CN114656432B - Self-assembled organic optical nonlinear chromophore, and synthesis method and application thereof - Google Patents

Abstract

The invention provides an organic optical nonlinear chromophore based on a novel single-donor self-assembly structure, which belongs to the field of optical materials, wherein the chromophore has a structural formula shown in an abstract drawing, OH groups are introduced into a single donor and an electronic bridge of a second-order nonlinear optical chromophore through nucleophilic reaction, the two OH groups provide connection sites for further modification, different self-assembly isolation functional groups are connected, and meanwhile, the test of an electro-optic coefficient proves that after the materials are self-assembled, the electro-optic coefficient is higher than that of other non-self-assembly materials.

Description

A self-assembled organic optical nonlinear chromophore and its synthesis method and application

Technical Field

The invention relates to the field of organic optical materials, and in particular to a self-assembled organic optical nonlinear chromophore and a synthesis method and application thereof.

Background Art

With the rapid development of information and communication technology, people's demand for high-speed data transmission, processing and large-capacity information computing is also increasing. Compared with traditional electronics as information carriers, photons as communication information carriers have the advantages of good parallelism, fast speed, large bandwidth, high frequency, strong anti-electronic interference ability, and good confidentiality. Among the many communication technologies, photon, electronics and other technologies are closely related to devices such as electro-optical modulators, optical switches, and optical information storage. The mutual conversion of electrical signals and optical signals has become an important part of today's communication technology. In the future era of high-speed information transmission, integrated optoelectronic technology will be a major trend. At present, electro-optical modulators are mainly based on this technology. At the same time, it is also an indispensable and important device in optical communication. Nonlinear optical materials have also become the core components of modulators, which has attracted widespread attention. A chromophore is a structure composed of an electron donor (D), an electron acceptor (A) and an electron bridge (π) (D-π-A structure). Various types of donors, bridges and acceptors have been developed in the prior art to enhance the first-order hyperpolarizability of chromophores, such as aniline donors (triarylamino, alkylaniline, etc.), heterocyclic or polyene bridges, and TCF or _CF3- TCF derivative acceptors, which are the most common chromophore structures. A reasonable combination of a strong donor, an acceptor and a suitable electron bridge will produce a large first-order hyperpolarizability.

In order to obtain a larger electro-optic coefficient, a larger first-order hyperpolarizability of the chromophore is required. However, chromophores with large first-order hyperpolarizability usually have larger dipole moments, which leads to stronger electrostatic interactions between molecules during the polarization of the chromophore, thus hindering the orientation of the molecules. This ultimately leads to molecular aggregation and low polarization efficiency of the chromophore. Many studies have reported that by introducing some isolation groups into the donor, acceptor and bridging parts of the chromophore, the dipole interactions between molecules can be reduced, the solubility of the chromophore and the electro-optic coefficient of the material can be improved, and the CLD bridge in the NLO chromophore can be functionalized with macromolecular substituents such as alkyl chains, silanes, carbazoles and various branched structures, which can effectively reduce the dipole-dipole interactions and improve the polarization efficiency of NLO.

The glass transition temperature ( _Tg ) of most dendrimer chromophore films is usually lower than that of high molecular weight polymer EO materials. The long-term stability of EO materials is another challenge for second-order nonlinear optics. Based on Diels-Alder cycloaddition reaction or ArH-ArF interaction, lattice hardening or intermolecular hydrogen bonding methods using sequential poling, cross-linking or self-assembly have successfully improved the electro-optic coefficient and high long-term stability. However, the design, synthesis, poling and cross-linking processes of cross-linked electro-optic materials are very complicated.

Summary of the invention

In view of the above problems, the present invention provides a new, self-assembled single donor structure, in which an OH group is introduced into the single donor and the electron bridge of the second-order nonlinear optical chromophore through a nucleophilic reaction, and the two OH groups connected at the donor end and the electron bridge end provide connection sites for further modification. By introducing a high-efficiency self-assembly group containing an aromatic phenyl dendron (HD), a pentafluorophenyl dendron (PFD) or a trifluorophenyl dendron (TFD), a new dendritic macromolecule, a main chain and a side chain self-assembled EO polymer are formed, thereby having an ultra-large electro-optical coefficient and high long-term stability.

The purpose of the present invention is achieved by the following technical solutions:

In the first aspect, the present invention provides an organic optical nonlinear chromophore based on a single donor self-assembly structure, wherein the chromophore comprises H1, H2, H3 and H4, and the specific molecular structure is as follows:

Wherein, the molecular structure formula of the chromophores H1, H2, and H3 is as follows:

Among them, R is

In a second aspect, the present invention provides a method for synthesizing an organic optical nonlinear chromophore based on a single donor self-assembly structure, including synthetic chromophores H1-H3 and synthetic chromophore H4.

Preferably, the method for synthesizing chromophores H1-H3 comprises the following steps:

S1, 4-((2-((tert-butyldimethylsilyl)oxy)ethyl)(methyl)amino)benzaldehyde (i.e. compound (2a)) and isophorone (compound 1) are reacted in sodium ethoxide and 2-mercaptoethanol to obtain compound (3a) by Knoevenagel condensation reaction;

S2, inserting a tert-butyldimethylsilyl protecting group onto the alcoholic hydroxyl group of the compound (3a) to obtain a compound (4a);

S3, the compound (4a) is reacted with diethyl cyanomethyl phosphate by Wittig-Hornor reaction to obtain compound (5a);

S4, reducing the cyano group in the compound (5a) to an aldehyde by diisobutylaluminum hydride to obtain compound (6a);

S5. The compound (6a) is subjected to acid hydrolysis to obtain a compound (7a);

S6, connecting different functionalized isolation groups to the alcoholic hydroxyl group of the compound (7a) by nucleophilic substitution or Steglich esterification to obtain compounds (8a-8c);

S7, the compounds (8a-8c) are condensed with receptor molecules to obtain the chromophores H1-H3;

Wherein, the compounds (1)-(H3) have the following structures:

Preferably, the method for synthesizing chromophore H4 comprises the following steps:

P1, using 4-(methyl(2-((tetrahydro-2H-pyran-2-yl)oxy)ethyl)amino)benzaldehyde (i.e., compound (2b)) and isophorone (compound 1) to obtain compound (3b) by knoevenagel condensation reaction in the presence of sodium ethoxide and 2-mercaptoethanol;

P2, inserting a tert-butyldiphenylsilyl protecting group onto the alcoholic hydroxyl group of the compound (3b) to obtain a compound (4b);

P3, the compound (4b) and diethyl cyanomethyl phosphate are reacted by Wittig-Hornor reaction to obtain compound (5b);

P4, reducing the cyano group in the compound (5b) by diisobutylaluminum hydride to obtain an aldehyde compound (6b);

P5, the compound (6b) is subjected to alkaline hydrolysis to remove the protecting group to obtain compound (7b);

P6, connecting a self-assembling isolation group to the alcoholic hydroxyl group of the compound (7b) by nucleophilic substitution or Steglich esterification to obtain compound (8d);

P7, the compound (8d) is subjected to acid hydrolysis to obtain compound (9);

P8, connecting a trifurcated isolation group to the alcoholic hydroxyl group of the compound (9) by nucleophilic substitution or Steglich esterification to obtain compound (10);

P9, the compound (10) and the receptor molecule are condensed to obtain the chromophore H4;

Wherein, the compounds (1)-(H4) have the following structures and the synthesis steps are as follows:

More preferably, the method for synthesizing H1, H2 and H3 specifically comprises the following steps:

S1. Under argon protection, slowly dissolve metallic sodium in ethanol, add 2-mercaptoethanol in an ice bath, mix thoroughly and stir, then add the compound (1) to react for 1 hour, then add the compound (2a), reflux at 65° C. overnight, extract and concentrate with ethyl acetate after the reaction is complete, purify by silica gel chromatography with ethyl acetate and petroleum ether as eluents, to obtain compound (3a);

S2. Slowly add imidazole and tert-butyldimethylsilyl chloride to the N,N-dimethylamide solution of the compound (3a) in a flask, react at room temperature for 3 hours under argon protection, extract with ethyl acetate, purify by silica gel chromatography, and purify with ethyl acetate and petroleum ether as eluents to obtain compound (4a);

S3. In an argon atmosphere, diethyl cyanomethyl phosphate was slowly added to a tetrahydrofuran solution of sodium hydride under ice bath conditions, and the compound (4a) was added, and the reaction was refluxed at 68° C. overnight. After the reaction was completed, the solvent was dried in vacuo, extracted with ethyl acetate, and purified by silica gel chromatography using ethyl acetate and petroleum ether as eluents to obtain compound (5a);

S4, slowly adding a hexane solution of diisobutylaluminum hydride to a dichloromethane solution of the compound (5a), reacting for a period of time at -78°C under an argon protective atmosphere, adding a certain amount of dichloromethane and water at 0°C for quenching, filtering after the reaction is completed, extracting the filtrate with dichloromethane, concentrating, and purifying by silica gel chromatography using ethyl acetate and petroleum ether as eluents to obtain compound (6a);

S5. The compound (6a) is subjected to acid hydrolysis to remove the dimethyl tert-butyl silicon group, extracted with dichloromethane, and purified by silica gel chromatography using ethyl acetate and petroleum ether as eluents to obtain compound (7a);

S6. Slowly add dichloromethane solution to a flask containing 4-dimethylaminopyridine, 1-ethyl-3(3-dimethylpropylamine)carbodiimide and 3,5-bis(benzyloxy)benzoic acid or 3,5-bis((3,4,5-trifluorobenzyl)oxy)benzoic acid or 3,5-bis((perfluorophenyl)methoxy)benzoic acid, react for a period of time at 0°C under a protective atmosphere, then slowly add the dichloromethane solution of the compound (7a), reflux at 40°C overnight, extract the organic phase with dichloromethane, evaporate the solvent, and purify by silica gel chromatography using ethyl acetate and petroleum ether as eluents to obtain compounds (8a-8c);

S7, the compound (8a-8c) reacts with the receptor molecule at 65° C. under argon protection, and the product is concentrated and purified by silica gel chromatography using ethyl acetate and petroleum ether as eluents to obtain the chromophores H1-H3;

Wherein, the receptor molecule is 2-(3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ethylidene)malononitrile.

More preferably, the method for synthesizing H4 specifically comprises the following steps:

P1. Under argon protection, slowly dissolve metallic sodium in ethanol, add 2-mercaptoethanol in an ice bath, mix thoroughly and stir, then add the compound (1) to react for 1 hour, then add the compound (2b), reflux at 65° C. overnight, extract and concentrate with ethyl acetate after the reaction is complete, purify by silica gel chromatography with ethyl acetate and petroleum ether as eluents to obtain compound (3b);

P2, slowly add imidazole and tert-butyldimethylsilyl chloride to the N,N-dimethylamide solution of the compound (3b) in a flask, react at room temperature for 3 hours under argon protection, extract with ethyl acetate, purify by silica gel chromatography, and purify with ethyl acetate and petroleum ether as eluents to obtain compound (4b);

P3. In an argon atmosphere, diethyl cyanomethylphosphonate was slowly added to a tetrahydrofuran solution of sodium hydride under ice bath conditions, and the compound (4b) was added, and the reaction was refluxed at 65° C. overnight. After the reaction was completed, the solvent was dried in vacuo, extracted with ethyl acetate, and purified by silica gel chromatography using ethyl acetate and petroleum ether as eluents to obtain compound (5b);

P4, slowly adding a hexane solution of diisobutylaluminum hydride to a dichloromethane solution of the compound (5b), reacting for a period of time at -78°C under an argon protective atmosphere, adding a certain amount of dichloromethane and water at 0°C for quenching, filtering after the reaction is completed, extracting the filtrate with dichloromethane, concentrating, and purifying by silica gel chromatography using ethyl acetate and petroleum ether as eluents to obtain compound (6b);

P5. Compound (6b) is subjected to alkaline hydrolysis to remove the tert-butyldiphenylsilyl chloride protecting group, extracted with ethyl acetate, and purified by silica gel chromatography using ethyl acetate and petroleum ether as eluents to obtain compound (7b);

P6, slowly add dichloromethane solution to a flask containing 4-dimethylaminopyridine, 1-ethyl-3 (3-dimethylpropylamine) carbodiimide and 3,5-bis ((3,4,5-trifluorobenzyl) oxy) benzoic acid, react for a period of time at 0 ° C. under a protective atmosphere, slowly add the dichloromethane solution of the compound (7b), heat and reflux to react, extract the organic phase with dichloromethane, evaporate the solvent and purify it by silica gel chromatography using ethyl acetate and petroleum ether as eluents to obtain compound (8d);

P7, the compound (8d) was subjected to acid hydrolysis to remove the (2-tetrahydropyran) protecting group, extracted with ethyl acetate, and purified by silica gel chromatography using ethyl acetate and petroleum ether as eluents to obtain compound (9);

P8, slowly add dichloromethane solution to a flask containing 4-dimethylaminopyridine, 1-ethyl-3 (3-dimethylpropylamine) carbodiimide and 6,6',6'-((ethane-1,1,1-triacyltris(benzene-4,1-diacyl))tri(oxy)trihexanoic acid, react for a period of time at 0°C under a protective atmosphere, slowly add the dichloromethane solution of the compound (9), heat and reflux to react, extract the organic phase with dichloromethane, spin dry to remove the solvent, and purify by silica gel chromatography using dichloromethane and ethyl acetate as eluents to obtain compound (10);

P9, the compound (10) and the acceptor molecule react under argon protection conditions, and the product is concentrated and purified by silica gel chromatography using ethyl acetate and petroleum ether as eluents to obtain the chromophore H4; wherein the acceptor molecule is 2-(3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ethylidene)malononitrile.

In a third aspect, the present invention provides an application of the organic optical nonlinear chromophores H1, H2, H3 and H4 based on the single donor self-assembly structure, specifically as electro-optical materials and in electro-optical modems.

The chromophore is prepared as an application of an electro-optical film, specifically, the chromophore is dissolved in redistilled 1,1,2-trichloroethane, the dissolved chromophore solution is filtered through a 0.2 mm PTFE filter, the filtered solution is spin-coated on an ITO glass substrate, and the solvent is removed to obtain the electro-optical film.

The beneficial effects of the present invention are:

1. The present invention provides a novel, self-assembled single donor structure. Four dendron macromolecules H1, H2, H3 and HLD1 were synthesized by introducing aromatic dendrons (HD), trifluorophenyl dendrons (TFD), pentafluorophenyl dendrons (PFD) and anthracene rings (AH) into the donor end and bridge end of the push-pull tetraene chromophore. In addition, a three-branched trifluorophenyl dendrimer containing multi-chromophore H4 was synthesized. Through the supramolecular self-assembly of the π-π interaction of HD-PFD/PFD-AH/TFD-TFD, the dipole-dipole interaction of the chromophore at high loading density is minimized and the eccentric order of the chromophore is maximized. High polarization efficiency and EO coefficient are obtained through the supramolecular self-assembly strategy of dendritic or multi-chromophore structures and π-π stacking of fluoroaromatics and aromatic hydrocarbons.

2. The present invention also provides a series of new chromophore structures for intermolecular assembly. Pure films containing 1:1 H1:H3, 1:2 H3:HLD1 and H4 respectively obtain large r ₃₃ (328, 317 and 279 pm/V) at 1310 nm. In addition, the non-covalent cross-linking bonds formed by π-π stacking between chromophores can improve the long-term arrangement stability of the material. After annealing at room temperature for 1000 hours, the initial electro-optic coefficient of the electrode self-assembled film can be maintained above 95%.

According to DFT theoretical calculations, this type of chromophore has a high hyperpolarizability. In addition to the large first-order hyperpolarizability, the special structure of the functionalized self-assembly group that isolates the intermolecular interactions also has a large spatial effect, which also leads to a higher polarization efficiency.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention is further described using the accompanying drawings, but the embodiments in the accompanying drawings do not constitute any limitation to the present invention. A person skilled in the art can obtain other drawings based on the following drawings without creative work.

FIG1 is the general structural formula of chromophores H1-H3 prepared in Example 1 of the present invention;

FIG2 is a specific structural formula of chromophores H1-H3 prepared in Example 1 of the present invention;

FIG3 is a synthetic route diagram of chromophores H1-H3 prepared in Example 1 of the present invention;

FIG4 is the structural formula of chromophore H4 prepared in Example 2 of the present invention;

FIG5 is a synthetic route diagram of chromophore H4 prepared in Example 2 of the present invention;

FIG6 is a thermogravimetric graph of chromophores H1-H4 prepared in Example 1 and Example 2 of the present invention;

FIG7 is a DSC graph of chromophores H1-H4 prepared in Examples 1 and 2 of the present invention;

FIG8 is a UV-visible spectroscopic diagram of chromophores H1-H4 prepared in Example 1 and Example 2 of the present invention in chloroform solvent;

9 is a UV-visible spectroscopic graph of chromophores H1-H4, H1-H3 mixture, and H3-HLD1 mixture in an electro-optical film prepared in Examples 1 and 2 of the present invention;

FIG10 is a graph showing ultraviolet spectra of chromophores H1-H4 prepared in Examples 1 and 2 of the present invention in different solvents;

FIG11 is a result of theoretical calculation of energy levels of chromophores H1-H4 prepared in Examples 1 and 2 of the present invention;

FIG12 is a graph showing the relationship between the electro-optic coefficient and the molecular density of the chromophores H1-H4 prepared in Examples 1 and 2 of the present invention;

FIG. 13 is a polarization efficiency curve (r ₃₃ value) of chromophores H1-H4 prepared in Examples 1 and 2 of the present invention as the electric field changes.

DETAILED DESCRIPTION

In order to more clearly illustrate the present invention and have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be construed as limiting the applicable scope of the present invention.

Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.

The present invention is further described in conjunction with the following examples.

Example 1

An organic optical nonlinear chromophore based on a single donor self-assembly structure includes H1-H3, and its structure is shown in FIG4. The chromophore H4 exhibits good solubility in common organic solvents, such as ethyl acetate, ethanol and acetone.

The preparation process includes the synthesis of chromophore H4, and the steps are as follows:

P1. Under argon atmosphere and ice bath conditions, sodium metal (88.23mmol, 2.0g) was added to a two-necked flask, dissolved with an appropriate amount of ethanol, and then 2-mercaptoethanol (88.23mmol, 6.89g, 7.65mL) was added. After 20mins, compound 1 (132.35mmol, 20.68g) was added. After 1h, compound 2b (88.23mmol, 23.23g) dissolved with an appropriate amount of ethanol was added. The reaction was refluxed overnight at 65°C, and after being spin-dried, EA was used for extraction. The mixture was spin-dried and passed through a chromatography column. The eluent ratio was 1:8-1:3 (EA:PE) to obtain compound 3b (30.30g, 65.9mmol) with a yield of 74.7%, which was a red oily liquid.

MS (MALDI) (M ⁺ , C ₂₆ H ₃₇ NO ₄ S): calcd: 459.24; found: 459.25. ¹ H NMR (600MHz, CDCl ₃ ) δ7.92 (d, J = 16.2Hz, 1H, CH), 7.46(d,J＝8.9Hz,2H,ArH),7.07(d,J＝16.1Hz,1H,CH),6.71(d,J＝8.9Hz,2H,ArH),4.58–4.56(m,1H, OCH),3.95–3.85(m,2H,NCH ₂ ),3.67–3.57(m,6H,OCH ₂ ),3.06(s,3H,NCH ₃ ),2.83–2.80(m,2H,SCH ₂ ),2.64(s,2H,CH ₂ ),2.44(s,2H,CH ₂ ),1.82–1.75(m,2H,CH ₂ ),1.72–1.64(m,2H,CH ₂ ),1.59–1.55( m,2H,CH ₂ ),1.08(s,6H,CH ₃ ). ¹³ C NMR (151MHz, CDCl ₃ ) δ197.5,160.6,150.4,138.8,129.6,126.9,123.9,122.9,111.9,99.0,64.7,62.2 ,60.2,52.2,51.7,41.4,39.0,32.4,30.6,28.4,25.4,19.3.

P2. Under argon atmosphere, imidazole (79.08mmol, 5.38g) and tert-butyldiphenylsilyl chloride (79.08mmol, 21.73g) were added to a two-necked flask, and then compound 3b (65.9mmol, 30.30g) dissolved in an appropriate amount of DMF was added, and the mixture was reacted at room temperature for 3h. After being spin-dried, the mixture was extracted with EA and passed through a chromatography column with an eluent ratio of 1:10-1:5 (EA:PE) to obtain compound 4b (31.32g, 44.87mmol) with a yield of 68.1%, which was a red oily liquid.

MS (MALDI) (M ⁺ , C ₄₂ H ₅₅ NO ₄ SSi): calcd: 697.36; found: 697.15. ¹ H NMR (600MHz, CDCl ₃ ) δ7.92 (d, J = 16.2Hz, 1H, CH), 7.67-7.64(m,4H,ArH),7.46–7.38(m,4H,ArH),7.37-7.33(m,4H,ArH),6.99(d,J＝16.2Hz,1H,CH),6.69(d ,J＝8.9Hz,2H,ArH),4.62–4.60(m,1H,OCH),3.77(t,J＝6.8Hz,2H,NCH ₂ ),3.97–3.79(m,2H,OCH ₂ ),3.65-3.62(m,2H,OCH ₂ ),3.62–3.47(m,2H,OCH ₂ ),3.08(s,3H,NCH ₃ ),2.97(t,J＝6.8Hz,2H,SCH ₂ ) ,2.58(s,2H,CH ₂ ),2.36(s,2H,CH ₂ ),1.87–1.77(m,2H,CH ₂ ),1.64–1.56(m,2H,CH ₂ ),1.55–1.49(m ,2H,CH ₂ ),1.05(m,15H,CH ₃ ). ¹³ C NMR (151MHz, CDCl ₃ )δ195.8,157.8,150.1,137.2,135.6,133.7,129.6,129.3,127.7,123.6,111.9,99.0,64.8,63.5,62.2,52.2,51.9,41.3,39.1,36.3,32.2,30.6 ,28.4,26.9,25.4 ,19.3.

P3. Under argon atmosphere, sodium hydride (60%, 189.0mmol, 7.17g) was added to a two-necked flask, dissolved with an appropriate amount of THF, and then diethyl cyanomethylphosphonate (189.0mmol, 33.65g) was added dropwise. When the solution became clear, compound 4b (47.5mmol, 33.15g) dissolved in THF was added. The reaction was refluxed overnight at 68°C. After the solvent was dried by spin drying, it was extracted with EA and purified by chromatography column. The eluent ratio was 1:15-1:6 (EA:PE) to obtain compound 5b (23.13g, 32.1mmol). The yield was 67.5%, which was a red oily liquid.

MS (MALDI) (M ⁺ , C ₄₄ H ₅₆ N ₂ O ₃ SSi): calcd: 720.37; found: 720.22. ¹ H NMR (600MHz, CDCl ₃ ) δ7.84 (d, J＝16.2Hz, 1H, CH ),7.67–7.63(m,4H,ArH),7.45–7.36(m,8H,ArH),6.84(d,J＝16.2Hz,1H,CH),6.69(d,J＝8.9Hz,2H,ArH ),6.20(d,J＝14.8Hz,1H,CH),4.62–4.60(m,1H,OCH),3.96–3.80(m,2H,NCH ₂ ),3.74(t,J＝6.8Hz,2H, OCH ₂ ),3.66–3.50(m,4H,OCH ₂ ),3.07(s,3H,NCH ₃ ),2.73(t,J＝6.8Hz,2H,SCH ₂ ),2.51(s,2H,CH ₂ ),2.42 (s,2H,CH ₂ ),1.85–1.70(m,2H,CH ₂ ),1.62–1.58(m,2H,CH ₂ ),1.55–1.50(m,2H,CH ₂ ),1.07(s,9H ,CH ₃ ),0.98(s,6H,CH ₃ ). ¹³ C NMR (151MHz, CDCl ₃ )δ158.5,149.7,149.1,135.5,134.9,133.5,129.7,128.8,127.7,125.9,124.1,119.3,99.0,94.6,64.8,63.1,62.2,52.3,43.4,41.6,39.1,37. 6,30.6,30.1,28.0 ,26.9,25.4,19.4,19.2.

P4. Under argon atmosphere, compound 5b (32.10 mmol, 23.13 g) dissolved in DCM was added to a two-necked flask, and diisobutylaluminum hydride (1.0 M, 64.20 mmol, 64.20 mL) was added dropwise at -78 °C. After reacting at low temperature for 3 h, 10 mL of DCM and 10 mL of water were slowly added at 0 °C, quenched for 1 h, extracted with DCM, and the solvent was dried by spin drying and purified by chromatography column. The eluent ratio was 1:10-1:5 (EA:PE), and compound 6b (18.91 g, 26.12 mmol) was obtained. The yield was 81.4%, which was a dark red oily liquid.

MS (MALDI) (M ⁺ , C ₄₄ H ₅₇ NO ₄ SSi): calcd: 723.38; found: 723.40. ¹ H NMR (600MHz, CDCl ₃ )δ10.12(d,J＝8.0Hz,1H,CHO),7.95(d,J＝16.2Hz,1H,CH),7.63(d,J＝6.7Hz,4H,ArH),7.42–7.39(m ,4H,ArH),7.35–7.33(m,4H,ArH,CH),6.97(d,J＝8.0Hz,1H,ArH),6.84(d,J＝16.2Hz,1H,CH),6.68(d ,J＝8.9Hz,1H,CH),4.62–4.60(m,1H,OCH),3.96–3.80(m,2H,NCH ₂ ),3.76(t,J＝7.0Hz,2H,OCH ₂ ),3.65 –3.50(m,4H,OCH ₂ ),3.07(s,3H,NCH ₃ ),2.74(t,J＝7.0Hz,2H,SCH ₂ ),2.65(s,2H,CH ₂ ),2.45(s,2H,CH ₂ ),1.83–1.70 (m,2H,CH ₂ ),1.62–1.57(m,2H,CH ₂ ),1.56–1.50(m,2H,CH ₂ ),1.05(s,9H,CH ₃ ),1.00(s,6H,CH ₃ ). ¹³ C NMR (151MHz, CDCl ₃ )δ191.6,156.6,150.1,149.7,135.5,134.8,133.6,128.2,129.6,128.9,127.7,126.8,124.8,111.9,99.0,64.8,63.3,62.2,52.3,41.6,39.8,3 9.0,37.3,30.6,30.0 ,28.3,26.9,25.4,19.4,19.2.

P5. In an argon environment, compound 6b (22.40 mmol, 16.22 g) was added to a two-necked flask, which was dissolved in THF, and tetraisobutylammonium fluoride (1.0 M, 44.80 mmol, 44.8 mL) was added. The mixture was reacted at room temperature for 1 h. The solvent was removed in vacuo and extracted with EA. The mixture was purified by chromatography with an eluent ratio of 1:6-2:1 (EA:PE) to obtain a dark red product compound 7b (9.79 g, 20.16 mmol) with a yield of 90.0%.

MS (MALDI) (M ⁺ , C ₂₈ H ₃₉ NO ₄ S): calcd: 485.26; found: 485.21. ¹ H NMR (600MHz, CDCl ₃ ) δ 10.13 (d, J = 8.1Hz, 1H, CH), 7.95(d,J＝16.2Hz,1H,CHO),7.43(d,J＝8.9Hz,2H,ArH),7.00(d,J＝8.1Hz,1H,ArH),6.90(d,J＝16.1Hz ,1H,CH),6.71(d,J＝8.9Hz,2H,ArH,CH),4.59–4.57(m,1H,OCH),3.93–3.81(m,2H,NCH ₂ ),3.65(t,J ＝6.0Hz,2H,OCH ₂ ),3.61–3.46(m,4H,OCH ₂ ),3.05(s,3H,NCH ₃ ),2.77(t,J＝6.1Hz,2H,SCH ₂ ),2.75(s,2H,CH ₂ ),2.52 (s,2H,CH ₂ ),1.59–1.48(m,6H,CH ₂ ),1.04(s,6H,CH ₃ ). ¹³ C NMR (151MHz, CDCl ₃ )δ191.6,135.5,128.9,127.3,126.7,124.7,124.3,112.0,99.0,64.8,62.2,61.22,52.2,41.73,39.9,39.0,38.2,30.6,30.1,28.3,25.4,19.4.

P6. Under argon atmosphere, 1-ethyl-3(3-dimethylpropylamine)carbodiimide (25.0mmol, 4.8g), 4-dimethylaminopyridine (2.5mmol, 0.31g), 3,5-bis((3,4,5-trifluorobenzyl)oxy)benzoic acid (7.5mmol, 3.32g) were added to a two-necked flask, and an appropriate amount of DCM was added at 0°C. After 45mins, compound 7b (6.26mmol, 3.04g) dissolved in an appropriate amount of DCM was added. After 2h, the reaction was refluxed overnight at 40°C, extracted with DCM, and the solvent was removed in vacuo and purified by chromatography column. The eluent ratio was 1:8-1:5 (EA:PE), and compound 8d (5.61g, 6.1mmol) was obtained. The yield was 97.8%, and it was a dark red oily liquid.

MS (MALDI) (M ⁺ , C ₄₉ H ₄₉ F ₆ NO ₇ S): calcd: 909.31; found: 909.21. ¹ H NMR (600MHz, CDCl ₃ ) δ 10.07 (d, J=8.1Hz, 1H, CHO ),7.83(d,J＝16.2Hz,1H,CH),7.23(d,J＝8.8Hz,2H,ArH),7.16(d,J＝2.4Hz,2H,ArH),6.98–6.91(m, 5H,ArH,CH),6.76(d,J＝16.1Hz,1H,CH),6.67–6.65(m,1H,ArH),6.48(d,J＝8.9Hz,2H,ArH),4.88(s, 4H,OCH ₂ ),4.49–4.47(m,1H,OCH),4.30(t,J＝6.2Hz,2H,NCH ₂ ),3.82–3.68(m,2H,OCH ₂ ),3.51–3.38(m,4H,OCH ₂ ),2.92(s,3H,NCH ₃ ),2.88(t,J＝6.2Hz,2H,SCH ₂ ),2.66(s,2H,CH ₂ ),2.38(s,2H,CH ₂ ),1.64–1.58 (m,2H,CH ₂ ),1.51–1.40(m,4H,CH ₂ ),0.95(s,6H,CH ₃ ). ¹³ C NMR (151MHz, CDCl ₃ )δ191.5,165.6,159.1,156.3,152.1(dm, ¹ J _FC ～253Hz),151.0,150.5(dm, ¹ J _FC ～260Hz),149.7,140.1(dm, ¹ J _FC ～246Hz),138.5(dm, ¹ J _FC ~258Hz),135.3,132.3,128.9,126.9,124.6,124.3,111.8,111.2,108.6,107.6,99.1,68.5,64.7,63.7,62.2,52.1,41.7,39.8,38.9,33.4,30.9 ,30.6,30.1, 28.3,25.4,19.4.

P7, add compound 8d (6.17 mmol, 5.61 g) dissolved in an appropriate amount of acetone into a single-necked flask, add 1N HCl (1N, 12.34 mmol, 12.34 mL), react at room temperature for 2 h, then add sodium bicarbonate for neutralization, spin dry, extract with EA, spin dry and pass through a chromatography column, the eluent ratio is 1:6-2:1 (EA:PE), and a dark red product compound 9 (3.91 g, 4.73 mmol) is obtained, and the yield is: 76.4%;

MS (MALDI) (M ⁺ , C ₄₄ H ₄₁ F ₆ NO ₆ S): calcd: 825.26; found: 825.15.1H NMR (600MHz, CDCl ₃ ) δ 10.17 (d, J = 8.1Hz, 1H, CHO) ,7.93(d,J＝16.2Hz,1H,CH),7.32(d,J＝8.8Hz,2H,ArH),7.26(d,J＝2.4Hz,2H,ArH),7.09–7.01(m,5H ,ArH,CH),6.85(d,J＝16.2Hz,1H,CH),6.77(t,J＝2.4Hz,1H,ArH),6.60(d,J＝8.7Hz,2H,ArH),4.99( s,4H,OCH ₂ ), 4.40 (t, J = 6.2Hz, 2H, NCH ₂ ), 3.82 (t, J = 5.7Hz, 2H, OCH ₂ ), 3.50 (t, J = 5.7Hz, 2H, OCH ₂ ), 3.00 (s ,3H,NCH ₃ ),2.97(t,J＝6.2Hz,2H,SCH ₂ ),2.76(s,2H,CH ₂ ),2.48(s,2H,CH ₂ ),1.05(s,4H,CH ₃ ). ¹³ CNMR(151MHz, CDCl ₃ )δ191.6,165.6,159.1,156.2,152.2(dm, ¹ J _FC ~260Hz),150.9,150.5(dm, ¹ J _FC ～256Hz),140.2(dm, ¹ J _FC ～246Hz),138.5(dm, ¹ J _FC ～253Hz),135.1,132.7,132.3,128.8,128.4,127.0,124.8,112.3,111.2,108.6,107.7,68.5, 63.6,60.2,54.7,41.7,39.8,38.8,33.5,30.1,28.3.

P8. In an argon atmosphere, 1-ethyl-3-(3-dimethylpropylamine)carbodiimide (12.02 mmol, 2.31 g), 4-dimethylaminopyridine (1.20 mmol, 0.15 g), 6,6',6'-((ethane-1,1,1-triacyltri(benzene-4,1-diacyl))tri(oxy)trihexanoic acid (0.89 mmol, 0.58 g) were added to a two-necked flask, and an appropriate amount of D CM, after 45mins, add compound 9 (4.01mmol, 3.31g) dissolved in an appropriate amount of DCM, after 2h, reflux the reaction at 40°C overnight, extract with DCM, remove the solvent in vacuo and purify with a chromatography column, the eluent ratio is 1:50-1:10 (EA:DCM), to obtain compound 10 (2.44g, 0.79mmol), the yield is 88.2%, it is a dark red oily liquid;

MS (MALDI) (M ⁺ ,C ₁₇₀ H ₁₆₅ F ₁₈ N ₃ O ₂₄ S ₃ ): calcd: 3070.07; found: 3070.14. ¹ H NMR (600MHz, CDCl ₃ )δ10.16(d,J＝8.0Hz,3H,CHO),7.93(d,J＝16.2Hz,3H,CH),7.33(d,J＝8.8Hz,6H,ArH),7.25(d,J ＝2.3Hz,6H,ArH),7.08–7.00(m,15H,ArH,CH),6.98(d,J＝8.8Hz,6H,ArH),6.84(d,J＝16.1Hz,3H,CH), 6.78–6.75(m,9H,ArH),6.58(d,J＝8.9Hz,6H,ArH),4.97(s,12H,OCH ₂ ),4.40(t,J＝6.2Hz,6H,NCH ₂ ), 4.25(t,J=6.0Hz,6H,OCH ₂ ),3.91(t,J＝6.3Hz,6H,OCH ₂ ),3.60(t,J＝6.0Hz,6H,OCH ₂ ),2.99(s,9H,NCH ₃ ),2.97(t,J＝6.2Hz ,6H,SCH ₂ ),2.75(s,6H,CH ₂ ),2.47(s,6H,CH ₂ ),2.30(t,J＝7.5Hz,6H,CH ₂ ),2.08(d,J＝20.0Hz ,3H,CH ₃ ),1.78–1.73(m,6H,CH ₂ ),1.68–1.62(m,6H,CH ₂ ),1.50–1.43(m,6H,CH ₂ ),1.04(s,18H,CH ₃ ) ^.13C NMR(151MHz,CDCl ₃ )δ191.5,173.5,171.2,165.5,159.1,157.0,156.2,152.1(dm, ¹ J _FC ～255Hz),150.9(dm, ¹ J _FC ～257Hz),150.5,149.4,141.7,140.1 (dm, ¹ J _FC ~258Hz),138.5(dm, ¹ J _FC ~247Hz),135.1,132.8,132.3,129.6,128.9,127.3,127.0,125.1,124.7,113.5,111.9,111.2,108.6,107.6,68.6,67.5,63.7,61.2,60.4,50.7, 50.6,41.7,39.8, 38.6,34.1,33.5,30.7,30.1,29.0,28.3,25.7,24.6,21.1,14.2.

Synthesis of chromophore H4:

Under argon atmosphere, compound 10 (0.32 mmol, 1.01 g) and 2-(3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ethylidene)malononitrile (1.15 mmol, 0.36 g) were added to a two-necked flask, dissolved with 5-6 mL of ethanol, reacted at 65 ° C for 3 h, and dried by chromatography column with an eluent ratio of 1:7-1:1 (EA:PE) to obtain chromophore H4 (0.53 g, 0.13 mmol) with a yield of 41.8%;

HRMS(ESI)(M ⁺ ,C ₂₁₈ H ₁₈₃ F ₂₇ N ₁₂ O ₂₄ S ₃ ): calcd: 3962.2277; found: 3962.2223. ¹ H NMR (600MHz, CDCl ₃ )δ7.98(d,J＝15.9Hz,6H,CH),7.63–7.49(m,15H,ArH),7.42(d,J＝12.4Hz,3H,CH),7.35(d,J＝8.9Hz ,6H,ArH),7.22(d,J＝2.3Hz,6H,ArH),7.05–7.02(m,12H,ArH),6.99–6.94(m,9H,ArH,CH),6.76(t,J＝ 6.1Hz,9H,ArH),6.57(d,J＝8.9Hz,6H,ArH),6.48(d,J＝14.6Hz,3H,CH),4.96(s,12H,OCH ₂ ),4.37(t, J＝6.2Hz,6H,NCH ₂ ),4.25(t,J＝6.0Hz,6H,OCH ₂ ),3.90(t,J＝6.3Hz,6H,OCH ₂ ),3.62(t,J＝6.0Hz,6H,OCH ₂ ),3.02(s ,9H,NCH ₃ ),2.95(t,J＝6.3Hz,6H,SCH ₂ ),2.54–2.45(m,6H,CH ₂ ),2.35–2.20(m,12H,CH ₂ ),1.79–1.72( m,6H,CH ₂ ),1.68–1.61(m,9H,CH ₃ ,CH ₂ ),1.50–1.42(m,6H,CH ₂ ),0.98(s,9H,CH ₃ ),0.89(s,9H , CH ₃ ). ¹³ C NMR (151MHz, CDCl ₃ ) δ175.4, 173.5, 165.4, 162.9, 159.1, 157.0, 154.2, 152.2 (dm, ¹ J _FC ~ 255Hz), 150.5 (dm, ¹ J _FC ~ 259Hz), 150.1, 147.3, 141.7 ,140.2(dm, ¹ J _FC ~249Hz),138.5(dm, ¹ J _FC ~258Hz),137.79,132.7,132.1,131.4,129.9,129.7,129.2,128.3,126.8,125.0,124.7,117.3,113.5,112.0,111.2,108.7,107.4,68.5,67.5,6 3.5,61.1,58.4,50.6, 41.7,41.1,38.7,34.1,30.4,29.0,28.6,27.8,25.7,24.6.

Example 2

An organic optical nonlinear chromophore based on a single donor self-assembly structure includes H1-H3, and its structure is shown in Figure 2. The chromophore H1-H3 exhibits good solubility in common organic solvents, such as ethyl acetate, ethanol and acetone.

The preparation process includes the synthesis of chromophores H1-H3, and the steps are as follows:

S1. Under argon atmosphere and ice bath conditions, sodium metal (32.03mmol, 0.74g) was added to a two-necked flask, dissolved with an appropriate amount of ethanol, and then 2-mercaptoethanol (32.03mmol, 2.26mL) was added. After 20mins, compound 1 (32.03mmol, 4.94g) was added. After 1h, compound 2a (32.03mmol, 9.4g) dissolved with an appropriate amount of ethanol was added. The reaction was refluxed overnight at 65°C, and after being spin-dried, EA was used for extraction. The mixture was spin-dried and passed through a chromatography column. The eluent ratio was 1:10-1:5 (EA:PE) to obtain compound 3a (6.7g, 13.6mmol) with a yield of 42.5%, which was a red oily liquid.

MS (MALDI) (M ⁺ , C ₂₇ H ₄₃ NO ₃ SSi): calcd: 489.79; found: 489.81. ¹ H NMR (300MHz, CDCl ₃ )d 7.92 (d, J=16.1Hz, 1H, CH), 7.46 (d,J＝8.6Hz,2H,ArH),7.04(d,J＝16.1Hz,1H,CH),6.68(d,J＝8.7Hz,2H,ArH),3.80–4.02(m,4H,NCH ₂ ,OCH ₂ ),3.48–3.60(m,4H,OCH ₂ ,SCH ₂ ),3.04(s,3H,NCH ₃ ),2.59(m,2H,CH ₂ ),2.45(m,2H,CH ₂ ),1.07(s,6H,CH ₃ ),0.87(s,9H,CH ₃₎ ,0.01(s,6H,CH ₃ ). ¹³ C{1H}NMR(126MHz,CDCl ₃ )d 197.05,160.19,149.93 ,138.56,129.33,127.09,126.69,123.69,122.42,111.62,60.29,60.13,54.31,51.45,40.94,38.99,38.42,31.96,28.17,25.70,17.97,5.45.

S2. In an argon atmosphere, imidazole (14.4 mmol, 0.98 g) and tert-butyldimethylsilyl chloride (14.4 mmol, 2.17 g) were added to a two-necked flask, and then compound 3a (2.93 g, 6.0 mmol) dissolved in an appropriate amount of DMF was added, and the mixture was reacted at room temperature for 3 h. After being spin-dried, the mixture was extracted with EA and passed through a chromatography column with an eluent ratio of 1:10-1:7 (EA:PE) to obtain compound 4a (3.02 g, 5.0 mmol) with a yield of 83.3%, which was a red oily liquid.

MS (MALDI) (M ⁺ , C ₃₃ H ₅₇ NO ₃ SSi ₂ ): calcd: 604.05; found: 603.95. ¹ H NMR (300MHz, CDCl ₃ )d 7.89 (d, J=16.2Hz, 1H, CH), 7.44(d,J＝8.6Hz,2H,ArH),6.98(d,J＝16.2Hz,1H,CH),6.66(d,J＝8.7Hz,2H,ArH),3.82–3.67(m,6H, CH ₂ ),3.51(m,2H,CH ₂ ),2.96–2.78(m,3H,NCH ₃ ),2.59(s,2H,CH ₂ ),2.39(s,2H,CH ₂ ),1.06(s, 6H,CH ₃ ),0.91–0.77(m,18H,CH ₃ ),0.08–0.02(m,12H,CH ₃ ). ¹³ C{1H}NMR(126MHz,CDCl ₃ )d 195.67,157.70,150.03,137.20,129.20,128.01 ,123.97,123.37,111.84,62.79,60.12,54.46,51.87,41.18,39.13,36.53,32.14,30.62,28.26,25.77,18.14,5.45,5.63.

S3. Under argon atmosphere, sodium hydride (60%, 20 mmol, 0.80 g) was added to a two-necked flask. After dissolving with an appropriate amount of THF, diethyl cyanomethyl phosphate (20.0 mmol, 3.54 g) was added dropwise. When the solution became clear, compound 4a (5.0 mmol, 3.02 g) dissolved in THF was added. The reaction was refluxed overnight at 68°C. After the solvent was dried by spin drying, it was extracted with EA and purified by chromatography column. The eluent ratio was 1:15-1:8 (EA:PE). Compound 5a (2.3 g, 3.7 mmol) was obtained. The yield was 74%, which was a red oily liquid.

(M ⁺ ,C ₃₅ H ₅₈ N ₂ O ₂ SSi ₂ ): calcd: 627.09; found: 627.13. ¹ H NMR (300MHz, CDCl ₃ )d 7.84 (d, J = 16.1Hz, 1H, CH), 7.38 ( d,J＝8.4Hz,2H,ArH),6.83(d,J＝16.1Hz,1H,CH),6.64(d,J＝8.4Hz,2H,ArH),6.23(s,1H,CH),3.82 –3.61(m,4H,CH ₂ ),3.48(m,2H,CH ₂ ),2.99(m,3H,NCH ₃ ),2.67(m,2H,CH ₂ ),2.53(s,2H,CH ₂ ),2.43(s,2H,CH ₂ ),0.99(s,6H,CH ₃ ),0.87(m,18H,CH ₃ ),0.05–0.02(m,12H,CH ₃ ). ¹³ C{1H}NMR (126MHz, CDCl ₃ )d 158.13,149.59,148.68,134.79,128.63,125.94,124.50,123.94,118.84,111.66,94.47,62.11,60.34,54.37,38.86 30.57,29.8829.53,27.84,25.76,22.51,17.99,14.01,5.45,5.61.

S4. Under argon atmosphere, compound 5a (3.7 mmol, 2.3 g) dissolved in DCM was added to a two-necked flask, and diisobutylaluminum hydride (1 M, 7.4 mmol, 7.4 mL) was added dropwise at -78 °C. After reacting at low temperature for 3 h, 10 mL of DCM and 10 mL of water were slowly added at 0 °C, quenched for 1 h, extracted with DCM, and the solvent was dried by spin drying. Purification was performed by chromatography column with an eluent ratio of 1:10-1:7 (EA:PE) to obtain compound 6a (1.54 g, 2.44 mmol) with a yield of 66%, which was a dark red oily liquid.

MS (MALDI) (M ⁺ , C ₃₅ H ₅₉ NO ₃ SSi ₂ ): calcd: 630.09; found: 630.15. ¹ H NMR (300MHz, CDCl ₃ )d 10.12 (d, J=6.4Hz, 1H, CHO), 7.94(d,J＝16.1Hz,1H,CH),7.40(d,J＝6.8Hz,2H,ArH),6.98(d,J＝6.6Hz,1H,CH),6.85(d,J＝16.1Hz ,1H,CH),6.65(d,J＝6.8Hz,2H,ArH),3.72(m,4H,CH ₂ ),3.49(m,2H,CH ₂ ),3.01(s,3H,NCH ₃ ), 2.70(s,2H,CH ₂ ),2.47(s,2H,CH ₂ ),2.11(s,2H,CH ₂ ),1.01(s,6H,CH ₃ ),0.86(m,18H,CH ₃ ),0.02(s,12H,CH ₃ ). ¹³ C{1H}NMR(126MHz, CDCl ₃ )d 190.77,156.09,149.77,149.50,134.66,128.57,127.97,126.58,124.35,111.44,62.08,60.25,54.48,41.36,39.62,38.82,37.39,30.42,29. 66,28.04,25.51,17.94,5.49,5.63.

S5. Add compound 6 (12.2 mmol, 7.7 g) dissolved in an appropriate amount of acetone into a single-necked flask, add 1N HCl (1N, 48.9 mmol), react at room temperature for 3 h, then neutralize with sodium bicarbonate, spin dry, extract with EA, spin dry and pass through a chromatography column, the eluent ratio is 1:5-2:1 (EA:PE), and a dark red product compound 7a (3.4 g, 8.8 mmol) is obtained, and the yield is 72.0%;

MS (MALDI) (M ⁺ , C ₂₃ H ₃₁ NO ₃ S): calcd: 401.56; found: 401.78. ¹ H NMR (300MHz, CDCl ₃ )d10.08 (d, J＝8.1Hz, 1H, CHO), 7.94(d,J＝16.2Hz,1H,CH),7.42(d,J＝8.8Hz,2H,ArH),6.97(d,J＝8.1Hz,1H,CH),6.86(d,J＝16.2Hz ,1H,CH),6.72(d,J＝8.8Hz,2H,ArH),3.81(m,2H,OH),3.62(m,2H,NCH ₂ ),3.52(m,2H,OCH ₂ ),3.02 (s,3H,NCH ₃ ),2.76(m,4H,SCH ₂ ,OCH ₂ ),2.49(m,2H,CH2),2.31(m,2H,CH ₂ ),1.02(s,6H,CH ₃ ). ¹³ C{1H}NMR (126MHz, CDCl ₃ )d 191.79157.37,150.83,150.17,135.29,128.85 127.50,126.49,124.92,124.52,112.12,61.06,59.86,54.54,41.95,39.78,38.7 4,38.02,29.97,28.17.

S6. Under argon atmosphere, 1-ethyl-3 (3-dimethylpropylamine) carbodiimide (3.28 mmol, 0.63 g), 4-dimethylaminopyridine (0.33 mmol, 0.040 g), 3,4-bis (benzyloxy) benzoic acid (1.63 mmol, 0.55 g) were added to a two-necked flask, and an appropriate amount of DCM was added at 0°C. After 45 minutes, compound 7a (0.82 mmol, 0.33 g) dissolved in an appropriate amount of DCM was added. After 2 hours, the reaction was refluxed overnight at 40°C, extracted with DCM, and dried by chromatography column. The eluent ratio was 1:8-1:5 (EA:PE), and compound 8a (0.70 mmol, 0.72 g) was obtained. The yield was 85%, and it was a dark red oily liquid.

MS (MALDI) (M ⁺ , C ₆₅ H ₆₃ NO ₉ S): calcd: 1033.42; found: 1033.36. ¹ H NMR (600MHz, CDCl ₃ ) δ 10.18 (d, J = 8.0Hz, 1H, CHO), 7.94(d,J＝16.2Hz,1H,CH),7.44–7.31(m,24H,ArH,CH),7.24(d,J＝2.3Hz,2H,ArH),7.03(d,J＝8.0Hz, 1H, ArH), 6.81 (t, J＝2.4Hz, 3H, ArH), 6.62 (d, J＝8.9Hz, 2H, ArH), 5.02 (d, J＝5.2Hz, 8H, OCH ₂ ), 4.45 (t, J = 5.9Hz, 2H, NCH ₂ ), 4.37 (t, J = 6.3Hz, 2H, OCH ₂ ), 3.70 (t, J = 5.8Hz, 2H, OCH ₂ ), 3.00 (s ,3H,NCH ₃ ),2.95(t,J＝6.3Hz,2H,SCH ₂ ),2.76(s,2H,CH ₂ ),2.44(s,2H,CH ₂ ),1.05(s,6H,CH ₃ ). ¹³ C NMR (151MHz, CDCl ₃ )δ191.6,166.2,165.9,159.8,156.1,151.1,149.4,136.5,135.1,131.9,131.7,128.9,128.6,128.1,127.6,127.2,126.9,125.2,124.8,111.9, 108.4,107.5,107.3,70.3,63.6 ,62.3,50.7,41.6,39.9,38.6,33.3,30.1,28.4,26.9.

S7. Under argon atmosphere, 1-ethyl-3(3-dimethylpropylamine)carbodiimide (2.76mmol, 0.53g), 4-dimethylaminopyridine (0.28mmol, 0.034g), 3,5-bis((3,4,5-trifluorobenzyl)oxy)benzoic acid (1.4mmol, 0.61g) were added to a two-necked flask, and an appropriate amount of DCM was added at 0°C. After 45mins, compound 7a (0.69mmol, 0.28g) dissolved in an appropriate amount of DCM was added. After 2h, the reaction was refluxed overnight at 40°C, extracted with DCM, and the solvent was removed in vacuo and purified by chromatography column. The eluent ratio was 1:8-1:5 (EA:PE), and compound 8b (0.58g, 0.48mmol) was obtained. The yield was 69.6%, which was a dark red oily liquid.

MS (MALDI) (M ⁺ , C ₆₅ H ₅₁ F ₁₂ NO ₉ S): calcd: 1250.31; found: 1250.32. ¹ H NMR (600MHz, CDCl ₃ )δ10.18(d,J＝8.0Hz,1H,CHO),7.90(d,J＝16.2Hz,1H,CH),7.34(d,J＝8.8Hz,2H,ArH),7.25(d,J ＝2.4Hz,2H,ArH),7.17(d,J＝2.4Hz,2H,ArH),7.06–7.01(m,9H,ArH,CH),6.79(d,J＝16.2Hz,1H,CH), 6.76(t,J＝2.4Hz,1H,ArH),6.72(t,J＝2.3Hz,1H,ArH),6.66(d,J＝8.9Hz,1H,ArH),4.97(s,4H,OCH ₂ ),4.93(s,4H,OCH ₂ ),4.49(t,J＝5.8Hz,2H,NCH ₂ ),4.39(t,J＝6.2Hz,2H,OCH ₂ ),3.74(t,J＝5.8Hz,2H,OCH ₂ ),3.05(s ,3H,NCH ₃ ),2.96(t,J＝6.2Hz,2H,SCH ₂ ),2.76(s,2H,CH ₂ ),2.43(s,2H,CH ₂ ),1.05(s,6H,CH ₃ ). ¹³ C NMR (151MHz, CDCl ₃ ) δ191.5, 165.8, 165.5, 159.1, 156.1, 152.2 (dm, ¹ J _FC ~260Hz), 150.5 (dm, ¹ J _FC ~246Hz),149.5,140.2(dm, ¹ J _FC ~258Hz),138.5(dm, ¹ J _FC ~257Hz),134.7,132.6,132.1,128.9,128.4,127.6,127.1,125.2,124.9,111.9,111.2 , 108.6,107.5,68.5,63.6,62.4,50.6,41.6,39.8,38.3,33.5,30.0,28.3.

S8. Under argon atmosphere, 1-ethyl-3(3-dimethylpropylamine)carbodiimide (2.92mmol, 0.56g), 4-dimethylaminopyridine (0.30mmol, 0.036g), 3,5-bis((perfluorophenyl)methoxy)benzoic acid (1.5mmol, 0.75g) were added to a two-necked flask, and an appropriate amount of DCM was added at 0°C. After 45mins, compound 7a (0.73mmol, 0.29g) dissolved in an appropriate amount of DCM was added. After 2h, the reaction was refluxed overnight at 40°C, extracted with DCM, and dried through a chromatography column. The eluent ratio was 1:8-1:5 (EA:PE) to obtain compound 8c (0.55g, 0.40mmol) with a yield of 54.8%, which was a dark red oily liquid.

MS (MALDI) (M ⁺ , C ₆₅ H ₄₃ F ₂₀ NO ₉ S): calcd: 1393.23; found: 1393.33. ¹ H NMR (600MHz, CDCl ₃ ) δ 10.18 (d, J=8.0Hz, 1H, CHO ),7.88(d,J＝16.1Hz,1H,CH),7.34–7.29(m,4H,ArH),7.27–7.23(m,2H,ArH),7.01(d,J＝8.0Hz,1H,ArH ),6.81–6.72(m,3H,ArH,CH),6.64(d,J＝8.8Hz,2H,ArH),5.09(s,4H,OCH ₂ ),5.02(s,4H,OCH ₂ ),4.50(t,J＝5.8Hz,2H,NCH ₂ ),4.38(t,J＝6.3Hz,2H,OCH ₂ ),3.78(t,J＝5.8Hz,2H,OCH ₂ ),3.07(s ,3H,NCH ₃ ),2.96(t,J＝6.3Hz,2H,SCH ₂ ),2.76(s,2H,CH ₂ ),2.44(s,2H,CH ₂ ),1.05(s,6H,CH ₃ ). ¹³ C NMR (151MHz, CDCl ₃ ) δ191.6,165.9,165.5,159.2,159.0,156.2,156.0,149.5,146.7(dm, ¹ J _FC ~253Hz),145.1(dm, ¹ J _FC ~260Hz),141.6(dm, ¹ J _FC ~257Hz),139.8(dm, ¹ J _FC ~245Hz),139.2,134.9,132.2,132.0,128.8,127.3,126.9 ,125.1,124.6,111.8,108.6,107.6,63.7,62.3,62.1,57.9,50.4,41.5,39.8,38.3,33.2,30.9,30.0,28.3.

Synthesis of chromophore H1:

Under argon atmosphere, compound 8a (0.34 mmol, 0.35 g) and 2-(3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ethylidene)malononitrile (0.41 mmol, 0.13 g) were added to a two-necked flask, dissolved with 5-6 mL of ethanol, reacted at 65 ° C for 3 h, and dried by chromatography column with an eluent ratio of 1:10-1:3 (EA:PE) to obtain chromophore H1(0F) (0.26 g, 0.20 mmol) with a yield of 58.8%;

HRMS (ESI) (M ⁺ ,C ₈₁ H ₆₉ F ₃ N ₄ O ₉ S): calcd: 1331.4816; found: 1331.4815. ¹ H NMR (600MHz, CDCl ₃ )δ7.95(d,J＝16.0Hz,1H,CH),7.55–7.48(m,5H,ArH),7.44–7.33(m,22H,ArH),7.32–7.28(m,2H,ArH), 7.22(d,J＝2.3Hz,2H,ArH),7.20(d,J＝2.3Hz,2H,ArH),6.89(d,J＝16.0Hz,1H,CH),6.82–6.75(m,2H, CH),6.60(d,J＝9.0Hz,2H,ArH),6.47(d,J＝14.6Hz,1H,CH),4.99(s,8H,OCH ₂ ),4.43(t,J＝5.8Hz, 2H,NCH ₂ ), 4.32 (t, J = 6.2Hz, 2H, OCH ₂ ), 3.69 (t, J = 5.8Hz, 2H, OCH ₂ ), 3.00 (s, 3H, NCH ₃ ), 2.91 (t, J = 6.3Hz ,2H,SCH ₂ ),2.44(s,2H,CH ₂ ),2.34–2.21(m,2H,CH ₂ ),0.96(s,3H,CH ₃ ),0.88(s,3H,CH ₃ ). ¹³ C NMR (151MHz, CDCl ₃ )δ175.6,166.2,165.9,162.8,159.8,157.2,154.5,150.1,147.3,137.9,136.4,131.7,131.4,129.9,129.7,129.2,128.7,128.2,127.6,126.8,1 25.1,124.7,117.2,112.0,110.7,108.6,108.4,107.5,107.1,70.3,63.4,62.2,58.2,50.6,41.7,41.1,38.7,34.2,30.4,29.7,29.3,28.6,27. 9.

Synthesis of chromophore H2:

Under argon atmosphere, compound 8b (0.52 mmol, 0.65 g) and 2-(3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ethylidene)malononitrile (0.62 mmol, 0.20 g) were added to a two-necked flask, dissolved with 5-6 mL of ethanol, reacted at 65°C for 3 h, and dried by chromatography column with an eluent ratio of 1:10-1:3 (EA:PE) to obtain chromophore H2(3F) (0.43 g, 0.28 mmol) with a yield of 53.8%.

HRMS (ESI) (M ⁺ ,C ₈₁ H ₅₇ F ₁₅ N ₄ O ₉ S): calcd: 1547.3685; found: 1547.3687. ¹ H NMR (600MHz, CDCl ₃ ) δ7.95 (d, J=16.0Hz, 2H ,CH),7.60–7.50(m,5H,ArH),7.42(d,J＝12.3Hz,1H,CH),7.36(d,J＝8.9Hz,2H,ArH),7.22(d,J＝2.3 Hz,2H,ArH),7.16(d,J＝2.4Hz,2H,ArH),7.05– 6.99(m,8H,ArH),6.91(d,J＝16.0Hz,1H,CH),6.76(t,J＝2.3Hz,1H,ArH),6.72(t,J＝2.3Hz,1H,ArH) ,6.65(d,J＝9.0Hz,2H,ArH),6.50(d,J＝14.7Hz,1H,CH),4.95(s,4H,OCH ₂ ),4.94(s,4H,OCH ₂ ),4.49(t,J＝5.8Hz,2H,NCH ₂ ),4.36(t,J＝6.2Hz,2H,OCH ₂ ),3.76(t,J＝5.8 Hz,2H,OCH ₂ ),3.07(s,3H,NCH ₃ ),2.94(t,J＝6.3Hz,2H,SCH ₂ ),2.45(s,2H,CH ₂ ),2.31(s,2H,CH ₂ ),0.99(s,3H,CH ₃ ),0.89(s,3H,CH ₃ ). ¹³ C NMR (151MHz, CDCl ₃ )δ175.4,165.8,165.4,163.0,159.1,156.8,153.8,152.2(dm, ¹ J _FC ～257Hz),150.5(dm, ¹ J _FC ～245Hz),150.1,147.3,140.2(dm, ¹ J _FC ～260Hz ),138.5(dm, ¹ J _FC ~253Hz),137.3,132.6,132.1,132.0,131.4,129.9,129.7,129.6,129.3,128.3,126.8,125.1,124.8,117.5,112.0,111.2,110.6,108.7,108.6, 107.5,107.3,68.5,63.5, 62.3,58.5,50.6,41.7,41.0,38.5,34.1,31.9,30.3,29.7,29.3,28.6,27.7,27.2,22.7,14.1.

Synthesis of chromophore H3:

In an argon atmosphere, compound 8c (0.38 mmol, 0.53 g) and 2-(3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ethylidene)malononitrile (0.38 mmol, 0.13 g) were added to a two-necked flask, dissolved in 5-6 mL of ethanol, reacted at 65°C for 3 h, and dried by chromatography column with an eluent ratio of 1:10-1:3 (EA:PE) to obtain chromophore H3(5F) (0.33 g, 0.20 mmol) with a yield of 52.6%.

HRMS (ESI) (M ⁺ ,C ₈₁ H ₄₉ F ₂₃ N ₄ O ₉ S): calcd: 1691.2931; found: 1691.2937. ¹ H NMR (600MHz, CDCl ₃ )δ7.93(d,J＝16.0Hz,1H,CH),7.59–7.49(m,5H,ArH),7.44(d,J＝12.3Hz,1H,CH),7.33(d,J＝9.0Hz ,3H,ArH),7.28-7.22(m,4H,ArH),6.89(d,J＝15.9Hz,1H,CH),6.82–6.70(m,2H,ArH,CH),6.65(d,J＝ 8.8Hz,2H,ArH),6.51(d,J＝14.6Hz,1H,CH),5.07(s,4H,OCH ₂ ),5.02(s,4H,OCH ₂ ),4.51(t,J＝5.7Hz ,2H,NCH ₂ ), 4.36 (t, J = 6.2Hz, 2H, OCH ₂ ), 3.80 (t, J = 5.8Hz, 2H, OCH ₂ ), 3.09 (s, 3H, NCH ₃ ), 2.94 (t, J = 5.6Hz ,2H,SCH ₂ ),2.46(s,2H,CH ₂ ),2.33(s,2H,CH ₂ ),0.99(s,3H,CH ₃ ),0.90(s,3H,CH ₃ ). ¹³ C NMR (151MHz, CDCl ₃ ) δ175.5,165.8,165.5,162.9,159.2,159.0,150.2,147.3,146.7(dm, ¹ J _FC ~260Hz),145.1(dm, ¹ J _FC ~258Hz),141.6(dm, ¹ J _FC ~246Hz),139.9(dm, ¹ J _FC ~254Hz),139.6,137.48,132.0,131.4,129.8,129.4,129.2,128.3,126.8,125.0,124.6,117.28,111.9,111.1,110.7,108.9,108.6,107.5,107. 3,63.5,62.1,60.4,58.3, 57.9,50.4,41.6,41.1,38.4,34.0,30.3,29.3,28.5,27.8,21.1,14.2.

In order to more clearly illustrate the present invention, the present invention also conducted the following characterization experiments on the chromophores H1-H4 prepared in the examples:

(1) Spectral absorption characteristics and thermal stability

① The thermal stability of chromophores H1-H4 is characterized by thermogravimetric curves, as shown in Figure 6;

② The UV-visible spectra of chromophores H1-H4 in chloroform solution are shown in FIG8 ;

③ The UV-visible spectra of chromophores H1-H4 in the film are shown in Figure 9;

Among them, the main parameters of the spectral absorption characteristics and thermal stability of the four chromophore molecules are shown in Table 1;

Table 1 Spectral absorption and thermal stability parameters of four chromophore molecules

Wherein, λ _max ^a , λ _max ^b , λ _max ^d are the measurement results of the chromophore molecule in chloroform, 1,4-dioxane and electro-optical film, respectively, and Δλ ^c is the difference between λ _max ^a and λ _max ^b ;

Chromophores H1-H4 have similar color shift behavior, with color shift occurring between 52nm and 57nm. In different solvents, the maximum absorption wavelengths of the chromophores in chloroform are 749nm, 728nm, 742nm, and 739nm, respectively. From the approximate maximum absorption wavelength data of chromophores H1-H4 in chloroform, it can be seen that the addition of different self-assembly spacer groups will not hinder the charge transfer of effective molecules in the conjugated structure. Their absorption wavelengths are above 725nm, which roughly indicates that they have a large first-order hyperpolarizability.

The maximum absorption wavelengths (λ _max ) of chromophores H1-H4 in the film are 773 nm, 759 nm, 759 nm and 755 nm, respectively, which are different from those in solution. This phenomenon suggests that there may be different interactions between chromophores composed of different separation groups and polymers.

(2) Energy level calculation

The charge transfer interaction within the chromophore can be calculated by the energy gap difference between the HOMO-LUMO molecular orbitals. In order to analyze the composition of HOMO-LUMO and the in-depth information of the frontier orbitals, the inventors ran the Multiwfn program using Ros-Schuit (SCPA) partitioning and DFT calculations;

The chromophores were divided into three parts: donor, π-bridge, and acceptor, and the contribution percentages were calculated: For the four chromophores H1–H4, the HOMO was mainly stabilized by the contributions of the donor (42.90%–45.38%) and π-bridge (32.15–33.73%), while the LUMO was mainly stabilized by the contributions of the acceptor (42.48%–44.02%) and π-bridge (40.65%–40.95%).

DFT calculations are used to calculate the HOMO-LUMO energy gap (ΔE). The calculation results are shown in Figure 11. The ΔE of chromophores H1-H4 are 1.958 eV, 1.981 eV, 1.977 eV and 1.938 eV, respectively. These four chromophores have similar isolation groups, which are attached to the electron bridge and the donor, respectively. These chromophores all have similar conjugated structures. It can be seen from the UV absorption data that the substituted steric groups do not affect the conjugated structure.

(3) Electro-optic coefficient

The present invention compares the efficiency of converting the microscopic hyperpolarizability of four chromophores with different isolated functional groups into macroscopic r ₃₃ values. First, the chromophores are prepared into electro-optical films: the above chromophores are dissolved in redistilled 1,1,2-trichloroethane, the dissolved chromophore solution is filtered through a 0.2 mm PTFE filter, the filtered solution is spin-coated on an ITO glass substrate, and after removing the solvent, the synthetic film of the chromophore composite material is heated at 50°C overnight in a vacuum to ensure the removal of residual solvent. The contact polarization process is carried out above the glass transition temperature (T _g ) of the electro-optical material and at a temperature of 5-10°C. The electro-optic coefficient r ₃₃ of the polarized film at a wavelength of 1310 nm is calculated using the Teng-Man simple reflection method, which uses a thin ITO electrode with low reflectivity and good transparency to minimize multiple reflections. As mentioned earlier, controlling the geometry and delocalization of the molecules by introducing steric isolation groups into the chromophores may be an effective approach to minimize the interactions between chromophores and, therefore, these approaches may have distinct advantages in best converting β values into R _values , thereby improving the macroscopic electro-optical activity.

(4) Assembled device performance

The various performance indicators of the four small molecule chromophores assembled into devices were measured, and the results are shown in Table 2;

Table 2 Performance indicators of several small molecule chromophore assembly devices

The average polarization efficiency (r ₃₃ /polarization field or r ₃₃ /E _p ) of H1, H2, H3 and H4 are 1.63±0.07, 2.26±0.08, 1.36±0.07 and 2.76±0.08 nm ² /V ² , respectively, which are higher than those of the host and guest polymer materials, as shown in FIG13 . Under the condition of similar first-order hyperpolarizability, the difference in polarization efficiency between H1 and H3 is mainly attributed to the number of chromophores per unit volume. Although the chromophore concentration of the electro-optical film H2 is lower, its polarization efficiency is higher. H3 obtains a highly polarization-induced order by π-π stacking through an electrostatic mechanism. Due to the multi-chromophore structure, the polarization efficiency of H4 is further improved to 2.76±0.08 nm ² /V ² : three chromophore molecules are connected to the middle core in the form of covalent bonds, which not only ensures that the chromophore molecules can rotate freely under the action of the electric field, but also effectively separates the chromophores and weakens the electrostatic interaction between molecules. Of course, the improved polarization efficiency of chromophore H4 also benefits from the π-π stacking of trifluorobenzene, which results in a highly polarization-induced order.

In order to evaluate the influence of the self-assembly effect of HD-PFD and PFD-AH on the EO performance, the basic devices of 1:1H1:H3 and 1:2H3:HLD 1 were fabricated, in which the chromophore HLD 1 was synthesized from known literature. The polarization treatment was carried out and the polarization efficiency was calculated.

The average polarization efficiencies of the chromophore mixing ratios 1:1H1:H3 and 1:2H3:HLD 1 were 3.26±0.10 and 3.17±0.09nm ² /V ² , respectively, which were significantly higher than those of chromophore H1 and chromophore HLD 1. The intermolecular interactions between the electronegative aromatic benzene ring groups and the electronegative pentafluorophenyl groups or the π-π stacking of trifluorobenzene contributed to the high polarization-induced order. When the temperature rose to the glass transition temperature of the electro-optic film, the molecular arrangement formed by the intermolecular hydrogen bonds would be polarized and dissociated by the electric field. Then, under the action of the electric field, the electro-optic film was gradually cooled to room temperature, and the polarization orientation under the action of the electric field was fixed by the non-covalent cross-linking network, which enhanced and stabilized the order of the eccentric chromophores. The optimal r ₃₃ values of 1:1H1:H3 and 1:2H3:HLD 1 were 328 and 317 pm/V, respectively, which were much higher than those of the previously reported chromophores with diethylamine phenyl donors.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims (10)

1. The self-assembled organic optical nonlinear chromophore is characterized in that the chromophore molecule is H4, and the structural formula is shown as follows:

。

2. a method of synthesizing a self-assembled organic optical nonlinear chromophore according to claim 1, wherein said method of synthesizing chromophore H4 comprises the steps of:

p1, 4- (methyl (2- ((tetrahydro-2H-pyran-2-yl) oxy) ethyl) amino) benzaldehyde and a compound 1 are subjected to Knoevenagel condensation reaction under the conditions of sodium ethoxide and 2-mercaptoethanol to obtain a compound 3b;

p2, connecting a tert-butyl diphenyl silicon-based protecting group to the alcoholic hydroxyl of the compound 3b to obtain a compound 4b;

p3, the compound 4b and diethyl cyanomethylphosphate react through a Wittig-Hornor reaction to obtain a compound 5b;

p4, reducing cyano groups in the compound 5b through diisobutylaluminum hydride to obtain aldehyde compound 6b;

p5, removing the protecting group of the compound 6b through alkaline hydrolysis to obtain a compound 7b;

p6, connecting a self-assembled isolating group on the alcoholic hydroxyl group of the compound 7b through Steglich esterification to obtain a compound 8d;

p7, the compound 8d is subjected to acid hydrolysis to obtain a compound 9;

p8, connecting a tri-furcation isolation group on the alcoholic hydroxyl group of the compound 9 through Steglich esterification to obtain a compound 10;

p9, condensing the compound 10 with an acceptor molecule to prepare the chromophore H4;

。

3. the method for synthesizing a self-assembled organic optical nonlinear chromophore according to claim 2, wherein the steps P1 and P2 are specifically:

p1, slowly dissolving metallic sodium in ethanol under the protection of argon, adding 2-mercaptoethanol under the ice bath condition, adding the compound 1 for reaction for 1 hour after fully mixing and stirring, adding the compound 2b, refluxing at 65 ℃ for overnight, extracting and concentrating with ethyl acetate after the reaction is finished, purifying by silica gel chromatography, and using ethyl acetate and petroleum ether as eluent to obtain a compound 3b;

p2, slowly adding the mixture into an N, N-dimethylamide solution of the compound 3b in a flask filled with imidazole and tert-butyldimethyl chlorosilane, reacting for 3 hours at room temperature under the protection of argon, extracting with ethyl acetate, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain the compound 4b.

4. The method for synthesizing a self-assembled organic optical nonlinear chromophore according to claim 2, wherein the step P3 specifically comprises:

and P3, slowly adding diethyl cyanomethylphosphate into tetrahydrofuran solution of sodium hydride under the condition of argon protection and ice bath, adding the compound 4b, carrying out reflux reaction at 65 ℃ overnight, carrying out vacuum spin-drying on the solvent after the reaction is finished, extracting with ethyl acetate, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain the compound 5b.

5. The method for synthesizing a self-assembled organic optical nonlinear chromophore according to claim 2, wherein the step P4 specifically comprises:

p4, slowly adding a hexane solution of diisobutyl aluminum hydride into a dichloromethane solution of the compound 5b, reacting for a period of time at the temperature of minus 78 ℃ under the protection of argon, adding a certain amount of dichloromethane and water for quenching at the temperature of 0 ℃, carrying out suction filtration after the reaction is finished, extracting filtrate with dichloromethane, concentrating, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain the compound 6b.

6. The method for synthesizing a self-assembled organic optical nonlinear chromophore according to claim 2, wherein the step P5 specifically comprises:

and P5, removing the tertiary butyl diphenyl chlorosilane protecting group of the compound 6b through alkaline hydrolysis treatment, extracting with ethyl acetate, purifying through silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain the compound 7b.

7. The method for synthesizing a self-assembled organic optical nonlinear chromophore according to claim 2, wherein the P6 and P7 steps are specifically:

p6, slowly adding the mixture into a dichloromethane solution in a flask filled with 4-dimethylaminopyridine, 1-ethyl-3 (3-dimethylpropylamine) carbodiimide and 3, 5-di ((3, 4, 5-trifluorobenzyl) oxy) benzoic acid, reacting for a period of time at 0 ℃ under a protective atmosphere, slowly adding the dichloromethane solution of the compound 7b, heating and refluxing the mixture for reaction, extracting an organic phase with dichloromethane, removing a solvent by spin drying, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain a compound 8d;

and (3) removing the (2-tetrahydropyran) protecting group of the compound 8d through acid hydrolysis treatment, extracting with ethyl acetate, purifying through silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluents to obtain the compound 9.

8. The method for synthesizing a self-assembled organic optical nonlinear chromophore according to claim 2, wherein the step P8 is specifically:

p8, slowly adding into a dichloromethane solution in a flask filled with 4-dimethylaminopyridine, 1-ethyl-3 (3-dimethylpropylamine) carbodiimide and 6,6' - ((ethane-1, 1-triacyltris (benzene-4, 1-diacyl)) tris (oxy)) tricarboxylic acid, reacting for a period of time under the protection of argon at 0 ℃, slowly adding into the dichloromethane solution of the compound 9, heating and refluxing to react, extracting an organic phase with dichloromethane, removing the solvent by spin drying, purifying by silica gel chromatography, and purifying by using dichloromethane and ethyl acetate as eluent to obtain the compound 10.

9. The method for synthesizing a self-assembled organic optical nonlinear chromophore according to claim 2, wherein the step P9 specifically comprises:

p9, reacting the compound 10 with an acceptor molecule under the protection of argon, concentrating a product, purifying by silica gel chromatography, and eluting with ethyl acetate and petroleum ether to obtain the chromophore H4; wherein the acceptor molecule is 2- (3-cyano-4-methyl-5-phenyl-5- (trifluoromethyl) furan-2 (5H) -ethylene) malononitrile.

10. Use of a self-assembled organic optical nonlinear chromophore according to claim 1 as electro-optic material and in an electro-optic modem.

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