110.97,110.86,107.96,61.27,52.05,50.84,45.35,29.51,26.89,20.41,19.15,14.07,12.28.

[0116] Step v: Synthesize compound M3FPCl :

[0117]

[0118] Compound 4 (344 mg, 0.54 mmol), compound 5 (325 mg, 0.54 mmol), 10 mL of ethanol, and 87 μL of pyridine were added to a flask. The mixture was reacted for 2 days, cooled, filtered, and passed through a column with dichloromethane. The mixture was then recrystallized from methanol (453 mg, 70.5%).

[0119] The compound M3FPCl 1 The H NMR detection results are as follows, and the specific spectra are shown below. Figure 9 As shown:

[0120] 1H NMR(400MHz,Chloroform-d)δ7.82–7.62(m,5H),7.52–7.35(m,7H),7.31(dd,J=9.0,5.1Hz,3H),7.27(d,J=5.3Hz,2H), 7.21(d,J=8.4Hz,1H),7.10(dt,J=16.3,7.9Hz,6H),6.76(dd,J=18.6,12.3Hz,1H),6.68–6.58(m,3H),6.53(dd,J=18.2 ,8.5Hz,2H),3.84(q,J=6.2Hz,2H),3.51(d,J=6.9Hz,2H),3.46–3.23(m,6H),3.07(d,J=14.9Hz,1H),2.65(d,J=15.5Hz ,1H),2.09(t,J=14.0Hz,2H),1.63(s,4H),1.55–1.33(m,5H),1.22–1.12(m,3H),1.07(s,9H),1.00(d,J=14.2Hz,15H).

[0121] The compound M3FPCl 13 The C NMR detection results are as follows, and the specific spectra are shown below. Figure 10 As shown:

[0122] 13 C NMR (101MHz, CDCl3) δ175.47,169.27,164.66,162.16,162.14,155.93,149.16,148.81,147.77,146.92,139.89 ,135.64,133.39,133.23,132.91,132.88,132.86,132.82,132.19,131.25,130.40,130.33,130.24,129.80,127 .79,125.94,119.57,116.26,116.24,116.04,116.02,113.83,112.41,111.78,111.12,110.75,101.44,96.14,61.30,55.48,51.90,50.84,45.41,42.42,32.41,29.52,28.21,27.61,27.38,26.87,20.36,19.12,14.03,12.23.

[0123] Example 2

[0124] This embodiment provides a chromophore compound (compound M3FPPhON), the structure of which is shown below:

[0125]

[0126] This optical chromophore compound was prepared by the following steps:

[0127] Step 1: Synthesize compound M3FPPhON:

[0128]

[0129] In a flask, compound M3FPCl (200 mg, 0.17 mmol), 4,5-diphenyl-2-mercaptooxazole (88 mg, 0.34 mmol), 5 mL acetonitrile, and 47 μL triethylamine were added, and the mixture was refluxed for 0.5 h. Silica gel was added, the solvent was evaporated to dryness, and the mixture was column-filtered using n-hexane:ethyl acetate (v / v 10:1) (163 mg, 68.8%).

[0130] The compound M3FPPhON 1 The H NMR detection results are as follows, and the specific spectra are shown below. Figure 11 As shown:

[0131] 1 H NMR(400MHz,Chloroform-d)δ8.05(dd,J=15.3,6.1Hz,1H),7.85–7.56(m,7H), 7.49–7.28(m,16H),7.22(dd,J=31.7,8.4Hz,4H),7.13–6.70(m,8H),6.60(d,J= 8.6Hz,1H),6.52–6.21(m,3H),3.87–3.10(m,11H),2.78(d,J=16.6Hz,1H),2.3 3–2.06(m,2H),1.40(dddd,J=59.3,51.7,18.1,8.4Hz,9H),1.18–0.87(m,27H).

[0132] The compound M3FPPhON 13 The C NMR detection results are as follows, and the specific spectra are shown below. Figure 12 As shown:

[0133] 13C NMR (151MHz, CDCl3) δ175.20,169.59,164.12,164.03,162.45,162.36,155.94,155.12,149.23,148.56,147.18,143.11,140.00,136.71 ,135.61,133.41,133.09,132.96,132.55,132.52,131.74,131.13,1 30.34,130.29,129.77,129.69,129.14,128.84,128.78,128.66,128 .50,128.32,127.82,127.72,126.10,125.66,119.76,116.14,116.00,115.88,114.72,112.21,111.62,111.06,110.90,110.73,110.62,101.64,97.44,61.39,61.11,55.89,51.62,50.84,50.55,45.37,42.51,32.48,29.48,28.40,27.36,26.83,20.31,19.07,14.01,12.10.

[0134] Example 3

[0135] In this embodiment, a chromophore compound (compound M3FPSN) was prepared, the structure of which is shown below:

[0136]

[0137] This optical chromophore compound was prepared by the following steps:

[0138] Step ⅷ: Synthesize compound M3FPSN :

[0139]

[0140] In a flask, compound M3FPCl (200 mg, 0.17 mmol), 2-mercaptobenzothiazole (56 mg, 0.34 mmol), 5 mL acetonitrile, and 47 μL triethylamine were added, and the mixture was refluxed for 40 min. After cooling, the mixture was filtered, and the solid was dissolved in dichloromethane, then silica gel was added. The solvent was evaporated to dryness, and the solution was passed through a column using dichloromethane (172 mg, 77.3%).

[0141] The compound M3FPSN 1 The H NMR detection results are as follows, and the specific spectra are shown below. Figure 13 As shown:

[0142] 1H NMR(600MHz,Chloroform-d)δ7.91(d,J=15.4Hz,1H),7.88–7.31(m,16H),7.21(d,J=36.1Hz,6H),6.8 2(dd,J=27.6,12.0Hz,6H),6.54(dd,J=63.5,8.4Hz,3H),6.35–6.08(m,2H),3.79(d,J=21.8Hz,2H),3 .53–3.14(m,9H),2.86(d,J=16.4Hz,1H),2.27(dd,J=16.6,10.9Hz,1H),2.15(t,J=13.9Hz,1H),1.62 (s,1H),1.57(d,J=19.9Hz,4H),1.38(d,J=8.2Hz,4H),1.09(d,J=15.5Hz,21H),0.99(t,J=7.4Hz,6H).

[0143] The compound M3FPSN 13 The C NMR detection results are as follows, and the specific spectra are shown below. Figure 14 As shown:

[0144] 13 C NMR (151MHz, CDCl3) δ174.99,169.43,167.50,163.94,162.27,155.93,153.70,149.34,147.92,144.28,140.48, 139.87,136.18,135.62,135.09,133.42,133.19,132.32,131.30,130.23,130.17,129.75,129.03,127.74,126. 55,124.63,121.68,120.76,119.90,115.89,115.74,115.18,112.11,111.58,111.06,110.76,110.50,101.71,97.96,61.33,55.99,51.84,50.81,45.39,42.25,32.52,29.50,28.28,27.36,26.85,20.33,19.10,13.98,12.21.

[0145] Example 4

[0146] In this embodiment, a chromophore compound (compound M3FPON) was prepared, the structure of which is shown below:

[0147]

[0148] This optical chromophore compound was prepared by the following steps:

[0149] Step IX: Synthesize compound M3FPON:

[0150]

[0151] In a flask, compound M3FPCl (200 mg, 0.17 mmol), 2-mercaptobenzoxazole (51 mg, 0.34 mmol), 5 mL acetonitrile, and 47 μL triethylamine were added, and the mixture was refluxed for 40 min. After cooling, the mixture was filtered, and the solid was dissolved in dichloromethane, then silica gel was added. The solvent was evaporated to dryness, and the mixture was passed through a column with dichloromethane and recrystallized from ethanol (164 mg, 74.7%).

[0152] The compound M3FPON 1 The H NMR detection results are as follows, and the specific spectra are shown below. Figure 15 As shown:

[0153] 1 H NMR(600MHz,Chloroform-d)δ7.91(d,J=15.4Hz,1H),7.75–7.57(m,6H),7.48–7 .30(m,9H),7.27–7.11(m,6H),7.10–6.38(m,10H),6.33–5.98(m,2H),3.91–3.6 8(m,2H),3.54–3.14(m,9H),2.82(d,J=16.3Hz,1H),2.42–2.13(m,2H),1.60–1. 50(m,4H),1.37(p,J=7.1Hz,4H),1.08(d,J=9.4Hz,22H),0.99(q,J=6.8Hz,6H).

[0154] The compound M3FPON 13 The C NMR detection results are as follows, and the specific spectra are shown below. Figure 16 As shown:

[0155] 13C NMR (151MHz, CDCl3) δ175.06,169.35,164.04,163.92,162.37,162.25,161.67,155.26,151.61,149.02,148.04,141.92,140. 54,140.18,136.78,135.61,133.39,133.08,132.43,131.18,130.24,130.21,130.18,130.15,129.76,127.74,124.73,124.41 ,119.96,118.94,116.02,115.87,115.71,115.06,112.13,111.55,111.05,110.79,110.43,110.30,109.83,101.58,97.74,61.29,56.02,51.92,51.75,50.82,50.63,45.33,42.13,32.52,29.49,28.34,28.28,27.37,26.84,20.33,19.10,13.98,12.19.

[0156] Example 5

[0157] In this embodiment, a chromophore compound (compound M3FPSO2) was prepared, the structure of which is shown below:

[0158]

[0159] This optical chromophore compound was prepared by the following steps:

[0160] Step X: Synthesize compound M3FPSO2 :

[0161]

[0162] In a flask, add compound M3FPCl (200 mg, 0.17 mmol), sodium benzenesulfinate (55 mg, 0.34 mmol), and 5 mL of acetonitrile, and reflux for 30 min. Add silica gel, evaporate the solvent to dryness, pass through a column with dichloromethane, and recrystallize from ice-cold ethanol (175 mg, 80.1%).

[0163] The compound M3FPSO2 1 The H NMR detection results are as follows, and the specific spectra are shown below. Figure 17 As shown:

[0164] 1H NMR(300MHz,Chloroform-d)δ8.83(d,J=15.6Hz,1H),7.81–7.62(m,4H),7.49–7.3 4(m,9H),7.31(dd,J=5.9,2.9Hz,3H),7.23–6.85(m,13H),6.58(t,J=27.2Hz,5H),3 .82(d,J=12.8Hz,2H),3.37(s,8H),3.10–2.80(m,2H),2.17(dd,J=16.9,11.9Hz,1H ),1.90(t,J=13.7Hz,1H),1.61(s,4H),1.50–1.34(m,5H),1.04(d,J=21.0Hz,27H).

[0165] The compound M3FPSO2 13 The C NMR detection results are as follows, and the specific spectra are shown below. Figure 18 As shown:

[0166] 13 C NMR (151MHz, CDCl3) δ174.69,170.29,164.32,164.23,162.66,162.56,154.24,147.57,144.92,142.53,138.77,138.62,1 36.60,135.61,133.41,132.60,132.19,132.17,131.63,131.60,130.59,130.56,130.53,130.50,130.27,129.77,129.44, 128.81,127.76,127.59,125.72,119.11,118.06,116.25,116.23,116.10,116.08,111.68,111.11,110.97,110.31,102.42,100.96,57.55,52.01,50.83,45.42,42.08,32.36,29.96,29.70,29.51,28.48,27.17,26.85,20.34,19.12,13.98,12.22.

[0167] Example 6

[0168] In this embodiment, a chromophore compound (compound M3F3PCl) was prepared, the structure of which is shown below:

[0169]

[0170] This optical chromophore compound was prepared by the following steps:

[0171] Step ⅵ: Synthesize compound M3F3PCl :

[0172]

[0173] Compound 4 (142 mg, 0.23 mmol), compound 6 (125 mg, 0.23 mmol), 6 mL of ethanol, and 36 μL of pyridine were added to a flask. The mixture was refluxed for 30 min, evaporated to dryness, cooled, and then ice-cold methanol was added. The mixture was filtered, and the solid was dissolved in dichloromethane. The solid was then loaded onto silica gel and packed into a column with n-hexane. The column was then permeated with n-hexane:ethyl acetate (v / v ratio 8:1). The solid was recrystallized from methanol (164 mg, 63.7%).

[0174] The compound M3F3PCl 1 The H NMR detection results are as follows, and the specific spectra are shown below. Figure 19 As shown:

[0175] 1 H NMR(400MHz,Chloroform-d)δ7.69(t,J=9.0Hz,4H),7.60–7.33(m,8H),7.28(s,2H),7 .22(d,J=8.2Hz,1H),7.15(d,J=8.2Hz,1H),7.09(d,J=8.2Hz,1H),7.02(s,2H),6.83–6 .41(m,6H),3.94–3.73(m,2H),3.61–3.25(m,8H),3.07(d,J=15.0Hz,1H),2.66(d,J=1 5.6Hz,1H),2.11(d,J=3.8Hz,5H),1.64(s,4H),1.53–1.34(m,5H),1.22–0.93(m,27H).

[0176] Example 7

[0177] In this embodiment, a chromophore compound (compound M3F3PPhON) was prepared, the structure of which is shown below:

[0178]

[0179] This optical chromophore compound was prepared by the following steps:

[0180] Step xi: Synthesis of compound M3F3PPhON :

[0181]

[0182] In a flask, compound M3FPCl (120 mg, 0.11 mmol), 2-mercapto-4,5-diphenyloxazole (54 mg, 0.21 mmol), 5 mL acetonitrile, and triethylamine (40 μL, 0.21 mmol) were added, and the mixture was refluxed for 20 min. Silica gel was added, the solvent was evaporated, and the mixture was purified by column chromatography using n-hexane:ethyl acetate (10:1 v / v). Recrystallization was performed using methanol (116 mg, 80.9%).

[0183] The compound M3F3PPhON 1 The H NMR detection results are as follows, and the specific spectra are shown below. Figure 20 As shown:

[0184] 1 H NMR(400MHz,Chloroform-d)δ7.97(td,J=15.7,7.1Hz,2H),7.79–7.57(m,6H),7.40(tq, J=19.2,13.1,9.6Hz,15H),7.27–6.94(m,5H),6.86(dd,J=18.0,12.2Hz,1H),6.69–6.43( m,4H),6.35(dd,J=8.5,4.3Hz,1H),3.93–3.62(m,2H),3.57–3.08(m,9H),2.75(d,J=16.4 Hz,1H),2.31–1.94(m,5H),1.64(d,J=7.8Hz,1H),1.59–1.23(m,8H),1.17–0.90(m,27H).

[0185] The compound M3F3PPhON 13 The C NMR detection results are as follows, and the specific spectra are shown below. Figure 21 As shown:

[0186] 13C NMR (151MHz, CDCl3) δ175.33,171.19,155.72,150.66,136.86,135.62,133.39,131.64,131.28,129.75,1 28.98,128.84,128.68,128.60,128.22,128.19,127.78,127.74,126.26,126.23,120.03,112.77,112.21 ,111.57,111.33,111.09,110.65,96.34,61.41,61.15,55.93,51.94,51.71,50.85,50.64,45.34,42.33,32.50,32.48,29.50,28.47,28.22,27.38,27.33,26.83,24.68,24.64,20.32,19.09,14.00,12.21,12.08.

[0187] Test Example 1

[0188] Cyclic voltammetry tests were performed on the compounds obtained in Examples 1-7 using 0.1 M 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 ferrocene was used for calibration. Figure 22 The cyclic voltammetry curves for the chromophore compounds are shown. Table 1 summarizes the cyclic voltammetry results and absorption results. Figure 22 It can be seen that this type of material exhibits reversible redox peaks, demonstrating a reversible redox process. Due to the presence of the same donor group, the HOMO energy level of the chromophore changes very little, approximately -4.89 eV to -4.93 eV. The band gaps of the two acceptors are similar, indicating comparable electron-withdrawing abilities. CV results show that the side-chain-connected groups have a greater impact on the LUMO energy level than the HOMO energy level. When the conjugated bridge is connected to Cl, the band gap is 1.06 eV. After the Cl atom is replaced by a more sterically hindered group, the band gap decreases. The benzenesulfonyl group has the greatest impact on the band gap, decreasing it from 1.06 eV to 0.97 eV.

[0189] Table 1. Summary of cyclic voltammetric results and absorption results for chromophores.

[0190]

[0191] Test Example 2

[0192] The compounds obtained in Examples 1-7 were subjected to absorption spectroscopy using UV-vis-NIR absorption spectroscopy. The compounds in Examples 1-7 were diluted to a concentration of 1×10⁻⁶. -5The solutions of M were prepared using dioxane (1,4-dioxane), chloroform, dichloromethane, acetone, acetonitrile, and dimethyl sulfoxide (DMSO) as solvents. Tests were conducted at room temperature using a 1 cm quartz cuvette. The extinction coefficient (ε) of the material was calculated using the formula: A = εcb, where A is the absorbance of the maximum absorption peak; c is the molar concentration of the material; and b is the thickness of the cuvette. Figures 23-29 This is a graph showing the extinction coefficient. A pure film is formed by dissolving the compound in chloroform and spin-coating it onto glass. Figure 30 This is the normalized absorbance result for the pure membrane. (From...) Figures 23-29 It can be seen that this type of material exhibits strong near-infrared absorption and lyochromic results. According to... Figure 30 According to formula E g =1240 / λ onset The absorption band gap of the thin film was calculated, where λ onset The wavelength at which the thin film begins absorption is shown. The optical band gap and electrochemical band gap exhibit similar trends; when chlorine atoms are replaced by groups such as oxazole and thiazole derivatives, the band gap decreases, and the absorption spectrum red-shifts. M3FPSO2 shows the lowest band gap.

[0193] Test Example 3

[0194] The refractive index of compound M3FPPhON from Example 2 was measured using a prism-coupled waveguide, with an incident wavelength of 1304 nm.

[0195] Test method references Wang, W.; Wu, J.; Chen, K.; Huang, Q.; Luo, J.; Chiang, KS, Graphene electrodes for electric poling of electro-optic polymer films. Optics Letters, 2020, 45, 2383-2386. Kuzyk, MG and CWDirk, Characterization Techniques and Tabulations for Organic Nonlinear Optical Materials.1998:Marcel Dekker.

[0196] Chromophore compounds and polymers, specifically methyl methacrylate-styrene copolymers, were mixed in a specific ratio (10-40 wt% chromophore compound). Dibromomethane was added to fully dissolve and mix the mixture homogeneously. The resulting solution was then spin-coated onto ITO glass. After vacuum drying, the mixture was processed and tested. The film thickness was measured using a profilometer. Gold plating was used as the positive electrode, and ITO as the negative electrode, with an applied electric field (100 V / μm). The temperature was increased; upon reaching the glass transition temperature range of 100-110 °C, the leakage current increased significantly. The film was then cooled while maintaining the voltage. The refractive index of the film was measured; a large birefringence indicated successful polarization. A commercially available prism coupling tester, Model 2010 / M, was used for prism coupling testing.

[0197] Test results are as follows Figure 31 As shown in Tables 2 and 3. Figure 31 The polarized thin film of M3FPPhON contains 33.88 wt% chromophore compounds, equivalent to a number density N of 1.6 × 10⁻⁶ in the polymer. 20 cm -1 The graph shows the test results of the reflection intensity of TE and TM waves on the unpolarized and polarized films, respectively, at a laser wavelength of 1304 nm. Figure 31 It can be seen that the TE and TM refractive indices of the polarized film change after polarization, with TM being significantly greater than TE. Table 2 shows the refractive index test results of the M3FPPhON polarized film at 1304 nm using a prism-coupled waveguide. Under the application of a certain voltage, the refractive index of the compound changes significantly (the change in refractive index at 1304 nm is 0.01 under an electric field of 0-30 V / μm), indicating that the compound M3FPPhON of Example 2 has a good electro-optic effect.

[0198] Table 3 summarizes the electro-optic performance results of Examples 1-7. The chromophore M3FPCl in Example 1, at a number concentration of 1.3 × 10⁻⁶, showed excellent electro-optic performance. 20 cm -1 At that time, the electro-optic coefficient (r) 33 The electro-optic coefficient was 111.2 pm / V. After replacing the Cl atom with a sterically hindered diphenyloxazole thio group, the electro-optic coefficient was 121.5 pm / V. Further increasing the number concentration to 1.6 × 10⁻⁶ pm / V... 20 cm -1 At that time, the electro-optic coefficient was 135.6 pm / V. Hyperpolarizability reflects the potential of chromophores in electro-optic applications. The hyperpolarizability of Examples 1-5 is higher than 6000 × 10⁻⁶. -30 esu, but when trifluorobenzyl TCF is used as the acceptor, the hyperpolarizability is less than 5200 × 10 -30ESU. Experiments show that when a silicon-containing asymmetric Michaelis base is used as the donor, a diphenyloxazolyl-substituted cyclohexene derivative is used as the conjugated bridge, and p-fluorobenzene TCF is used as the acceptor, the chromophore exhibits excellent electro-optic properties.

[0199] Table 2 shows the refractive index test results of the prism-coupled waveguide at 1304 nm for the polarized film of compound M3FPPhON.

[0200]

[0201] Table 3. Different chromophore compounds in number densities N of 1.3–2.0 × 10⁻⁶ 20 cm -1 The maximum absorption wavelength λ max (Polymer-blended films), electro-optic coefficient (r) 33 ), order parameter (Φ) and hyperpolarizability (β) μ )

[0202]

[0203] The chromophore compound of this invention uses a silicon-containing asymmetric Michaelis base as the donor, cyclohexene derivatives with different side chain modifications as the conjugated bridge, and p-fluorobenzene TCF or trifluorobenzenemethyl TCF as the electron acceptor. When the conjugated bridge is a diphenyloxazolylthio-modified cyclohexene derivative and the acceptor is p-fluorobenzene TCF, the number concentration is 1.3 × 10⁻⁶. 20 cm -1 At that time, the electro-optic coefficient was 121.5 pm / V, and the number concentration was further increased to 1.6 × 10⁻⁶. 20 cm -1 At that time, the electro-optic coefficient was 135.6 pm / V.

[0204] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. It is impossible to exhaustively list all the implementation methods here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A push-pull type silicon-containing asymmetric Michaelis base derivative heptamethrin chromophore compound, wherein, The general structural formula of the chromophore compound is shown in Formula 1: R1-R2=R3 Equation 1; In Equation 1, the structure of R1 is shown in Equation 2: In Formula 2, R4 and R5 are independently selected from C1-12 alkyl groups, and R6 is selected from the following silicon-containing groups: Among them, R 10 Alkyl groups selected from C1-12, where n is an integer from 1 to 5; The structure of R2 is shown in Equation 3: In Formula 3, R7 is selected from Cl atoms, Benzenesulfonyl group and its derivatives; wherein X is O or S, R 11 R 12 Independently selected from phenyl, substituted phenyl, or R 11 and R 12 The condensation is an aromatic group; The structure of R3 is selected from Equation 4: In Formula 4, R8 and R9 are independently selected from methyl and fluorophenyl.

2. The chromophore compound according to claim 1, wherein, R4 is butyl, R5 is ethyl, and R6 is 2-((tert-butyldiphenylsilyl)oxy)ethyl.

3. The chromophore compound according to claim 1, wherein, R7 is a Cl atom, (4,5-diphenyloxazol-2-yl)thio, (phenyloxazol-2-yl)thio, (phenylthiazol-2-yl)thio, or benzenesulfonyl.

4. The chromophore compound according to claim 1, wherein, The fluorophenyl group is p-fluorophenyl or trifluorophenyl.

5. The chromophore compound according to claim 4, wherein, Equation 4 is selected from the following structure:

6. The chromophore compound according to claim 1, wherein, The chromophore compound has one of the following structural formulas:

7. A composite material comprising the chromophore compound according to any one of claims 1-6.

8. The composite material according to claim 7, wherein, The content of the chromophore compound is 10%-40% based on the total weight of the composite material.

9. The composite material according to claim 8, wherein, The composite material also includes polymers.

10. The composite material according to claim 9, wherein, The polymer includes one or more of polymethyl methacrylate, methyl methacrylate-styrene copolymer, and polycarbonate.

11. The composite material according to claim 7, wherein, Within the wavelength range of 1000nm-1600nm, the electro-optic coefficient r of the composite material is... 33 The time ranges from 50 pm / V to 160 pm / V.

12. The composite material according to claim 7, wherein, Under an electric field of 0V-40V / μm, the refractive index of the composite material changes from 0.0005 to 0.02 within a wavelength range of 1000nm-1600nm.

13. The composite material according to claim 7, wherein, The hyperpolarizability β of the composite material μ (4000-8000)×10 -30 esu.

14. A film made of the composite material according to any one of claims 7-13.

15. An optoelectronic integrated device having the thin film of claim 14.

16. The optoelectronic integrated device according to claim 15, wherein, The optoelectronic integrated device is an electro-optical device.

Images