CN114656432A

CN114656432A - Self-assembled organic optical nonlinear chromophore and synthetic method and application thereof

Info

Publication number: CN114656432A
Application number: CN202210338231.8A
Authority: CN
Inventors: 刘锋钢; 黄泽铃; 王家海; 曾紫莹
Original assignee: Guangzhou University
Current assignee: Guangzhou University
Priority date: 2022-04-01
Filing date: 2022-04-01
Publication date: 2022-06-24
Anticipated expiration: 2042-04-01
Also published as: CN114656432B

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 figure, 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 accessed, and meanwhile, the electro-optic coefficient is tested and verified, and the materials have higher electro-optic coefficients compared with other non-self-assembly materials after self-assembly.

Description

Self-assembled organic optical nonlinear chromophore and synthetic method and application thereof

Technical Field

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

Background

With the rapid development of information and communication technologies, people have greater and greater requirements on high-speed data transmission, processing and large-capacity information calculation compared with the traditional electronic information carrier, and photons as a communication information carrier have the advantages of good parallelism, high speed, large bandwidth, high frequency, strong anti-electronic interference capability, good confidentiality and the like. Among the communication technologies, the interconversion between electrical signals and optical signals, which is closely related to the technologies of photons, electronics, etc. and the devices such as electro-optical modulators, optical switches, optical information storage, etc., has become an important component of the current communication technologies. In the future era of high-speed information transmission, integrated electro-optical technology will be the major trend, and electro-optical modulators are mainly based on this technology. Meanwhile, it is also an essential device indispensable in optical communication. Nonlinear optical materials have also become a core component of modulators, attracting a wide range of attention. The chromophore is a structure (D-pi-A structure) composed of an electron donor (D), an electron acceptor (A) and an electron bridge (pi), and various types of donors, bridges and acceptors have been developed in the prior art to enhance the first-order hyperpolarizability of the chromophore, such as anilino donors (triarylamino, alkylanilines, etc.), heterocyclic or polyene bridges, TCF or CF₃TCF derivative acceptors are the most common chromophore structures, and a reasonable combination of strong donors, acceptors, and appropriate electronic bridges will yield large first-order hyperpolarizabilities.

In order to obtain a larger electro-optic coefficient, a larger chromophore first-order hyperpolarizability is required. However, chromophores with a high first order hyperpolarizability generally have a large dipole moment, which results in strong electrostatic interactions between molecules during the polarization of the chromophore, thereby hindering the orientation of the molecules. Ultimately resulting in aggregation of the molecules and low efficiency of the chromophore polarization. Many researches report that by introducing some isolating groups into a donor, an acceptor and a bridging part of a chromophore, the dipolar interaction between molecules can be reduced, the solubility of the chromophore and the electro-optic coefficient of a material are improved, and a CLD bridge in an NLO chromophore can be functionalized by utilizing macromolecular substituents such as alkyl chains, silane and carbazole and various dendritic structures, so that the dipolar-dipolar interaction can be effectively reduced, and the polarization efficiency of NLO is improved.

Glass transition temperature (T) of most dendritic chromophore films_g) Generally lower than 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, the method successfully improves the photoelectric coefficient and the high long-term stability by adopting sequential polarization, crosslinking or self-assembly lattice hardening or intermolecular hydrogen bond. However, the design, synthesis, polarization and crosslinking process of crosslinked electro-optic materials is very complicated.

Disclosure of Invention

Aiming at the problems, the invention provides a novel self-assembly single donor structure, OH groups are introduced into a single donor and an electron bridge of a second-order nonlinear optical chromophore through nucleophilic reaction, two OH groups connected at a donor end and an electron bridge end provide connection sites for further modification, and a novel dendrimer, a main chain and a side chain self-assembly EO polymer are formed by introducing a high-efficiency self-assembly group containing aromatic phenyl dendron (HD), pentafluorophenyl dendron (PFD) or trifluorophenyl dendron (TFD), so that the novel dendrimer, the main chain and the side chain self-assembly EO polymer have an ultra-large electro-optic coefficient and high long-term stability.

The purpose of the invention is realized by adopting the following technical scheme:

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

the molecular structural general formulas of the chromophores H1, H2 and H3 are shown as follows:

wherein R is

In a second aspect, the invention provides a method for synthesizing an organic optical nonlinear chromophore based on a single-donor self-assembled structure, which comprises synthesizing chromophores H1-H3 and synthesizing chromophores 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)) with isophorone (compound 1) in sodium ethoxide and 2-mercaptoethanol by Knoevenagel condensation reaction to give compound (3 a);

s2, grafting a tert-butyl dimethyl silicon-based protecting group on the alcoholic hydroxyl group of the compound (3a) to obtain a compound (4 a);

s3, reacting the compound (4a) with diethyl cyanomethylphosphonate by a Wittig-Hornor reaction to obtain a compound (5 a);

s4, reducing the cyano group in the compound (5a) to an aldehyde by diisobutylaluminum hydride to obtain a compound (6 a);

s5, hydrolyzing the compound (6a) with acid to obtain a compound (7 a);

s6, attaching different functionalized separation groups on the alcoholic hydroxyl group of the compound (7a) through nucleophilic substitution or Steglich esterification to obtain a compound (8a-8 c);

s7, condensation of said compound (8a-8c) with an acceptor molecule to obtain said chromophore H1-H3;

wherein the compounds (1) - (H3) have the following structures:

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

p1, compound (3b) obtained by knoevenagel condensation reaction using 4- (methyl (2- ((tetrahydro-2H-pyran-2-yl) oxy) ethyl) amino) benzaldehyde (i.e. compound (2b)) with isophorone (compound 1) under the conditions of sodium ethoxide and 2-mercaptoethanol;

p2, grafting a tert-butyl diphenyl silicon group protecting group on the alcoholic hydroxyl group of the compound (3b) to obtain a compound (4 b);

p3, the compound (4b) and diethyl cyanomethylphosphonate are reacted by Wittig-Hornor to obtain a compound (5 b);

p4, reduction of the cyano group in the compound (5b) by diisobutylaluminum hydride to give an aldehyde compound (6 b);

p5, the compound (6b) is subjected to alkaline hydrolysis to remove the protecting group to obtain a compound (7 b);

p6, attachment of a self-assemblable spacer group via nucleophilic substitution or Steglich esterification on the alcoholic hydroxyl group of said compound (7b) to give compound (8 d);

hydrolyzing the compound (8d) with acid and P7 to obtain a compound (9);

p8, attachment of a tridentate spacer group on the alcoholic hydroxyl group of said compound (9) by nucleophilic substitution or Steglich esterification to give compound (10);

p9, said chromophore being obtained by condensation of said compound (10) with an acceptor molecule, 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, slowly dissolving sodium metal in ethanol under the protection of argon, adding 2-mercaptoethanol under the condition of ice bath, fully mixing and stirring, adding the compound (1) to react for 1 hour, adding the compound (2a), refluxing at 65 ℃ overnight, extracting and concentrating by using ethyl acetate after the reaction is finished, purifying by silica gel chromatography, and taking ethyl acetate and petroleum ether as an eluent to obtain a compound (3 a);

s2, slowly adding the mixture into an N, N-dimethylamide solution of the compound (3a) in a flask filled with imidazole and tert-butyldimethylchlorosilane, 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 a compound (4 a);

s3, in an argon protective environment, under an ice bath condition, slowly adding cyanomethyl diethyl phosphate into a tetrahydrofuran solution of sodium hydride, adding the compound (4a), carrying out reflux reaction at 68 ℃ overnight, after the reaction is finished, carrying out vacuum spin-drying on the solvent, extracting ethyl acetate, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluents to obtain a compound (5 a);

s4, slowly adding a hexane solution of diisobutylaluminum hydride into a dichloromethane solution of the compound (5a), reacting at-78 ℃ under an argon protective atmosphere for a period of time, adding a certain amount of dichloromethane and water at 0 ℃ for quenching, performing suction filtration after the reaction is finished, extracting a filtrate with dichloromethane, concentrating, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluents to obtain a compound (6 a);

s5, removing dimethyl tert-butyl silicon base from the compound (6a) by acid hydrolysis, extracting with dichloromethane, purifying by silica gel chromatography with ethyl acetate and petroleum ether as eluent to obtain a compound (7 a);

s6, slowly adding dichloromethane solution into 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, reacting for a while at 0 ℃ and under a protective atmosphere, slowly adding dichloromethane solution of the compound (7a), refluxing at 40 ℃ overnight, extracting an organic phase with dichloromethane, distilling off the solvent, purifying by silica gel chromatography with ethyl acetate and petroleum ether as eluents to obtain compounds (8a-8 c);

s7, reacting the compounds (8a-8c) with an acceptor molecule under the protection of argon at 65 ℃, concentrating the product, purifying by silica gel chromatography, and taking ethyl acetate and petroleum ether as eluents to obtain chromophores H1-H3;

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

p2, slowly adding the mixture into an N, N-dimethylamide solution of the compound (3b) in a flask containing imidazole and tert-butyldimethylchlorosilane, reacting for 3 hours at room temperature under the environment of argon gas, extracting with ethyl acetate, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain a compound (4 b);

p3, under the condition of ice bath in an argon protective environment, slowly adding diethyl cyanomethylphosphonate into a tetrahydrofuran solution of sodium hydride, adding the compound (4b), carrying out reflux reaction at 65 ℃ overnight, after the reaction is finished, carrying out vacuum spin-drying on the solvent, extracting ethyl acetate, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluents to obtain a compound (5 b);

p4, slowly adding a hexane solution of diisobutylaluminum hydride into a dichloromethane solution of the compound (5b), reacting at-78 ℃ under an argon protective atmosphere for a period of time, adding a certain amount of dichloromethane and water at 0 ℃ for quenching, performing suction filtration after the reaction is finished, extracting a filtrate with dichloromethane, concentrating, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluents to obtain a compound (6 b);

p5, the compound (6b) is subjected to alkaline hydrolysis treatment to remove a tert-butyldiphenylchlorosilane protective group, extracted by ethyl acetate, purified by silica gel chromatography, and purified by using ethyl acetate and petroleum ether as an eluent to obtain a compound (7 b);

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

p7 and the compound (8d) are subjected to acid hydrolysis treatment to remove the (2-tetrahydropyran) protecting group, and then extracted with ethyl acetate, purified by silica gel chromatography, and purified with ethyl acetate and petroleum ether as eluents to obtain a compound (9);

p8, slowly adding dichloromethane solution into 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, reacting at 0 ℃ under a protective atmosphere for a while, slowly adding dichloromethane solution of the compound (9), heating and refluxing, extracting an organic phase with dichloromethane, removing the solvent by spin-drying, purifying by silica gel chromatography with dichloromethane and ethyl acetate as eluents to obtain a compound (10);

p9, the compound (10) and an acceptor molecule react under the protection of argon, the product is concentrated and purified by silica gel chromatography, and ethyl acetate and petroleum ether are used as eluent 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 invention provides an application of the organic optical nonlinear chromophores H1, H2, H3 and H4 based on the single-donor self-assembled structure, in particular an application as an electro-optical material and in an electro-optical modem.

The chromophore is prepared into the application of the electro-optic film, specifically, the chromophore is dissolved in

redistilled

1,1, 2-trichloroethane, the dissolved chromophore solution is filtered through a 0.2mm PTFE filter, the filtered solution is coated on an ITO glass substrate in a rotating mode, and the electro-optic film is prepared after the solvent is removed.

The invention has the beneficial effects that:

1. the present invention provides a new, self-assemblable single donor structure. Four dendritic macromolecules H1, H2, H3 and HLD1 were synthesized by introducing aromatic dendrons (HD), trifluorobenzene dendrons (TFD), pentafluorophenyl dendrons (PFD) and Anthracyclines (AH) into the donor and bridge ends of push-pull tetraene chromophores. In addition, a trifentryfluorene dendrimer containing multichromophore H4 was synthesized. The dipolar-dipolar interaction of chromophores at high loading densities is minimized by supramolecular self-assembly of pi-pi interactions of HD-PFD/PFD-AH/TFD-TFD, maximizing the order of eccentricity of the chromophores. The higher polarization efficiency and EO coefficient are obtained through a dendritic or multichromophore structure and a supermolecular self-assembly strategy of pi-pi accumulation of the fluorine aromatic hydrocarbon and the aromatic hydrocarbon.

2. The invention also provides a series of novel chromophore structures for intermolecular assembly, and pure films respectively containing 1:1H1: H3, 1:2H3: HLD1 and H4 obtain larger r at 1310nm₃₃(328, 317 and 279 pm/V). In addition, noncovalent crosslinking bonds formed by pi-pi stacking between chromophores can improve the long-term arrangement stability of the material. After annealing for 1000h at room temperature, the initial electrooptical coefficient of the electrode self-assembled film can be kept above 95%.

According to DFT theoretical calculation, the hyperpolarizability of the chromophore is high, and besides a large first-order hyperpolarizability, a special structure for isolating intermolecular interaction by the functional self-assembly group also has a large space effect, so that higher polarization efficiency is achieved.

Drawings

The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, other drawings can be obtained on the basis of the following drawings without inventive effort.

FIG. 1 is a general structural formula of chromophores H1-H3 prepared in example 1 of the present invention;

FIG. 2 is a specific structural formula of chromophores H1-H3 prepared according to example 1 of the present invention;

FIG. 3 is a synthetic scheme for chromophores H1-H3 prepared in example 1 of the present invention;

FIG. 4 is a structural formula of chromophore H4 prepared in example 2 of the present invention;

FIG. 5 is a synthetic scheme of chromophore H4 prepared according to example 2 of the present invention;

FIG. 6 is a thermogravimetric plot of chromophores H1-H4 made in examples 1 and 2 of the present invention;

FIG. 7 is a DSC plot of chromophores H1-H4 prepared in examples 1 and 2 of the present invention;

FIG. 8 is a chart of the UV-Vis spectra of chromophores H1-H4 in chloroform solvent prepared in examples 1 and 2 of the present invention;

FIG. 9 is a graph of the UV-Vis spectra of chromophores H1-H4, H1-H3 blend, and H3-HLD1 blended in an electro-optic film, prepared in examples 1 and 2 of the present invention;

FIG. 10 is a chart of UV spectrograms of chromophores H1-H4 in different solvents prepared in examples 1 and 2 of the present invention;

FIG. 11 is a theoretical calculated energy level result for chromophores H1-H4 prepared in examples 1 and 2 of the present invention;

FIG. 12 is a graph of the electro-optic coefficient versus molecular density for chromophores H1-H4 prepared in examples 1 and 2 of the present invention;

FIG. 13 is a plot of the polarization efficiency as a function of electric field for chromophores H1-H4 prepared in examples 1 and 2 of the present invention (r)₃₃Value).

Detailed Description

For the purpose of more clearly illustrating the present invention and more clearly understanding the technical features, objects and advantages of the present invention, the technical solutions of the present invention will now be described in detail below, but are not to be construed as limiting the implementable scope of the present invention.

The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.

The invention is further described with reference to the following examples.

Example 1

An organic optical nonlinear chromophore based on a single-donor self-assembly structure comprises H1-H3, the structure of which is shown in figure 4, and the chromophore H4 shows good solubility in common organic solvents, such as ethyl acetate, ethanol, acetone and the like.

The preparation process comprises the synthesis of chromophore H4, and comprises the following steps:

p1, under the condition of argon atmosphere and ice bath, adding metal sodium (88.23mmol, 2.0g) into a double-neck flask, dissolving the metal sodium with a proper amount of ethanol, adding 2-mercaptoethanol (88.23mmol, 6.89g, 7.65mL), adding a compound 1(132.35mmol, 20.68g) after 20mins, adding a compound 2b (88.23mmol, 23.23g) dissolved with a proper amount of ethanol after 1h, refluxing the reaction overnight at 65 ℃, extracting with EA after spin-drying, and passing through a chromatographic column by spin-drying to obtain a compound 3b (30.30g, 65.9mmol) with the eluent ratio of 1:8-1:3 (EA: PE), wherein the yield is as follows: 74.7% as red oily liquid;

MS(MALDI)(M⁺,C₂₆H₃₇NO₄S):calcd:459.24；found:459.25.¹H NMR(600MHz,CDCl₃)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,NCH₂),3.67–3.57(m,6H,OCH₂),3.06(s,3H,NCH₃),2.83–2.80(m,2H,SCH₂),2.64(s,2H,CH₂),2.44(s,2H,CH₂),1.82–1.75(m,2H,CH₂),1.72–1.64(m,2H,CH₂),1.59–1.55(m,2H,CH₂),1.08(s,6H,CH₃).¹³C NMR(151MHz,CDCl₃)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, adding imidazole (79.08mmol, 5.38g) and tert-butyldiphenylchlorosilane (79.08mmol, 21.73g) into a double-neck flask, adding a compound 3b (65.9mmol, 30.30g) dissolved in an appropriate amount of DMF, reacting at room temperature for 3h, spinning, extracting with EA, spinning to pass through a chromatographic column, wherein the ratio of an eluent to an eluent is 1:10-1:5 (EA: PE), and obtaining a compound 4b (31.32g, 44.87mmol), wherein the yield is as follows: 68.1% as red oily liquid;

MS(MALDI)(M⁺,C₄₂H₅₅NO₄SSi):calcd:697.36；found:697.15.¹H NMR(600MHz,CDCl₃)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,NCH₂),3.97–3.79(m,2H,OCH₂),3.65-3.62(m,2H,OCH₂),3.62–3.47(m,2H,OCH₂),3.08(s,3H,NCH₃),2.97(t,J＝6.8Hz,2H,SCH₂),2.58(s,2H,CH₂),2.36(s,2H,CH₂),1.87–1.77(m,2H,CH₂),1.64–1.56(m,2H,CH₂),1.55–1.49(m,2H,CH₂),1.05(m,15H,CH₃).¹³C NMR(151MHz,CDCl₃)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, sodium hydride (60%, 189.0mmol, 7.17g) was added to a two-necked flask under an argon atmosphere, after dissolving with an appropriate amount of THF, 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 ℃, after spin-drying the solvent, extracted with EA, purified with a chromatography column, and the ratio of the eluates was 1:15 to 1:6 (EA: PE), to give compound 5b (23.13g, 32.1mmol) with the yield: 67.5% as a red oily liquid;

MS(MALDI)(M⁺,C₄₄H₅₆N₂O₃SSi):calcd:720.37；found:720.22.¹H NMR(600MHz,CDCl₃)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,NCH₂),3.74(t,J＝6.8Hz,2H,OCH₂),3.66–3.50(m,4H,OCH₂),3.07(s,3H,NCH₃),2.73(t,J＝6.8Hz,2H,SCH₂),2.51(s,2H,CH₂),2.42(s,2H,CH₂),1.85–1.70(m,2H,CH₂),1.62–1.58(m,2H,CH₂),1.55–1.50(m,2H,CH₂),1.07(s,9H,CH₃),0.98(s,6H,CH₃).¹³C NMR(151MHz,CDCl₃)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, compound 5b (32.10mmol, 23.13g) dissolved in DCM was added dropwise to a two-necked flask under argon atmosphere, diisobutylaluminum hydride (1.0M, 64.20mmol, 64.20mL) was added dropwise at-78 ℃ to react at low temperature for 3h, 10mL of DCM and 10mL of water were slowly added at 0 ℃ to quench for 1h, extraction was performed with DCM, the solvent was dried and purified by column chromatography with an eluent ratio of 1:10-1:5 (EA: PE) to give compound 6b (18.91g, 26.12mmol) with yield: 81.4% as a dark red oily liquid;

MS(MALDI)(M⁺,C₄₄H₅₇NO₄SSi):calcd:723.38；found:723.40.¹H NMR(600MHz,CDCl₃)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,NCH₂),3.76(t,J＝7.0Hz,2H,OCH₂),3.65–3.50(m,4H,OCH₂),3.07(s,3H,NCH₃),2.74(t,J＝7.0Hz,2H,SCH₂),2.65(s,2H,CH₂),2.45(s,2H,CH₂),1.83–1.70(m,2H,CH₂),1.62–1.57(m,2H,CH₂),1.56–1.50(m,2H,CH₂),1.05(s,9H,CH₃),1.00(s,6H,CH₃).¹³C NMR(151MHz,CDCl₃)δ191.6,156.6,150.1,149.7,135.5,134.8,133.6,128.2,129.6,128.9,127.7,126.8,124.8,111.9,99.0,64.8,63.3,62.2,52.3,41.6,39.8,39.0,37.3,30.6,30.0,28.3,26.9,25.4,19.4,19.2.

p5, under argon atmosphere, adding compound 6b (22.40mmol, 16.22g) into a double-neck flask, dissolving the compound with THF, adding tetraisobutylammonium fluoride (1.0M, 44.80mmol, 44.8mL), reacting at room temperature for 1h, removing the solvent under vacuum, extracting with EA, purifying with a chromatographic column, and obtaining a dark red product, compound 7b (9.79g, 20.16mmol), with a yield of 90.0%, wherein the ratio of the eluent is 1:6-2:1 (EA: PE);

MS(MALDI)(M⁺,C₂₈H₃₉NO₄S):calcd:485.26；found:485.21.¹H NMR(600MHz,CDCl₃)δ10.13(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,NCH₂),3.65(t,J＝6.0Hz,2H,OCH₂),3.61–3.46(m,4H,OCH₂),3.05(s,3H,NCH₃),2.77(t,J＝6.1Hz,2H,SCH₂),2.75(s,2H,CH₂),2.52(s,2H,CH₂),1.59–1.48(m,6H,CH₂),1.04(s,6H,CH₃).¹³C NMR(151MHz,CDCl₃)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, an appropriate amount of DCM was added at 0 ℃ and 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 ℃, extracted with DCM, the solvent was removed in vacuo and purified with a chromatography column at an eluent ratio of 1:8-1:5 (EA: PE) to give compound 8d (5.61g, 6.1mmol) with the yield: 97.8% as a dark red oily liquid;

MS(MALDI)(M⁺,C₄₉H₄₉F₆NO₇S):calcd:909.31；found:909.21.¹H NMR(600MHz,CDCl₃)δ10.07(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,OCH₂),4.49–4.47(m,1H,OCH),4.30(t,J＝6.2Hz,2H,NCH₂),3.82–3.68(m,2H,OCH₂),3.51–3.38(m,4H,OCH₂),2.92(s,3H,NCH₃),2.88(t,J＝6.2Hz,2H,SCH₂),2.66(s,2H,CH₂),2.38(s,2H,CH₂),1.64–1.58(m,2H,CH₂),1.51–1.40(m,4H,CH₂),0.95(s,6H,CH₃).¹³C NMR(151MHz,CDCl₃)δ191.5,165.6,159.1,156.3,152.1(dm,¹J_FC～253Hz),151.0,150.5(dm,¹J_FC～260Hz),149.7,140.1(dm,¹J_FC～246Hz),138.5(dm,¹J_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, compound 8d (6.17mmol, 5.61g) dissolved in an appropriate amount of acetone was added to a single-neck flask, 1N HCl (1N, 12.34mmol, 12.34mL) was added, reaction was carried out at room temperature for 2h, then sodium bicarbonate was added for neutralization, after drying, extraction was carried out with EA, chromatography was carried out with spin-drying at an eluent ratio of 1:6-2:1 (EA: PE) to give compound 9(3.91g, 4.73mmol), a dark red product, compound, in yield: 76.4 percent;

MS(MALDI)(M⁺,C₄₄H₄₁F₆NO₆S):calcd:825.26；found:825.15.1H NMR(600MHz,CDCl₃)δ10.17(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,OCH₂),4.40(t,J＝6.2Hz,2H,NCH₂),3.82(t,J＝5.7Hz,2H,OCH₂),3.50(t,J＝5.7Hz,2H,OCH₂),3.00(s,3H,NCH₃),2.97(t,J＝6.2Hz,2H,SCH₂),2.76(s,2H,CH₂),2.48(s,2H,CH₂),1.05(s,4H,CH₃).¹³C NMR(151MHz,CDCl₃)δ191.6,165.6,159.1,156.2,152.2(dm,¹J_FC～260Hz),150.9,150.5(dm,¹J_FC～256Hz),140.2(dm,¹J_FC～246Hz),138.5(dm,¹J_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, adding 1-ethyl-3 (3-dimethylpropylamine) carbodiimide (12.02mmol, 2.31g), 4-dimethylaminopyridine (1.20mmol, 0.15g), 6,6',6' - ((ethane-1, 1, 1-triacyltris (benzene-4, 1-diacyl)) tris (oxy) trihexanoic acid (0.89mmol, 0.58g) in a two-necked flask under an argon atmosphere, adding an appropriate amount of DCM at 0 ℃, after 45mins adding compound 9(4.01mmol, 3.31g) dissolved in an appropriate amount of DCM, after 2h, refluxing at 40 ℃ overnight, extracting with DCM, removing the solvent under vacuum, purifying with a chromatographic column to obtain compound 10(2.44g, 0.79mmol) in an eluent ratio of 1:50-1:10 (EA: DCM), and obtaining compound 10(2.44g, 0.79mmol) with a yield of 88.2% as a dark red oily liquid;

MS(MALDI)(M⁺,C₁₇₀H₁₆₅F₁₈N₃O₂₄S₃):calcd:3070.07；found:3070.14.¹H NMR(600MHz,CDCl₃)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,OCH₂),4.40(t,J＝6.2Hz,6H,NCH₂),4.25(t,J＝6.0Hz,6H,OCH₂),3.91(t,J＝6.3Hz,6H,OCH₂),3.60(t,J＝6.0Hz,6H,OCH₂),2.99(s,9H,NCH₃),2.97(t,J＝6.2Hz,6H,SCH₂),2.75(s,6H,CH₂),2.47(s,6H,CH₂),2.30(t,J＝7.5Hz,6H,CH₂),2.08(d,J＝20.0Hz,3H,CH₃),1.78–1.73(m,6H,CH₂),1.68–1.62(m,6H,CH₂),1.50–1.43(m,6H,CH₂),1.04(s,18H,CH₃).¹³C NMR(151MHz,CDCl₃)δ191.5,173.5,171.2,165.5,159.1,157.0,156.2,152.1(dm,¹J_FC～255Hz),150.9(dm,¹J_FC～257Hz),150.5,149.4,141.7,140.1(dm,¹J_FC～258Hz),138.5(dm,¹J_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:

in a two-neck flask under argon atmosphere, compound 10(0.32mmol, 1.01g), 2- (3-cyano-4-methyl-5-phenyl-5- (trifluoromethyl) furan-2 (5H) -ethylene) malononitrile (1.15mmol, 0.36g) were added, dissolved in 5-6mL ethanol, reacted at 65 ℃ for 3H, spin dried through a chromatography column with an eluent ratio of 1:7-1:1 (EA: PE) to give chromophore H4(0.53g, 0.13mmol) in yield: 41.8 percent;

HRMS(ESI)(M⁺,C₂₁₈H₁₈₃F₂₇N₁₂O₂₄S₃):calcd:3962.2277；found:3962.2223.¹H NMR(600MHz,CDCl₃)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,OCH₂),4.37(t,J＝6.2Hz,6H,NCH₂),4.25(t,J＝6.0Hz,6H,OCH₂),3.90(t,J＝6.3Hz,6H,OCH₂),3.62(t,J＝6.0Hz,6H,OCH₂),3.02(s,9H,NCH₃),2.95(t,J＝6.3Hz,6H,SCH₂),2.54–2.45(m,6H,CH₂),2.35–2.20(m,12H,CH₂),1.79–1.72(m,6H,CH₂),1.68–1.61(m,9H,CH₃,CH₂),1.50–1.42(m,6H,CH₂),0.98(s,9H,CH₃),0.89(s,9H,CH₃).¹³C NMR(151MHz,CDCl₃)δ175.4,173.5,165.4,162.9,159.1,157.0,154.2,152.2(dm,¹J_FC～255Hz),150.5(dm,¹J_FC～259Hz),150.1,147.3,141.7,140.2(dm,¹J_FC～249Hz),138.5(dm,¹J_FC～258Hz),137.79,132.7,132.1,131.4,129.9,129.7,129.2,128.3,126.8,125.0,124.7,117.3,113.5,112.0,111.2,108.7,107.4,68.5,67.5,63.5,61.1,58.4,50.6,41.7,41.1,38.7,34.1,30.4,29.0,28.6,27.8,25.7,24.6.

example 2

An organic optical nonlinear chromophore based on a single-donor self-assembly structure comprises H1-H3, the structure of which is shown in figure 2, and the chromophores H1-H3 show good solubility in common organic solvents, such as ethyl acetate, ethanol, acetone and the like.

The preparation process comprises the synthesis of chromophores H1-H3, and comprises the following steps:

s1, under the condition of argon atmosphere and ice bath, adding metal sodium (32.03mmol, 0.74g) into a double-neck flask, dissolving the metal sodium with a proper amount of ethanol, adding 2-mercaptoethanol (32.03mmol, 2.26mL), adding a compound 1(32.03mmol, 4.94g) after 20mins, adding a compound 2a (32.03mmol, 9.4g) dissolved with a proper amount of ethanol after 1h, refluxing the reaction overnight at 65 ℃, performing spin-drying, extracting with EA, performing spin-drying on a chromatographic column, and obtaining a compound 3a (6.7g,13.6mmol) with the eluent ratio of 1:10-1:5 (EA: PE), wherein the yield is as follows: 42.5% as red oily liquid;

MS(MALDI)(M⁺,C₂₇H₄₃NO₃SSi):calcd:489.79；found:489.81.¹H NMR(300MHz,CDCl₃)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,NCH₂,OCH₂),3.48–3.60(m,4H,OCH₂,SCH₂),3.04(s,3H,NCH₃),2.59(m,2H,CH₂),2.45(m,2H,CH₂),1.07(s,6H,CH₃),0.87(s,9H,CH₃₎,0.01(s,6H,CH₃).¹³C{1H}NMR(126MHz,CDCl₃)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, under the argon atmosphere, adding imidazole (14.4mmol, 0.98g) and tert-butyldimethylchlorosilane (14.4mmol, 2.17g) into a double-neck flask, adding a compound 3a (2.93g, 6.0mmol) dissolved in a proper amount of DMF, reacting at room temperature for 3h, after drying in a rotary manner, extracting with EA, and passing through a chromatographic column in a rotary manner, wherein the ratio of an eluent is 1:10-1:7 (EA: PE), so as to obtain a compound 4a (3.02g, 5.0mmol), wherein the yield is: 83.3 percent of red oily liquid;

MS(MALDI)(M⁺,C₃₃H₅₇NO₃SSi₂):calcd:604.05；found:603.95.¹H NMR(300MHz,CDCl₃)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,CH₂),3.51(m,2H,CH₂),2.96–2.78(m,3H,NCH₃),2.59(s,2H,CH₂),2.39(s,2H,CH₂),1.06(s,6H,CH₃),0.91–0.77(m,18H,CH₃),0.08–0.02(m,12H,CH₃).¹³C{1H}NMR(126MHz,CDCl₃)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, adding sodium hydride (60%, 20mmol, 0.80g) into a double-neck flask, dissolving with a proper amount of THF, dropwise adding diethyl cyanomethylphosphonate (20.0mmol, 3.54g), adding a compound 4a (5.0mmol, 3.02g) dissolved with THF after the solution becomes clear, reacting at 68 ℃ under reflux overnight, after spin-drying the solvent, extracting with EA, purifying with a chromatographic column, wherein the ratio of the eluent is 1:15-1:8 (EA: PE), obtaining a compound 5a (2.3g, 3.7mmol), and the yield is: 74% as red oily liquid;

(M⁺,C₃₅H₅₈N₂O₂SSi₂):calcd:627.09；found:627.13.¹H NMR(300MHz,CDCl₃)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,CH₂),3.48(m,2H,CH₂),2.99(m,3H,NCH₃),2.67(m,2H,CH₂),2.53(s,2H,CH₂),2.43(s,2H,CH₂),0.99(s,6H,CH₃),0.87(m,18H,CH₃),0.05–0.02(m,12H,CH₃).¹³C{1H}NMR(126MHz,CDCl₃)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, adding compound 5a (3.7mmol, 2.3g) dissolved in DCM into a double-neck flask, dropwise adding diisobutylaluminum hydride (1M, 7.4mmol, 7.4mL) at-78 ℃, reacting for 3h at low temperature, slowly adding 10mL DCM and 10mL water at 0 ℃, quenching for 1h, extracting with DCM, spin-drying the solvent, purifying with a chromatographic column with an eluent ratio of 1:10-1:7 (EA: PE) to obtain compound 6a (1.54g, 2.44mmol), with the yield: 66% as a dark red oily liquid;

MS(MALDI)(M⁺,C₃₅H₅₉NO₃SSi₂):calcd:630.09；found:630.15.¹H NMR(300MHz,CDCl₃)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,CH₂),3.49(m,2H,CH₂),3.01(s,3H,NCH₃),2.70(s,2H,CH₂),2.47(s,2H,CH₂),2.11(s,2H,CH₂),1.01(s,6H,CH₃),0.86(m,18H,CH₃),0.02(s,12H,CH₃).¹³C{1H}NMR(126MHz,CDCl₃)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, adding a compound 6(12.2mmol, 7.7g) dissolved in an appropriate amount of acetone into a single-neck flask, adding 1N HCl (1N, 48.9mmol), reacting at room temperature for 3h, then neutralizing with sodium bicarbonate, performing acid-base neutralization, performing extraction with EA after spin-drying, and performing spin-drying on a chromatographic column to obtain a dark red product, namely a compound 7a (3.4g, 8.8mmol), with a ratio of eluent of 1:5-2:1 (EA: PE), wherein the yield is as follows: 72.0 percent;

MS(MALDI)(M⁺,C₂₃H₃₁NO₃S):calcd:401.56；found:401.78.¹H NMR(300MHz,CDCl₃)d 10.08(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,NCH₂),3.52(m,2H,OCH₂),3.02(s,3H,NCH₃),2.76(m,4H,SCH₂,OCH₂),2.49(m,2H,CH2),2.31(m,2H,CH₂),1.02(s,6H,CH₃).¹³C{1H}NMR(126MHz,CDCl₃)d 191.79 157.37,150.83,150.17,135.29,128.85 127.50,126.49,124.92,124.52,112.12,61.06,59.86,54.54,41.95,39.78,38.74,38.02,29.97,28.17.

s6, under argon atmosphere, adding 1-ethyl-3 (3-dimethylpropylamine) carbodiimide (3.28mmol, 0.63g), 4-dimethylaminopyridine (0.33mmol, 0.040g), 3, 4-bis (benzyloxy) benzoic acid (1.63mmol, 0.55g) into a double-neck flask, adding a proper amount of DCM and 45mins at 0 ℃, adding a compound 7a (0.82mmol, 0.33g) dissolved with a proper amount of DCM, after 2h, refluxing the reaction overnight at 40 ℃, extracting with DCM, spin-drying the mixture through a chromatographic column, and obtaining a compound 8a (0.70mmol,0.72g) with an eluent ratio of 1:8-1:5 (EA: PE), wherein the yield is as follows: 85% as a dark red oily liquid;

MS(MALDI)(M⁺,C₆₅H₆₃NO₉S):calcd:1033.42；found:1033.36.¹H NMR(600MHz,CDCl₃)δ10.18(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,OCH₂),4.45(t,J＝5.9Hz,2H,NCH₂),4.37(t,J＝6.3Hz,2H,OCH₂),3.70(t,J＝5.8Hz,2H,OCH₂),3.00(s,3H,NCH₃),2.95(t,J＝6.3Hz,2H,SCH₂),2.76(s,2H,CH₂),2.44(s,2H,CH₂),1.05(s,6H,CH₃).¹³C NMR(151MHz,CDCl₃)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, adding 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), adding an appropriate amount of DCM and 45mins at 0 ℃, adding a compound 7a (0.69mmol, 0.28g) dissolved in an appropriate amount of DCM, after 2h, refluxing the reaction overnight at 40 ℃, extracting with DCM, removing the solvent under vacuum, purifying with a chromatographic column at an eluent ratio of 1:8-1:5 (EA: PE) to obtain a compound 8b (0.58g, 0.48mmol), with the yield: 69.6% as a dark red oily liquid;

MS(MALDI)(M⁺,C₆₅H₅₁F₁₂NO₉S):calcd:1250.31；found:1250.32.¹H NMR(600MHz,CDCl₃)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,OCH₂),4.93(s,4H,OCH₂),4.49(t,J＝5.8Hz,2H,NCH₂),4.39(t,J＝6.2Hz,2H,OCH₂),3.74(t,J＝5.8Hz,2H,OCH₂),3.05(s,3H,NCH₃),2.96(t,J＝6.2Hz,2H,SCH₂),2.76(s,2H,CH₂),2.43(s,2H,CH₂),1.05(s,6H,CH₃).¹³C NMR(151MHz,CDCl₃)δ191.5,165.8,165.5,159.1,156.1,152.2(dm,¹J_FC～260Hz),150.5(dm,¹J_FC～246Hz),149.5,140.2(dm,¹J_FC～258Hz),138.5(dm,¹J_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, a two-neck flask was charged with 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), after addition of an appropriate amount of DCM at 0 ℃ and 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 ℃, extracted with DCM, spin-dried through a chromatography column at an eluent ratio of 1:8-1:5 (EA: PE) to give compound 8c (0.55g, 0.40mmol) with a yield of: 54.8% as a dark red oily liquid;

MS(MALDI)(M⁺,C₆₅H₄₃F₂₀NO₉S):calcd:1393.23；found:1393.33.¹H NMR(600MHz,CDCl₃)δ10.18(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,OCH₂),5.02(s,4H,OCH₂),4.50(t,J＝5.8Hz,2H,NCH₂),4.38(t,J＝6.3Hz,2H,OCH₂),3.78(t,J＝5.8Hz,2H,OCH₂),3.07(s,3H,NCH₃),2.96(t,J＝6.3Hz,2H,SCH₂),2.76(s,2H,CH₂),2.44(s,2H,CH₂),1.05(s,6H,CH₃).¹³C NMR(151MHz,CDCl₃)δ191.6,165.9,165.5,159.2,159.0,156.2,156.0,149.5,146.7(dm,¹J_FC～253Hz),145.1(dm,¹J_FC～260Hz),141.6(dm,¹J_FC～257Hz),139.8(dm,¹J_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 (0.34mmol, 0.35g), 2- (3-cyano-4-methyl-5-phenyl-5- (trifluoromethyl) furan-2 (5H) -ethylene) malononitrile (0.41mmol, 0.13g) were added to a two-necked flask, dissolved in 5-6mL ethanol, reacted at 65 ℃ for 3H, spun through a chromatography column, and eluted at a ratio of 1:10-1:3 (EA: PE) to give chromophore H1(0F) (0.26g, 0.20mmol) with yield: 58.8 percent;

HRMS(ESI)(M⁺,C₈₁H₆₉F₃N₄O₉S):calcd:1331.4816；found:1331.4815.¹H NMR(600MHz,CDCl₃)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,OCH₂),4.43(t,J＝5.8Hz,2H,NCH₂),4.32(t,J＝6.2Hz,2H,OCH₂),3.69(t,J＝5.8Hz,2H,OCH₂),3.00(s,3H,NCH₃),2.91(t,J＝6.3Hz,2H,SCH₂),2.44(s,2H,CH₂),2.34–2.21(m,2H,CH₂),0.96(s,3H,CH₃),0.88(s,3H,CH₃).¹³C NMR(151MHz,CDCl₃)δ175.6,166.2,165.9,162.8,159.8,157.2,154.5,150.1,147.3,137.9,136.4,131.7,131.4,129.9,129.7,129.2,128.7,128.2,127.6,126.8,125.1,124.7,117.2,112.0,110.7,108.6,108.4,107.5,107.1,70.3,63.4,62.2,58.2,50.6,41.7,41.1,38.7,34.2,30.4,29.7,29.3,28.6,27.9.

synthesis of chromophore H2:

under argon atmosphere, compound 8b (0.52mmol, 0.65g), 2- (3-cyano-4-methyl-5-phenyl-5- (trifluoromethyl) furan-2 (5H) -ethylene) malononitrile (0.62mmol, 0.20g) were added to a two-necked flask, dissolved in 5-6mL ethanol, reacted at 65 ℃ for 3H, spin-dried over a chromatographic column with an eluent ratio of 1:10-1:3 (EA: PE) to give chromophore H2(3F) (0.43g, 0.28mmol) with yield: 53.8 percent;

HRMS(ESI)(M⁺,C₈₁H₅₇F₁₅N₄O₉S):calcd:1547.3685；found:1547.3687.¹H NMR(600MHz,CDCl₃)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＝2.3Hz,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,OCH₂),4.94(s,4H,OCH₂),4.49(t,J＝5.8Hz,2H,NCH₂),4.36(t,J＝6.2Hz,2H,OCH₂),3.76(t,J＝5.8Hz,2H,OCH₂),3.07(s,3H,NCH₃),2.94(t,J＝6.3Hz,2H,SCH₂),2.45(s,2H,CH₂),2.31(s,2H,CH₂),0.99(s,3H,CH₃),0.89(s,3H,CH₃).¹³C NMR(151MHz,CDCl₃)δ175.4,165.8,165.4,163.0,159.1,156.8,153.8,152.2(dm,¹J_FC～257Hz),150.5(dm,¹J_FC～245Hz),150.1,147.3,140.2(dm,¹J_FC～260Hz),138.5(dm,¹J_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:

under argon atmosphere, compound 8c (0.38mmol, 0.53g), 2- (3-cyano-4-methyl-5-phenyl-5- (trifluoromethyl) furan-2 (5H) -ethylene) malononitrile (0.38mmol, 0.13g) were added to a two-necked flask, dissolved in 5-6mL ethanol, reacted at 65 ℃ for 3H, spin dried through a chromatography column with an eluent ratio of 1:10-1:3 (EA: PE) to give chromophore H3(5F) (0.33g, 0.20mmol) with a yield of: 52.6 percent;

HRMS(ESI)(M⁺,C₈₁H₄₉F₂₃N₄O₉S):calcd:1691.2931；found:1691.2937.¹H NMR(600MHz,CDCl₃)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,OCH₂),5.02(s,4H,OCH₂),4.51(t,J＝5.7Hz,2H,NCH₂),4.36(t,J＝6.2Hz,2H,OCH₂),3.80(t,J＝5.8Hz,2H,OCH₂),3.09(s,3H,NCH₃),2.94(t,J＝5.6Hz,2H,SCH₂),2.46(s,2H,CH₂),2.33(s,2H,CH₂),0.99(s,3H,CH₃),0.90(s,3H,CH₃).¹³C NMR(151MHz,CDCl₃)δ175.5,165.8,165.5,162.9,159.2,159.0,150.2,147.3,146.7(dm,¹J_FC～260Hz),145.1(dm,¹J_FC～258Hz),141.6(dm,¹J_FC～246Hz),139.9(dm,¹J_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 illustrate the invention more clearly, the invention also carried out the following characterization experiments for the chromophores H1-H4 obtained in the examples:

(1) spectral absorption characteristics and thermal stability

Thermal stability of chromophores H1-H4 is characterized by a thermogravimetric curve, which is shown in FIG. 6;

② the ultraviolet visible spectrum of chromophores H1-H4 in chloroform solution is shown in figure 8;

(iii) ultraviolet and visible spectra of chromophores H1-H4 in the film are shown in FIG. 9;

wherein the main parameters of the spectral absorption characteristics and the thermal stability of the four chromophore molecules are shown in table 1;

TABLE 1 spectral absorption, thermal stability parameters of four chromophore molecules

Wherein λ is_max ^a、λ_max ^b、λ_max ^dIs the measurement result of the chromophore molecule in chloroform, 1, 4-dioxane and electro-optical film separately, and has high Δ λ^cIs λ_max ^a、λ_max ^bThe difference therebetween;

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

Maximum absorption wavelength (. lamda.) of chromophores H1-H4 in thin films_max) 773nm, 759nm and 755nm, respectively, different from the solution. This phenomenon suggests that there may be different interactions between chromophores consisting of different spacer groups and polymers.

(2) Energy level calculation

The charge transfer interaction within the chromophore can be calculated by the difference in energy gap between the HOMO-LUMO molecular orbitals. To analyze the composition of the HOMO-LUMO and the depth of the leading edge trajectory, the inventors run the Multiwfn program using Ros-Schuit (SCPA) partitioning and DFT calculations;

the chromophore is divided into three parts: donor, pi-bridge and acceptor, and calculating the percent contribution: for the four chromophores H1-H4, HOMO is stabilized predominantly by the donor (42.90% -45.38%) and pi-bridge (32.15-33.73%) contributions, while LUMO is stabilized predominantly by the acceptor (42.48% -44.02%) and pi-bridge (40.65% -40.95%) contributions.

DFT calculations were used to calculate the HOMO-LUMO gap (. DELTA.E), which is shown in FIG. 11 for chromophores H1-H4, which have Δ E values of 1.958eV, 1.981eV, 1.977eV, and 1.938eV, respectively. The four chromophores have similar spacer groups attached to the electron bridge and the donor, respectively. These chromophores all have similar conjugated structures, and as can be seen from the uv absorption data, the substituted steric hindrance group does not affect the conjugated structure.

(3) Electro-optic coefficient

The invention compares the micro hyperpolarizability of four chromophores with different isolation functional groups to convert into the macro r₃₃Efficiency of the value. The chromophores were first prepared into electro-optic films: the above chromophores were dissolved in

redistilled

1,1, 2-trichloroethane, the dissolved chromophore solution was filtered through a 0.2mm PTFE filter, the filtered solution was spin coated on an ITO glass substrate, and after removal of the solvent, the resulting film of chromophore composite was heated in vacuum at 50 ℃ overnight to ensure removal of residual solvent. Contact polarization process at the glass transition temperature (T) of the electro-optic material_g) The above is carried out at a temperature of 5 to 10 ℃. The electro-optic coefficient r of the polarizing film under the wavelength of 1310nm is calculated by adopting a Teng-Man simple reflection method₃₃The method uses thin ITO electrodes of low reflectivity and good transparency to minimize multiple reflections. As previously mentioned, controlling the geometry and delocalization of molecules by introducing steric spacer groups in chromophores may be an effective way to minimize interactions between chromophores, and therefore, these methods may have the significant advantage that the β value can be optimally converted to r₃₃Thereby increasing macroscopic electro-optic activity.

(4) Performance of assembled device

Measuring each performance index of the device assembled by the four small molecular chromophores, and the result is shown in table 2;

TABLE 2 Performance index of several small molecule chromophore assembled devices

Average polarization efficiencies (r) of H1, H2, H3, and H4₃₃A polarizing field or r₃₃/E_p) 1.63 +/-0.07, 2.26 +/-0.08, 1.36 +/-0.07 and 2.76 +/-0.08 nm respectively²/V²Higher than the host-guest polymer material, as shown in figure 13. In the case of similar first-order hyperpolarizabilities, the difference in polarization efficiencies between H1 and H3 is mainly attributed to the number of chromophores per unit volume, and the polarization efficiency of the electro-optic film H2 is higher although the concentration of chromophores is lower. H3 was subjected to pi-pi stacking by electrostatic mechanism to obtain a highly polarization-induced sequence. Due to the multichromophore structure, the polarization efficiency of H4 is further improved to 2.76 +/-0.08 nm²/V²: the three chromophore molecules are connected to the intermediate core in a covalent bond mode, so that the chromophore molecules can rotate freely under the action of an electric field, the chromophores can be effectively separated, and the electrostatic interaction among the molecules is weakened. Of course, the improvement of the polarization efficiency of chromophore H4 also benefits from the pi-pi stacking of trifluorobenzene, resulting in a highly polarization-induced sequence.

To evaluate the effect of HD-PFD and PFD-AH self-assembly on EO performance, basic devices of 1:1H1: H3 and 1:2H3: HLD1 were made, where chromophore HLD1 was synthesized in the known literature. And carrying out polarization treatment and calculating polarization efficiency.

The average polarization efficiencies of the chromophore mixing ratios 1:1H1: H3 and 1:2H3: HLD1 were 3.26 + -0.10 and 3.17 + -0.09 nm, respectively²/V²Significantly higher than the chromophore H1 and the chromophore HLD 1. Intermolecular interactions between electronegative aromatic phenyl ring groups and electropositive pentafluorophenyl groups or pi-pi stacking of trifluorobenzenes contribute to a highly polarization-induced sequence. When the temperature rises to the glass transition temperature of the electro-optical film, the molecular arrangement formed by intermolecular hydrogen bonds is dissociated by electric field polarization. Then, under the action of an electric field, the electro-optic film is gradually cooled to room temperature, and the polarization orientation under the action of the electric field is fixed through the non-covalent cross-linked network, so that the order degree of the eccentric chromophore is enhanced and stabilized. Optimal r for 1:1H1: H3 and 1:2H3: HLD1₃₃The values are 328 and 317pm/V respectively, which are much higher than the diethylamine reported previouslyA chromophore of a phenyl donor.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. A self-assembled organic optical nonlinear chromophore, wherein the chromophore molecule is H4, and the structural formula is as follows:

2. a method for synthesizing the self-assembled organic optically nonlinear chromophore of claim 1, wherein the method for synthesizing the chromophore H4 comprises the following steps:

p1, condensation reaction of 4- (methyl (2- ((tetrahydro-2H-pyran-2-yl) oxy) ethyl) amino) benzaldehyde with isophorone under the conditions of sodium ethoxide and 2-mercaptoethanol to give compound (3 b);

p6, attaching a self-assemblable spacer group to the alcoholic hydroxyl group of said compound (7b) by nucleophilic substitution or Steglich esterification to give compound (8 d);

hydrolyzing the compound (8d) with acid and P7 to obtain a compound (9);

p9, the chromophore H4, is obtained after condensation of the compound (10) with an acceptor molecule.

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

p2, in a flask containing imidazole and tert-butyldimethylsilyl chloride, was slowly added to the N, N-dimethylamide solution of the compound (3b), reacted at room temperature for 3 hours under an argon atmosphere, extracted with ethyl acetate, purified by silica gel chromatography, and purified with ethyl acetate and petroleum ether as an eluent to obtain the compound (4 b).

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

p3, under the condition of ice bath in an argon protective environment, slowly adding diethyl cyanomethylphosphonate into a tetrahydrofuran solution of sodium hydride, adding the compound (4b), carrying out reflux reaction at 65 ℃ overnight, after the reaction is finished, carrying out vacuum spin-drying on the solvent, extracting with ethyl acetate, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluents to obtain the compound (5 b).

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

p4, slowly adding a hexane solution of diisobutylaluminum hydride into a dichloromethane solution of the compound (5b), reacting at-78 ℃ under an argon protective atmosphere for a period of time, adding a certain amount of dichloromethane and water at 0 ℃ for quenching, performing suction filtration after the reaction is finished, extracting the filtrate with dichloromethane, concentrating, purifying by silica gel chromatography, and purifying by using ethyl acetate and petroleum ether as eluent to obtain the compound (6 b).

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

p5, the compound (6b) is subjected to alkaline hydrolysis treatment to remove the tert-butyldiphenylchlorosilane protecting group, extracted with ethyl acetate, and purified by silica gel chromatography using ethyl acetate and petroleum ether as eluents to obtain the compound (7 b).

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

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

p7 and the compound (8d) were subjected to acid hydrolysis to remove the (2-tetrahydropyran) protecting group, followed by extraction with ethyl acetate and purification by silica gel chromatography using ethyl acetate and petroleum ether as eluents to give the compound (9).

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

p8, slowly adding dichloromethane solution into 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, reacting for a while at 0 ℃ under an argon atmosphere, slowly adding dichloromethane solution of the compound (9), heating and refluxing, extracting an organic phase with dichloromethane, removing the solvent by spin-drying, purifying by silica gel chromatography using dichloromethane and ethyl acetate as eluents to obtain the compound (10).

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

10. The use of the self-assembled organic optical nonlinear chromophore of claim 1, wherein the self-assembled organic optical nonlinear chromophore H4 is used as an electro-optic material and in an electro-optic modem.