Organic compound and application thereof

Abstract

The embodiment of the invention provides an organic compound and application thereof. The organic compound has a structural general formula shown in a formula (I): # imgabs0 #, A represents an electron acceptor, D represents an electron donor, Z represents a sulfur atom, an oxygen atom or NH, and R1 is selected from substituted or unsubstituted C1-C10 alkylene; n is an integer selected from 0-2; x1 comprises at least one first cross-linkable group, X2 comprises at least one second cross-linkable group, and the first cross-linkable group and the second cross-linkable group can be subjected to a ring addition cross-linking reaction. The organic compound with the structural characteristics can simultaneously have higher glass transition temperature, higher electro-optic coefficient, higher polarization efficiency and the like, and can be used for electro-optic active films, electro-optic devices and the like with excellent performance.

Description

Technical Field

[0001] The embodiments of the present application relate to the technical field of organic electro-optical materials, and in particular, to an organic compound and its application. Background Art

[0002] Electro-optic modulators are the core devices for realizing photoelectric information conversion, and are also the key link to break through the two major technical challenges of bandwidth and energy consumption of optical communication networks. As the core component of electro-optic modulators, electro-optic materials have attracted widespread attention. Among them, organic electro-optic materials are considered to have broad application prospects because of their advantages such as being able to design structures at the molecular level, higher electro-optic coefficients than inorganic optical materials such as lithium niobate, faster response speed, and good processability.

[0003] According to the interaction between molecules after polarization orientation, organic electro-optical materials can be divided into self-assembly type and cross-linking type. Among them, cross-linking electro-optical materials have become a research hotspot in recent years due to their high stability in polarization orientation. Existing cross-linking electro-optical materials usually include chromophores and cross-linking agents (such as small molecules, polymers), or include at least two chromophores, but the content of the effective active ingredient-chromophore in the former is low, and the room for improving the electro-optic coefficient is limited, while the latter can better improve the electro-optic coefficient. Among them, the binary chromophore cross-linking system requires the two chromophores to be adjusted in ratio and then mixed, which is cumbersome to operate, and the glass transition temperature (T g ) usually have differences, resulting in uncertainty in the polarization process and cumbersome polarization steps. Therefore, it is necessary to develop a new cross-linked electro-optical material that is more conducive to practical applications. Summary of the invention

[0004] In view of this, an embodiment of the present application provides a self-crosslinking organic compound, which can undergo a cycloaddition crosslinking reaction between two crosslinkable groups, thereby avoiding the problem of needing to regulate the ratio of the two chromophores and the problem of difficult Tg matching of the two chromophores in a binary chromophore crosslinking system.

[0005] Specifically, the first aspect of the embodiment of the present application provides an organic compound, wherein the organic compound has the general structural formula shown in formula (I):

[0006]

[0007] In formula (I), A represents an electron acceptor, D represents an electron donor, Z represents a sulfur atom, an oxygen atom or NH, and R1 is selected from substituted or unsubstituted C1-C 10 Alkylene; n is an integer selected from 0-2; X1 includes at least one first crosslinkable group, X2 includes at least one second crosslinkable group, and a cycloaddition crosslinking reaction can occur between the first crosslinkable group and the second crosslinkable group.

[0008] In the above organic compound provided in the embodiment of the present application, the two cross-linkable groups that can react with each other are respectively connected in the same chromophore (i.e., the organic compound) by covalent bonds, which makes the organic compound a self-cross-linking chromophore. When using it to prepare an electro-optically active film, there is no need to introduce a second chromophore, which accordingly avoids the problem of regulating the ratio of the two chromophores and the difficulty in matching the Tg of the two chromophores. Moreover, the electro-optically active film prepared by using the self-cross-linking organic compound takes into account both high electro-optic coefficient and thermal stability, which is conducive to the actual stable and effective operation of the electro-optical device.

[0009] In some embodiments of the present application, Z is a sulfur atom and R1 is -CH2-CH2. In this case, the organic compound represented by formula (I) is easier to synthesize and has a higher yield.

[0010] In the embodiment of the present application, the first crosslinkable group and the second crosslinkable group are independently selected from one or more of anthracene, acrylate, maleamide, furanyl, aryl azide, and alkynyloxy. In this case, the first crosslinkable group and the second crosslinkable group mentioned above must still be able to undergo a cycloaddition crosslinking reaction.

[0011] In some embodiments of the present application, X1 and X2 are independently selected from One or more of; the position marked with * is the connection position.

[0012] In the embodiment of the present application, the D independently comprises an aromatic amine structure or a heteroaromatic amine structure containing a tertiary amino nitrogen atom. D with a tertiary amino nitrogen atom may have a stronger electron-donating ability.

[0013] In some implementation modes of the present application, A is specifically X is an oxygen atom, a sulfur atom, NH or CH2. The organic compound represented by the formula (I) having this A is relatively easy to synthesize.

[0014] A second aspect of an embodiment of the present application provides a film, which includes a cross-linked product of the organic compound as described above in the embodiment of the present application.

[0015] In some embodiments of the present application, the film is an electro-optically active film, the electro-optic coefficient of the electro-optically active film is greater than or equal to 190 pm / V, and the glass transition temperature is greater than or equal to 150° C. The electro-optically active film can take into account both high thermal stability and electro-optic coefficient, and is suitable for manufacturing components of optical communication systems that require high thermal stability.

[0016] A third aspect of the present application also provides a method for preparing an electro-optically active film, comprising the following steps:

[0017] Applying a solution containing the organic compound of the present embodiment on a substrate and drying it to form a film layer;

[0018] Applying an electric field to the film layer and heating it at a first temperature to polarize the organic compound;

[0019] The polarized film layer is further heated to a second temperature to allow the organic compound to self-crosslink, and then the temperature is lowered to obtain an electro-optically active film.

[0020] The electro-optically active film obtained through the above-mentioned polarization and cross-linking steps has high polarization stability and high glass transition temperature, can work stably for a long time at a relatively high temperature, and is particularly suitable for the manufacture of electro-optical devices.

[0021] The fourth aspect of the embodiments of the present application also provides the use of the above-mentioned organic compounds, the above-mentioned films, and the electro-optically active films prepared by the above-mentioned electro-optically active film preparation method of the embodiments of the present application in components of optical communication systems, solar cells, organic electroluminescent devices, and organic photoluminescent devices.

[0022] The components of the optical communication system include one or more of electro-optical devices, optical switches, straight waveguides, bent waveguides, single-mode optical splitters, routers, filters, optical interconnectors, and resonators.

[0023] The embodiments of the present application also provide an electro-optical device, including the film described above in the embodiments of the present application, or an electro-optical active film prepared by the method for preparing the electro-optical active film described above in the embodiments of the present application.

[0024] In the implementation manner of the present application, the electro-optical device includes one or more of an electro-optical modulator, a coupler, a terahertz detector, an electro-optical frequency shifter, and a frequency comb source. The electro-optical modulator includes one or more of a Mach-Zehnder modulator, a phase modulator, a silicon-organic hybrid modulator, and a plasma-organic hybrid modulator.

[0025] The embodiments of the present application also provide an optical communication system, at least some components of the optical communication system include the film described above in the embodiments of the present application, or an electro-optically active film prepared by the method for preparing the electro-optically active film described above in the embodiments of the present application.

[0026] The embodiments of the present application also provide a phased array lidar system, which includes the film described above in the embodiments of the present application, or an electro-optical active film prepared by the method for preparing the electro-optical active film described above in the embodiments of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 A schematic diagram of the structure of an electro-optic modulator provided in an embodiment of the present application.

[0028] Figure 2A This is a thermogravimetric curve of the chromophore SLD1 provided in Example 1 of the present application.

[0029] Figure 2B This is a thermogravimetric curve of the chromophore SLD2 provided in Example 2 of the present application.

[0030] Figure 3 The UV-visible spectra of the chromophore SLD1 in different solvents and films are shown.

[0031] Figure 4 The UV-visible spectra of the chromophore SLD2 in different solvents and films are shown.

[0032] Figure 5 A schematic diagram showing the use of the Teng-Man simple reflection method to test the electro-optic coefficient of an electro-optically active film.

[0033] Figure 6 Shown is the polarization curve of the film of chromophore SLD1 after self-crosslinking.

[0034] Figure 7 Shown is the polarization curve of the film of chromophore SLD2 after self-crosslinking. DETAILED DESCRIPTION

[0035] The technical solution of the embodiment of the present application is described in detail below.

[0036] In view of the fact that the existing binary chromophore cross-linking system needs to regulate the ratio of the two chromophores, and the difficulty in matching the Tg of the two chromophores leads to the cumbersome polarization process, the embodiment of the present application provides a self-cross-linking organic compound. Among them, the term "chromophore" refers to a compound that can absorb light within a certain wavelength peak and can show a certain color. The organic compound provided in the present application is also a chromophore.

[0037] Specifically, the organic compound provided in the embodiments of the present application has the general structural formula shown in formula (I):

[0038]

[0039] In formula (I), A represents an electron acceptor, D represents an electron donor, Z is a sulfur atom (S), an oxygen atom (O) or NH, and R1 is selected from substituted or unsubstituted C1-C 10 Alkylene; n is an integer selected from 0-2; X1 includes at least one first crosslinkable group, X2 includes at least one second crosslinkable group, and a cycloaddition crosslinking reaction can occur between the first crosslinkable group and the second crosslinkable group.

[0040] In the above-mentioned organic compound provided by the present application, the two cross-linkable groups are respectively connected to the same chromophore (i.e., the organic compound) by means of covalent bonds, and the two cross-linkable groups can undergo a cycloaddition cross-linking reaction with each other, which makes the organic compound a self-cross-linking chromophore with high polarization orientation. When the organic compound is used to prepare an electro-optically active film, the polarized organic compound itself can undergo a cross-linking reaction to obtain an electro-optically active film with a high electro-optic coefficient, without the need to introduce an external substance as a cross-linking agent, for example, without the need to introduce a second chromophore that can undergo a cross-linking reaction with the organic compound, which avoids the problem of regulating the ratio of the two chromophores and the problem of the T of the two chromophores. g The polarization process is complicated and unstable due to the difficulty in matching. In addition, since the organic compound can self-crosslink, the crosslinking density of its crosslinked product is large, and the T of the electro-optically active film containing its crosslinked product is g It is relatively high and is not easily stimulated by high temperature and loses its electro-optical activity. It is suitable for making electro-optical devices that can operate stably at high temperatures and can meet the requirements of the communication industry for the thermal stability of electro-optical devices.

[0041] In addition, the electro-optical activity of cross-linked organic electro-optical materials is usually achieved by applying an electric field to polarize their molecules. Generally, an electric field is applied to a dry film containing the organic electro-optical material and the dry film is heated to a temperature close to the glass transition temperature T of the organic electro-optical material. g , so that its molecules are reoriented and its dipole moment is aligned with the electric field, and then it is further heated to the crosslinking temperature of the organic electro-optical material to cause intermolecular crosslinking and stabilize the already polarized molecules; then it is cooled while the electric field is still present to maintain the polarization induction and obtain an electro-optically active film. However, if the electro-optically active film is heated again to a temperature close to the T g When the electro-optical activity is lost, the self-crosslinking organic compound provided in the present application has a glass transition temperature T g Also higher, the T g The temperature difference between the crosslinking temperature and the crosslinking temperature is appropriate, and the crosslinking temperature of the organic compound can be polarized and crosslinked to smoothly exhibit electro-optical activity; and the crosslinking temperature of the organic compound is g The electro-optical active film containing the cross-linked product can withstand higher temperatures without losing its electro-optical activity. Therefore, the organic compound provided in the present application can take into account both high electro-optical coefficient and high T g The electro-optical active film made by it also has high electro-optical coefficient and high thermal stability.

[0042] In the present application, the first crosslinkable group and the second crosslinkable group may be reactive groups that can be crosslinked by (4+2) or (3+2) cycloaddition. Exemplarily, the first crosslinkable group and the second crosslinkable group may independently include, but are not limited to, one or more of anthracene, acrylate, maleamide, furanyl, azidoaryl, alkynyloxy or a derivative thereof, etc., but it is necessary to satisfy that a cycloaddition crosslinking reaction can occur between the first crosslinkable group and the second crosslinkable group.

[0043] Specifically, anthracene groups can be cross-linked with acrylate groups or maleamide groups through (4+2) cycloaddition, maleamide groups can be cross-linked with furan groups through (4+2) cycloaddition, and aryl azide groups can be cross-linked with alkynyloxy groups through (3+2) cycloaddition. The presence of active groups that can undergo cycloaddition cross-linking reactions with each other can ensure that the cross-linking temperature of the above-mentioned organic compounds is greater than their Tg, which is beneficial for them to polarize first and then cross-link under electric field stimulation to stabilize the orientation of the polarized molecules to maintain stable electro-optical activity. By regulating each X1 and X2 with cross-linkable groups, the types of the above-mentioned organic compounds can be enriched. Among them, the acrylate group or its derivative group can be CH2=CH-COO-, CH2=CH-CH2-COO-, CH2=CH-CH2-CH2-COO-, methacrylate group (CH2=C(CH3)-COO-), etc.

[0044] In some embodiments of the present application, X1 and X2 are independently selected from One or more of; the position marked with * is the connection position. In this case, the compound represented by formula (I) is easier to synthesize. It can be understood that when X1 is When X2 is Accordingly, when X2 is When X1 is In some embodiments, one of X1 and X2 is The other is At this time, the glass transition temperature of the compound represented by formula (I) is higher, and the electro-optic coefficient of the electro-optical active film formed by using the compound is higher.

[0045] In the present application, R1 is selected from substituted or unsubstituted C1-C 10Alkylene. Among them, alkylene is a group formed by removing two hydrogen atoms bound to the carbon atom in the alkane, that is, alkylene is a group formed by removing one hydrogen atom bound to the carbon atom on the basis of the corresponding alkyl. Substituted or unsubstituted alkylene can be linear or branched. The substituents in the substituted alkylene can include but are not limited to halogen atoms, alkyl groups, alkoxy groups, etc. In some embodiments, R1 is selected from substituted or unsubstituted C1-C8 alkylene, or substituted or unsubstituted C1-C6 alkylene, or substituted or unsubstituted C2-C4 alkylene, etc. R1 with an appropriate number of carbon atoms can ensure that -R1-Z can be smoothly bonded to the π bridge in formula (I), and ensure that X1 with the first cross-linkable group can be smoothly connected to -O-R1-Z, avoiding large steric hindrance during connection and the occurrence of side reactions, etc. In some embodiments, R1 can be ethylene (-CH2CH2-), propylene (-CH2CH2CH2-), or butylene (-CH2CH2CH2-), etc.

[0046] The organic compound represented by the above formula (I) is a compound having a D-π-A structure. The electron donor (represented by "D") has a lower electron affinity than the electron acceptor (represented by "A"), and the part with multiple conjugated double bonds connecting A and D can be called a π bridge, or a "conjugated bridge", etc. Electrons can be delocalized from the electron donor D to the electron acceptor A through the atomic orbitals in the π bridge. The electron donor D and the electron acceptor A will be introduced in more detail below.

[0047] In the present application, the electron donor D generally contains a tertiary ammonia nitrogen atom, which can use the lone electron pair of the tertiary ammonia nitrogen atom to have a stronger electron-donating ability. In the embodiment of the present application, D can be an aromatic amine structure or a heteroaromatic amine structure containing a tertiary ammonia nitrogen atom.

[0048] In some embodiments of the present application, D comprises any structure represented by formula (d-1) to formula (d-6) substituted or substituted:

[0049]

[0050]

[0051] in,*, The marked position is the connection position, the position marked with * is connected to -OCO-X2, each a is independently selected from an integer of 1-3, each b is independently selected from an integer of 0-3, and R2, R3, and R4 are independently selected from substituted or unsubstituted alkyl groups.

[0052] wherein each a can be independently 1, 2 or 3; b can be specifically 0, 1, 2 or 3. R2, R3, and R4 can be independently selected from substituted or unsubstituted C1-C 10Alkyl, further can be substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C4 alkyl, etc. Wherein, the substituent in the substituted alkyl can include but is not limited to halogen atoms (such as fluorine, chlorine, bromine, iodine, etc.), univalent polar groups (such as cyano, nitro, hydroxyl, carboxyl, amino, ester group, acyl, etc.), substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloheteroalkyl, substituted or unsubstituted aryl (such as aryloxy, halogenated aryl), substituted or unsubstituted heteroaryl (such as heteroaryloxy, halogenated heteroaryl), etc. One or more. Wherein, the ring heteroatoms in cycloheteroalkyl and heteroaryl can be independently selected from one or more of N, O, S, P, etc. The introduction of various substituents can enrich the types of compounds, obtain compound products with slightly different properties, and better realize applications. In some embodiments, R2, R3, and R4 can be methyl or ethyl.

[0053] In addition, the substituents in any of the structures represented by formula (d-1) to formula (d-6) may include, but are not limited to, substituted or unsubstituted alkyl groups. Specifically, the substituted or unsubstituted alkyl group may be a substituted or unsubstituted C1-C 10 Alkyl, or substituted or unsubstituted C1-C6 alkyl, or substituted or unsubstituted C1-C4 alkyl. Exemplarily, the substituted or unsubstituted alkyl may include one or more of methyl, ethyl, n-propyl, methoxy, ethoxy, etc.

[0054] For the substituted structure represented by formula (d-2), in some embodiments, it can be specifically or Each a may be the same or different.

[0055] In the embodiment of the present application, the electron acceptor A usually carries at least one electron-withdrawing group, and the electron-withdrawing group can be selected from at least one of a cyano group (-CN), a nitro group (-NO2), a fluorine atom (F), a sulfonic acid group (-SO3H), a trihalomethyl group (such as CF3), and a trifluoromethanesulfonyl group (-SO2CF3), but is not limited thereto.

[0056] For example, in some embodiments of the present application, A includes a structure shown in formula (A-1) or formula (A-2):

[0057]

[0058] in, The marked position is the connection position, X is independently selected from oxygen atom (O), sulfur atom (S), N (R8) or CH2, R5 and R6 are independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, R7 is independently selected from electron withdrawing groups each time it appears, and R8 is hydrogen atom (H) or substituted or unsubstituted alkyl. The * marked position is the connection position.

[0059] Specifically, in formula (A-1) or formula (A-2), each R7 may be the same or different, and each occurrence of R7 is independently selected from one or more of cyano (-CN), nitro (-NO2), trihalomethyl (such as trifluoromethyl-CF3), fluorine atom (F), sulfonic acid (-SO3H), trifluoromethanesulfonyl (-SO2CF3), with cyano and / or nitro being more common. In some embodiments, each R7 is cyano.

[0060] When R5 and R6 are substituted or unsubstituted alkyl, they can be substituted or unsubstituted C1-C 20 Alkyl, or substituted or unsubstituted C1-C 12 Alkyl, or substituted or unsubstituted C1-C 10 The substituted alkyl group may be selected from the group consisting of alkyl, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C4 alkyl, etc. The substituents in the substituted alkyl group may refer to the description in the previous text of this application. The substituents in the substituted alkyl group are commonly halogen atoms, alkoxy groups, hydroxyl groups, and aryl groups. For example, the substituted alkyl group may be trifluoromethyl or benzyl (i.e., a methyl group substituted with a phenyl group).

[0061] When R5 and R6 are substituted or unsubstituted aryl groups, they can be monocyclic aryl groups or polycyclic aryl groups. The polycyclic aryl groups can be condensed ring type or non-condensed ring type (such as biphenyls). For non-condensed ring type polycyclic aryl groups, the aromatic rings are directly connected or connected through at least one bridging group selected from oxygen atoms, sulfur atoms, alkylene groups, fluorenyl groups, etc. In the embodiment of the present application, the substituted or unsubstituted aryl group can be substituted or unsubstituted C6-C 20 Aryl, or substituted or unsubstituted C6-C 15 Aryl, or substituted or unsubstituted C6-C 12 Aryl. For example, the substituted or unsubstituted aryl group may be a substituted or unsubstituted group of phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl, binaphthyl, fluorenyl, spirofluorenyl, and the like.

[0062] When R5 and R6 are substituted or unsubstituted heteroaryl, they can be substituted or unsubstituted C3-C 20 Heteroaryl, or substituted or unsubstituted C4-C 15 Heteroaryl, or substituted or unsubstituted C5-C10 Heteroaryl, etc. Wherein, the ring heteroatoms in the heteroaryl can be selected from one or more of N, O, S, P, etc. In some embodiments, the substituted or unsubstituted heteroaryl can be specifically a substituted or unsubstituted thienyl, such as 2-thienyl, 5-phenyl-2-thienyl and 5-(3-methoxymethylpropyl ether)-2-thienyl.

[0063] The substituents in the substituted aryl and substituted heteroaryl may include one or more of halogen atoms, monovalent polar groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted cycloheteroalkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, etc. The substituents in the substituted aryl and substituted heteroaryl groups are commonly halogen atoms, halogenated alkyl groups (such as fluoroalkyl groups), alkoxy groups, hydroxyalkyl groups, aryl groups, etc. The number of carbon atoms in the substituted or unsubstituted cycloalkyl and substituted or unsubstituted cycloheteroalkyl groups may be 2-30, further 3-20, or 3-12, etc. The substituted or unsubstituted aryl group may be a substituted or unsubstituted C6-C 30 Aryl, further may be substituted or unsubstituted C6-C 20 Aryl, substituted or unsubstituted C6-C 12 The substituted or unsubstituted heteroaryl group may be a substituted or unsubstituted C3-C 30 Heteroaryl, for example, is a substituted or unsubstituted C5-C 20 Heteroaryl, substituted or unsubstituted C6-C 12 Heteroaryl.

[0064] In some embodiments, one of R5 and R6 is methyl or trifluoromethyl, and the other is a substituted or unsubstituted C1-C 10 One of alkyl, phenyl and thienyl; further, one of R5 and R6 may be trifluoromethyl (-CF3) and the other may be phenyl (-Ph).

[0065] When X is N(R8), R8 may be H, or a substituted or unsubstituted C1-C 10 In some embodiments, R8 is H.

[0066] In some embodiments, A is a structure represented by formula (A-1), and each R7 is a cyano group, one of R5 and R6 is a trifluoromethyl group (-CF3), and the other is a phenyl group (-Ph). X is O, S, NH or CH2, preferably O or NH.

[0067] By regulating X1, X2, A, D, etc. with cross-linkable reactive groups in the above formula (Ⅰ), the types of the above organic compounds can be enriched, and the glass transition temperature Tg of the organic compound can be regulated, thereby obtaining an electro-optical active film with good heat resistance and high electro-optical activity.

[0068] The following uses the compound represented by the following formula (IA) as an example to illustrate a method for preparing the above-mentioned organic compound in the embodiment of the present application.

[0069]

[0070] The preparation method of the compound represented by formula (IA) may include the following steps:

[0071] (1) protecting the hydroxyl group on the hydroxyl compound K0 that can provide the electron donor D with a precursor that can provide the first hydroxyl protecting group Q1 to obtain compound K1;

[0072] (2) reacting compound K1 with compound a and compound b of the general formula OH-R1-ZH to obtain compound K2;

[0073] (3) protecting the hydroxyl group on compound K2 using a precursor that can provide a second hydroxyl protecting group Q2 to obtain compound K4;

[0074] (4) reacting compound K3 with diethyl cyanomethylphosphonate to obtain compound K4;

[0075] (5) Reducing the compound K4 with diisobutylaluminum hydride (DIBAL), and then hydrolyzing the compound K5 to obtain the aldehyde group-containing compound;

[0076] (6) deprotecting the two second hydroxyl protecting groups on compound K5 to obtain compound K6;

[0077] (7) subjecting compound K6 to an esterification reaction with compound d having the general formula X1-COOH to obtain compound K7;

[0078] (8) subjecting compound K7 to an esterification reaction with compound e of the general formula X2-COOH to obtain compound K8;

[0079] (9) reacting compound K8 with compound f that can provide an electron acceptor A to obtain a compound represented by the above formula (IA);

[0080]

[0081] Wherein, Q1 is the first hydroxyl protecting group, Q2 is the second hydroxyl protecting group, a is an integer of 0-3, n is an integer of 0-2, and the meanings of Z, R1, R5, R6, X1, and X2 are as described above in this application.

[0082] In the above preparation method, the hydroxyl protection reaction of steps (1) and (3) can be carried out according to the hydroxyl protection technology known in the art. The above Q1 and Q2 can be the same or different hydroxyl protecting groups, and the hydroxyl protecting groups can include tetrahydropyranyl, or organosilicon groups, etc. Among them, the organosilicon group can be, for example, one or more of tert-butyldimethylsilyl (-Si(CH3)2-C(CH3)3, referred to as TMDS), tert-butyldiphenylsilyl (-Si(Ph)2-C(CH3)3), triisopropylsilyl (-Si(CH(CH3)2)3), etc. The compound after the hydroxyl group is protected by the organosilicon group is generally a silyl ether. In some embodiments, the above first hydroxyl protecting groups Q1 and Q2 are both tert-butyldimethylsilyl. At this time, the precursor of the corresponding hydroxyl protecting group can be tert-butyldimethylchlorosilane. At this time, -O-Q1 or -O-Q2 can be called tert-butyldimethylsiloxy. When the hydroxyl protecting group is Q1 or Q2 is tetrahydropyranyl, the corresponding precursor of the hydroxyl protecting group is 3,4-dihydro-2H-pyran.

[0083] Specifically, the reaction of step (1) is illustrated by taking the first hydroxyl protecting group Q1 as tert-butyldimethylsilyl, and the specific reaction formula is as follows:

[0084]

[0085] The reaction in step (2) can generate a conjugated polyene compound K2, and introduce a hydroxyl group to leave a reaction site for subsequent grafting of the group X1, so that X1 is connected to the final product. Wherein, -ZH (Z is S, O or NH) is an active group that can open the epoxy group in compound a, and can specifically be a thiol (-SH), a hydroxyl (-OH) or a primary amino group (-NH2). In order to improve the yield of the reaction in step (2), Z is preferably S or NH, and R1 is preferably a straight-chain alkylene group, such as -(CH2) 2～4 .

[0086] Taking compound b as 2-mercaptoethanol as an example, the reaction of step (2) is illustrated, and the specific reaction formula is as follows:

[0087]

[0088] The reaction carried out in step (4) can achieve the transformation of the cyclic ketone group on the cycloalkenone K3 to the cyano group, and the number of carbon atoms is increased so as to subsequently add a carbon-carbon double bond to the π bridge. The reaction equation involved in step (4) is as follows:

[0089]

[0090] In step (5), DIBAL can reduce the nitrile K4 to an amine, which is then hydrolyzed to obtain the above-mentioned aldehyde K5.

[0091] In step (6), the hydroxyl protected by the hydroxyl protecting groups Q1 and Q2 is deprotected to restore -OH to obtain a diol compound K6 with two -OH groups. The specific reaction parameters of the deprotection can be selected according to the specific Q1 and Q2. In some embodiments of the present application, when Q1 and Q2 are both tert-butyldimethylsilyl, they can be removed in the presence of hydrochloric acid.

[0092] In step (7), the esterification reaction between the diol compound K6 and the carboxylic acid compound can be carried out in the presence of a catalyst (also called an "activator") and a condensation agent (also called a "dehydrating agent"). In step (7), the esterification reaction mainly occurs between one hydroxyl group and the carboxyl group in compound K6, and the esterification reaction between the remaining hydroxyl group and the carboxyl group is carried out in step (8). In some embodiments of the present application, when carrying out the esterification reaction in step (7), the condensation agent used can be EDCI (1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride), and the catalyst used can be 4-dimethylaminopyridine (abbreviated as DMAP).

[0093] Similar to step (7), the esterification reaction in step (8) can also be carried out in the presence of a catalyst and a condensing agent. In some embodiments, in the reaction of step (8), EDCI can be used as a condensing agent and DMAP can be used as a catalyst.

[0094] In some embodiments, the compound d used in step (7) can be

[0095] In some embodiments, the compound e used in step (8) can be selected from any one of the following substances, but is not limited thereto:

[0096]

[0097] The reaction in step (9) is mainly that the carbon anion formed by the methyl group in compound f under certain conditions attacks the aldehyde group in compound K8, and a condensation reaction occurs, water is removed, and a carbon-carbon double bond is generated. After the reaction in step (9), the electron acceptor A can be connected to the π bridge.

[0098] The reaction equation in step (9) is as follows:

[0099]

[0100] The preparation of self-crosslinking organic electro-optical materials is usually difficult, but the preparation method of the compound represented by formula (IA) shown above provides a feasible route for preparing organic compounds with groups that can undergo crosslinking reactions with each other, and the yield of each step is high. The preparation method can be applied to the preparation of various organic compounds with different structures. Among them, the hydroxyl compound K0 that can provide the electron donor D in step (1) can be replaced to obtain an organic compound with a different D; the compound f in step (9) can be replaced to obtain an organic compound with a different A; the carboxyl compounds d and e in the above steps (7) and (8) can be replaced to obtain an organic compound with different X1 and X2.

[0101] It should be noted that in the above preparation method, the two hydroxyl protecting groups Q1 and Q2 are removed simultaneously in step (6), and then the esterification reactions of steps (7) and (8) are carried out in sequence. It is understood that in other embodiments of the present application, one of the hydroxyl groups may be deprotected first, and the deprotected hydroxyl group may be subjected to an esterification reaction, and then the deprotection and esterification reactions of the other hydroxyl group may be carried out.

[0102] The present application also provides a composition, which comprises the organic compound and a solvent described in the present application. The composition can be used to prepare a film containing a crosslinked product of the organic compound, in particular to prepare an electro-optically active film.

[0103] The solvent is capable of dissolving the organic compound. Exemplary solvents may include, but are not limited to, one or more of chloroform (ie, chloroform), dibromomethane, and dichloromethane.

[0104] In some embodiments of the present application, the composition does not contain an external crosslinking agent, and may only contain the above-mentioned organic compound and solvent. The organic compound is both an effective active component-chromophore and a crosslinking agent. The content of effective active components in the electro-optical active film prepared by the composition is large, and the electro-optical performance of the film is high.

[0105] The present application also provides a film, which comprises a cross-linked product of the above-mentioned composition of the present application, or a cross-linked product of the above-mentioned organic compound. The film is obtained by cross-linking the composition containing the above-mentioned organic compound.

[0106] In the embodiment of the present application, the film may be an electro-optically active film, which is generally polarized and oriented by an electric field before the film is cross-linked. The electro-optically active film is particularly suitable for making components of optical communication systems, such as electro-optic modulators.

[0107] In the embodiment of the present application, the glass transition temperature (Tg) of the above-mentioned film is greater than or equal to 150°C, and can be greater than or equal to 160°C, greater than or equal to 180°C, greater than or equal to 200°C, etc. The glass transition temperature of the film provided in the embodiment of the present application is relatively high, especially in the field of electro-optical active films. The high Tg film provided in the embodiment of the present application is particularly helpful for the stable operation of various components of optical communication systems using the film. Among them, Tg can be measured by differential scanning calorimetry (DSC) or thermogravimetric analysis (TGA).

[0108] In the embodiment of the present application, the electro-optic coefficient (r 33 ) is greater than or equal to 190pm / V. Among them, the electro-optic coefficient of the film (r 33 ) is the maximum electro-optic coefficient r measured by the simple reflection method (also known as the Teng-Man method, see CCTeng, HTMan, Simplerefection technique for measuring the electro-optic coefficient of poled polymers, Applied Physics Letters, 1990, 56 (18), 1734-1736.) 33 Therefore, it can also be said that the maximum r of the electro-optically active film provided in the embodiment of the present application is 33 is greater than or equal to 190 pm / V. In some embodiments, the maximum r 33 The electro-optical active film provided in the embodiment of the present application has a r greater than or equal to 195 pm / V, greater than or equal to 200 pm / V, greater than or equal to 230 pm / V, or even greater than or equal to 260 pm / V. 33 Therefore, the electro-optical active film provided by the embodiment of the present application can have both a higher Tg and a higher electro-optical coefficient r 33 , the overall performance is good.

[0109] In the embodiment of the present application, the average polarization efficiency of the film is greater than or equal to 1.5nm 2 / V 2 In some embodiments, the polarization efficiency of the film is greater than or equal to 1.8 nm 2 / V 2 Among them, through multiple polarization field data and corresponding r 33 The average polarization efficiency of the film was calculated by linear least squares regression. 33vs the slope of the linear fitting curve of the polarization field strength. In some embodiments, the polarization efficiency of the film is 1.5-2.5nm 2 / V 2 , for example, 1.5, 1.6, 1.8, 2.0, 2.2, 2.3 or 2.4 nm 2 / V 2 wait.

[0110] The present application also provides a method for preparing an electro-optically active thin film, the method comprising the following steps:

[0111] (1) coating a solution containing an organic compound according to an embodiment of the present application (such as the above-mentioned composition according to an embodiment of the present application) on a substrate and drying the solution to form a film layer;

[0112] (2) applying an electric field to the film layer and heating it at a first temperature to polarize the organic compound in the film layer;

[0113] (3) continuing to heat the polarized film layer to a second temperature so that the organic compound in the film layer undergoes self-crosslinking, and then lowering the temperature to obtain an electro-optically active film.

[0114] When an electric field is applied to the film layer obtained in step (1), at a first temperature, the molecules of the organic compound in the film layer are reoriented so that their dipole moments are aligned with the electric field; then, heating is continued in the presence of the electric field to cause a cross-linking reaction in the film layer to stabilize the molecules that have been polarized and oriented; then, the temperature is lowered while the electric field is still present to maintain the polarized orientation of the molecules and obtain an electro-optically active film. The glass transition temperature of the electro-optically active film is generally higher than that of the film layer in step (1), which is conducive to the long-term stable operation of the electro-optical device made using the electro-optically active film at high temperatures and avoids the electro-optically active film from losing its electro-optical activity due to its inability to withstand high temperatures.

[0115] The applied electric field may specifically be a direct current electric field. The electric field may be applied by connecting the film layer between the positive and negative electrodes. In addition, the second temperature is higher than the first temperature, and the second temperature may be referred to as a "cross-linking temperature". The first temperature is generally closer to the glass transition temperature Tg of the organic compound described in the embodiment of the present application. Generally, the second temperature may be 20-70°C higher than the first temperature.

[0116] The present application also provides the use of the above-mentioned organic compounds, the above-mentioned compositions, the above-mentioned films, and the electro-optically active films prepared by the above-mentioned methods for preparing electro-optically active films in the embodiments of the present application in components of optical communication systems, solar cells, organic electroluminescent devices, and organic photoluminescent devices.

[0117] Among them, in application scenarios such as solar cells, organic electroluminescent devices, and organic photoluminescent devices, there is no need to utilize the electro-optical activity of the above-mentioned organic compounds. The above-mentioned organic compounds or films are usually used as hole transport layers in solar cells, organic electroluminescent devices, and organic photoluminescent devices. Therefore, the above-mentioned film does not need to exhibit electro-optical activity. Therefore, when the film is prepared by the above-mentioned preparation method, it is not necessary to apply an electric field; of course, even if the film exhibits electro-optical activity, it does not affect the performance of its hole transport function. Among them, when the above-mentioned application is specifically used for organic electroluminescent devices or organic photoluminescent devices, the above-mentioned organic compounds or films can improve the luminous efficiency of the light-emitting device. When the above-mentioned application is used for solar cells, for example, when used as dye-sensitized solar cells, the utilization rate of solar light by solar cells can be improved and the photoelectric conversion efficiency can be improved. If the solar cell is installed on an electric car, solar charging can be achieved; if the solar cell is made into solar cell glass, solar energy can be used to power the room.

[0118] In more cases, the above-mentioned organic compounds, compositions, films, etc. provided in the present application can be used in optical communication systems, specifically for making components of optical communication systems. In the implementation mode of the present application, the components of the optical communication system include one or more of electro-optical devices, optical switches, straight waveguides, curved waveguides, single-mode optical splitters, routers, filters, optical interconnects, and resonators. Among them, the electro-optical devices include one or more of electro-optical modulators, terahertz detectors, electro-optical frequency shifters, and frequency comb sources. Optical switches can also be called "optical modulators."

[0119] The present application also provides a component of an optical communication system, wherein the component of the optical communication system includes the electro-optically active film described above in the present application. The component of the optical communication system may be as described above in the present application.

[0120] The embodiment of the present application also provides an electro-optical device, which includes the electro-optically active film described above in the embodiment of the present application, wherein the electro-optically active film can be used as an electro-optical functional layer of the electro-optical device.

[0121] In the implementation manner of the present application, the electro-optic device includes one or more of an electro-optic modulator, a coupler, a terahertz detector, an electro-optic frequency shifter, and a frequency comb source. The electro-optic modulator may include, but is not limited to, one or more of a Mach-Zehnder modulator (MZM), a phase modulator, a silicon-organic hybrid modulator, a plasma-organic hybrid modulator, and the like.

[0122] See also Figure 1, the present application provides a structural schematic diagram of an electro-optic modulator. The electro-optic modulator 100 includes a first electrode 20, a second electrode 50, and a waveguide layer 30 and an electro-optical functional layer 40 sandwiched therebetween, wherein the waveguide layer 30 is close to the first electrode, and the electro-optical functional layer 40 is close to the second electrode 50. The electro-optical functional layer 40 includes the electro-optically active film described above in the embodiment of the present application. In the embodiment of the present application, the electro-optical modulator 100 also includes a substrate 10, wherein the first electrode 20, the waveguide layer 30, the electro-optical functional layer 40 and the second electrode 50 are sequentially stacked on a surface of one side of the substrate 10.

[0123] The substrate 10 may be a Si wafer having a silicon oxide layer on the surface. The first electrode 20 may be aluminum or other metal materials. The waveguide layer 30 may include an input waveguide and an output waveguide both of which are Y-shaped in structure, and the input waveguide and the output waveguide are coupled through two modulation arms to form a Mach-Zehnder (MZI) waveguide structure, wherein each output end of the input waveguide is coupled and connected to the input end of the output waveguide through a modulation arm. The material of the waveguide layer 30 may be Si. The second electrode 50 may be a traveling wave type electrode, and the material may be Au (gold), and may include an electrode pair. The orthographic projection of the second electrode 50 on the waveguide layer 30 may fall on the two modulation arms of the band layer 3. In addition, a first dielectric layer 203 (such as SiO2) may be provided between the first electrode 20 and the waveguide layer 30, and a second dielectric layer 405 (such as SiO2) may be provided between the electro-optical functional layer 40 and the second electrode 50 to play an isolation and protection role.

[0124] When the electro-optical adjuster is working, the second electrode 50 can be electrically connected to the first electrode 20 to apply a modulation voltage on both sides of the electro-optical functional layer 40, and realize phase modulation through the electro-optical effect of the electro-optical material. Among them, the light generated by the laser light source can be input from the input end of the waveguide layer 30, and enter the two modulation arms of the waveguide layer 30 after being evenly split by the Y-shaped structure. When the voltage applied to both sides of the electro-optical functional layer 40 changes, the refractive index of the electro-optical functional layer 40 changes, and the characteristics of the light wave change, so as to realize the modulation of the phase, amplitude, intensity and polarization state of the optical signal of the upper and lower modulation arms. After modulation, the light of the upper and lower modulation arms is combined by the Y-shaped structure and output from the output end of the waveguide layer 30. The optical power of the output light changes with the modulation signal, realizing the electro-optical modulation function.

[0125] An embodiment of the present application further provides an optical communication system, comprising at least one component of the aforementioned optical communication system.

[0126] The embodiment of the present application also provides a phased array lidar system, which includes the electro-optical active film described above in the embodiment of the present application.

[0127] The embodiments of the present application are further described below with reference to a plurality of embodiments.

[0128] Example 1

[0129] An organic compound SLD1, whose structural formula is shown below:

[0130]

[0131] The preparation of organic compound SLD-1 comprises:

[0132] 1) Compound K1 1 Synthesis

[0133] The synthetic route is shown below:

[0134]

[0135] The hydroxy compound K0 1 and tert-butyldimethylsilyl chloride as the reaction raw materials, and the method described in reference (Chem.Mater.2020,32,1408-1421) was used to synthesize compound K1 1 .

[0136] 2) Compound K2 1 Synthesis

[0137] The synthetic route is shown below:

[0138]

[0139] Metallic sodium (0.46 g, 20.00 mmol) was added to 30 mL of ethanol to obtain a solution containing sodium ethoxide (C2H5ONa). The solution was transferred to a two-necked flask in a nitrogen atmosphere. After the sodium was completely dissolved, 2-mercaptoethanol (1.56 g, 1.47 mL, 20.00 mmol) was added to the solution. After reacting at room temperature for 15 minutes, compound a was added. 1 (isophorone oxide, 3.08 g, 20 mmol), stirred at room temperature for 1 h, and then added the above compound K2 1 (5.87 g, 20.0 mmol), and reacted at 65°C for 18 hours to obtain a reaction solution. The reaction solution was concentrated using a rotary evaporator, and the concentrated reaction solution was purified by column chromatography using ethyl acetate and hexane (volume ratio of 1:10 to 1:6) as eluents to obtain a red oily compound K2 1 , with a yield of 78.9% (7.81 g, 15.95 mmol).

[0140] Compound K2 1 The mass spectrometry characterization results are: MS (MALDI) (M + ,C 27 H43 NO3SSi): Calculated value: 489.79; Measured value: 489.81. Compound K2 1 The results of H NMR spectrum are 1 H NMR (300MHz, CDCl3) δ (ppm): 7.92 (d, J = 16.1Hz, 1H), 7.46 (d, J = 8.6Hz, 2H), 7.04 (d, J = 16.1Hz, 1H), 6.68 (d, J = 8.7Hz, 2H ),4.02-3.80(m,4H),3.60-3.48(m,4H),3.04(s,3H),2.59(s,2H),2.45(s,2H),1.07(s,6H),0.87(s,9H),0.01(s,6H). Compound K2 1 The results of the carbon NMR spectrum are: 13 C NMR (126MHz, CDCl3) δ (ppm): 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.

[0141] 3) Compound K3 1 Synthesis

[0142] The synthetic route is shown below:

[0143]

[0144] In a nitrogen atmosphere, tert-butyldimethylsilyl chloride (3.68 g, 24 mmol) was slowly added to the above compound K3. 1 (32.90 g, 60.72 mmol) and a basic catalyst imidazole (1.66 g, 121.45 mmol) in 20 mL of DMF (N, N-dimethylformamide) were stirred at room temperature for 3 h, and the resulting reaction solution was poured into 100 mL of water, extracted with hexane to obtain an organic phase, which was washed with brine and dried over MgSO4. After removing the solvent with a rotary evaporator, the crude product was purified by silica gel column chromatography using ethyl acetate / hexane (volume ratio of 1:15 to 1:10) as the eluent to obtain a red oily compound K3 1 , with a yield of 93.1% (5.49 g, 9.31 mmol).

[0145] Compound K3 1 The mass spectrometry characterization results are: MS (MALDI) (M+ ,C 33 H 57 NO3SSi2): Calculated value: 604.05; Measured value: 603.95. Compound K3 1 The results of the H NMR spectrum are: 1 H NMR (300MHz, CDCl3) δ (ppm): 7.89 (d, J = 16.2Hz, 1H), 7.44 (d, J = 8.6Hz, 2H), 6.98 (d, J = 16.2Hz, 1H), 6.66 (d, J = 8.7Hz, 2H), 3.77 (t, J = 5.7Hz, 2H), 3.68 (t,J=6.9Hz,2H),3.51(t,J=5.6Hz,2H),3.03(s,3H)2.96-2.78(m,2H),2.5 9(s,2H),2.39(s,2H),1.06(s,6H),0.9-0.77(m,18H),0.08-0.02(m,12H). Compound K3 1 The results of the carbon NMR spectrum are: 13 C NMR (126MHz, CDCl3) δ (ppm): 195.67, 157.70, 150.03, 137.20, 129.20, 128.01, 123.97, 123.37, 111.8 4,62.79,60.12,54.46,51.87,41.18,39.13,36.53,32.14,30.62,28.26,25.77,18.14,-5.45,-5.63.

[0146] 4) Compound K4 1 Synthesis

[0147] The synthetic route is shown below:

[0148]

[0149] Under nitrogen atmosphere, diethyl (cyanomethyl)phosphonate (compound c, 1.81 mL, 1.99 g, 11.2 mmol) was slowly added to a two-necked flask containing 12 mL of dry THF containing NaH (0.27 g, 11.2 mol) to obtain a mixture. 1 A solution of (1.69 g, 2.80 mmol) in THF (5 mL) was added to the above mixture, and after the system solution was clarified, it was directly refluxed at 68° C. for 24 hours to obtain a reaction solution. After THF in the reaction solution was removed by a rotary evaporator, the residue was purified by silica gel column chromatography and eluted with ethyl acetate / hexane (volume ratio of 1:15 to 1:10) to obtain compound K4 as a red solid.1 , with a yield of 73.1% (1.28 g, 2.04 mmol).

[0150] Compound K4 1 The mass spectrometry characterization results are: MS (MALDI) (M + ,C 35 H 58 N2O2SSi2): Calculated value: 627.09; Measured value: 627.13. Compound K4 1 The results of the H NMR spectrum are: 1 H NMR (300 MHz, CDCl3) δ (ppm): 7.84 (d, J = 16.1 Hz, 1H), 7.38 (d, J = 8.4 Hz, 2H), 6.83 (d, J = 16.1 Hz, 1H), 6.64 (d, J = 8.4 Hz, 2H), 6.23 (s, 1H), 3.82-3.61 (m, 4H), 3.48-3.46 (m, 2H), 2.99 (m, 3H), 2.67-2.65 (m, 2H), 2.53 (s, 2H), 2.43 (s, 2H), 0.99 (s, 6H), 0.87 (m, 18H), 0.05-0.02 (m, 12H). Compound K4 1 The results of the carbon NMR spectrum are: 13 C NMR (126MHz, CDCl3) δ (ppm): 158.13, 149.59, 148.68, 134.79, 128.63, 125.94, 124.50, 123.94, 118.84, 111.6 6,94.47,62.11,60.34,54.37,38.86,30.57,29.88,29.53,27.84,25.76,22.51,17.99,14.01,-5.45,-5.61.

[0151] 5) Compound K5 1 Synthesis

[0152] The synthetic route is shown below:

[0153]

[0154] The above compound K4 1(1.25 g, 2.00 mmol) was dissolved in 20.0 mL of freshly dried toluene, and the solution was cooled to -78 ° C under a nitrogen atmosphere. A 1.5 M diisobutylaluminum hydride (DIBAL) hexane solution (DIBAL is 4.00 mmol) was slowly added. After stirring and reacting at -78 ° C for 2 h, wet silica gel (1.0 g) containing 10.0 mL of water was added thereto, and reacted at 0 ° C for 2 h to obtain a reaction mass. The reaction mass was poured into water, extracted with ethyl acetate, and the obtained organic phase was concentrated with a rotary evaporator. The residue after concentration was purified by silica gel column chromatography and eluted with ethyl acetate / hexane (volume ratio of 1:8 to 1:5) to obtain compound K5 as a red solid. 1 , with a yield of 70.1% (0.88 g, 1.40 mmol).

[0155] Compound K5 1 The mass spectrometry characterization results are: MS (MALDI) (M + ,C 35 H 59 NO3SSi2): Calculated value: 630.09; Measured value: 630.15. Compound K5 1 The results of the H NMR spectrum are: 1 H NMR (300MHz, CDCl3) δ (ppm): 10.12 (d, J = 6.4Hz, 1H), 7.94 (d, J = 16.1Hz, 1H), 7 .40(d,J=6.8Hz,2H),6.98(d,J=6.6Hz,1H),6.85(d,J=16.1Hz,1H),6.65(d,J= 6.8Hz,2H),3.76-3.74(m,4H),3.49-3.48(m,2H),3.01(s,3H),2.70-2.67(m, 2H),2.47(s,2H),2.11(s,2H),1.01(s,6H),0.86-0.82(m,18H),0.02(s,12H). Compound K5 1 The results of the carbon NMR spectrum are: 13 C NMR (126MHz, CDCl3) δ (ppm): 190.77, 156.09, 149.77, 149.50, 134.66, 128.57, 127.97, 126.58, 124.35, 11 1.44,62.08,60.25,54.48,41.36,39.62,38.82,37.39,30.42,29.66,28.04,25.51,17.94,-5.49,-5.63.

[0156] 6) Compound K6 1 Synthesis

[0157] The synthetic route is shown below:

[0158]

[0159] Add 5.60 mmol of HCl to the above compound K5 1 The obtained reaction solution was neutralized with sodium bicarbonate, and the organic solvent was concentrated with a rotary evaporator. The residue after concentration was poured into 20 mL of water, extracted with 100 mL of dichloromethane, and then concentrated with a rotary evaporator, dried with Na2SO4 and concentrated to obtain a crude product. The crude product was purified by flash chromatography on silica gel, using a gradient eluent of dichloromethane / ethyl acetate (volume ratio of 10:1 to 5:1) to obtain a red solid compound K6. 1 , with a yield of 93.1% (0.52 g, 1.30 mmol).

[0160] Compound K6 1 The mass spectrometry characterization results are: MS (MALDI) (M + ,C 23 H 31 NO3S): Calculated value: 401.56; Measured value: 401.78. Compound K6 1 The results of the H NMR spectrum are: 1 H NMR (300MHz, CDCl3) δ (ppm): 10.08 (d, J = 8.1Hz, 1H), 7.94 (d, J = 16.2Hz, 1H), 7.42 (d, J = 8.8Hz, 2H), 6.97 (d, J = 8.1Hz, 1H), 6.86 (d, J = 16.2Hz, 1H), 6.72 ( d,J=8.8Hz,2H),3.84-3.81(m,2H),3.62(m,2H),3.52(m,2H),3.02(s,3H), 2.76-2.74(m,2H),2.71(s,2H)2.49(s,2H),2.36-2.32(m,2H),1.02(s,6H). Compound K6 1 The results of the carbon NMR spectrum are: 13 C NMR (126MHz, CDCl3) δ (ppm): 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.

[0161] 7) Compound K7 1 Synthesis

[0162] The synthetic route is shown below:

[0163]

[0164] Under nitrogen atmosphere, carboxylic acid compound d 1 (3,5-bis(acryloyloxy)benzoic acid, 3.24 g, 12.36 mmol), catalyst DMAP (0.15 g, 1.24 mmol), condensation agent EDCI (2.37 g, 12.36 mmol) and an appropriate amount of dichloromethane were placed in a clean and dry test tube, stirred at 0°C for 45 min to obtain a clear solution, and then the above compound K6 was added 1 (4.00 g, 10.30 mmol), continued stirring at 0°C for 2 h, then transferred to an oil bath for heating and reflux overnight to obtain a reaction mass. The reaction mass was extracted with dichloromethane, and the obtained organic layer crude product was concentrated in vacuo, and then purified by column chromatography using a mixed solvent of petroleum ether and ethyl acetate (volume ratio of 8:1 to 2:1) as eluent to obtain a dark red compound K7 1 , with a yield of 92.3% (5.09 g, 7.88 mmol).

[0165] Compound K7 1 The mass spectrometry characterization results are: MS (MALDI) (M+, C 36 H 39 NO8S): calculated value: 645.76; measured value: 645.75. Compound K7 1 The results of the H NMR spectrum are: 1H NMR (600MHz, CDCl3) δ (ppm): 10.13 (d, J = 8.0 Hz, 1H, CHO), 7.95-7.91 (m, 1H, CH), 7.70-7.63 (m, 2H, CH), 7.27 (dd, J = 10 .4,5.5Hz,3H,CH),6.97(t,J=7.6Hz,1H,ArH),6.82(d,J=16.2Hz,1H,CH),6.63-6.56(m,4H,ArH),6.33-6.27(m,2H,A rH),6.07-6.03(m,2H,CH),4.39-4.31(m,2H,OCH2),3.85-3.74(m,2H,NCH2),3.53-3.47(m,2H,OCH2),3.00(d,J=4.2 Hz,3H,CH3),2.93(dt,J=12.5,6.2Hz,2H,CH2),2.74(d,J=12.0Hz,2H,CH2),2.53-2.41(m,2H,CH2),1.03(s,6H,CH3). Compound K7 1 The results of the carbon NMR spectrum are: 13 C NMR (151MHz, CDCl3) δ (ppm): 191.69, 164.56, 164.01, 156.25, 151.60, 150.92, 150.30, 135.50, 133.66, 132.22, 128. 91,127.43,126.94,125.09,124.62,120.36,112.28,63.95,60.14,54.77,41.73,39.98,38.97,33.27,30.20,28.41.

[0166] 8) Compound K8 1 Synthesis

[0167] The synthetic route is shown below:

[0168]

[0169] Under nitrogen atmosphere, the carboxylic acid compound e 1 (specifically 3-(anthracen-9-yl)propionic acid, 9.46 mmol), DMAP (0.11 g, 0.95 mmol) and EDCI (1.81 g, 9.46 mmol) were placed in a clean and dry test tube and stirred at 0°C for 45 minutes until the solution became clear, and then compound K7 was added 1(5.09 g, 7.88 mmol), continued stirring at 0°C for 2 hours, transferred to an oil bath and heated under reflux overnight to obtain a reaction mass. The reaction mass was extracted with dichloromethane, the obtained organic layer crude product was concentrated in vacuo, and purified by column chromatography using a mixed solvent of petroleum ether and ethyl acetate (volume ratio of 8:1 to 2:1) as eluent to obtain a light red oily compound K8 1 The yield was 76.8% (5.31 g, 6.05 mmol).

[0170] Compound K8 1 The mass spectrometry characterization results are: MS (MALDI) (M+, C 53 H 51 NO9S): calculated value: 878.05; measured value: 878.06. Compound K8 1 The results of the H NMR spectrum are: 1 H NMR (600MHz, CDCl3) δ (ppm): 10.19 (dd, J = 7.9, 3.3Hz, 1H, CHO), 8.44-8.34 (m, 2H, ArH), 8.30-8.23 (m, 3H, CH), 8.03-7.98 (m, 4H, ArH), 7.67-7.64 (m, 2H ,ArH),7.49-7.43(m,3H,ArH),7.41-7.39(m,2H,ArH),6.67-6.62(m,2H,CH ),6.62-6.52(m,3H,ArH),6.36-6.30(m,2H,CH),6.09-6.05(m,2H,CH),4.39 (t,J=6.3Hz,2H,OCH2),4.20(dd,J=11.1,4.5Hz,2H,OCH2),4.14(ddd,J=22 .6,14.6,7.7Hz,2H,NCH2),3.93(dt,J=11.6,4.2Hz,2H,SCH2),3.59(t,J=6. 0Hz,2H,CH2),2.92(d,J=2.5Hz,3H,CH3),2.82(dd,J=15.0,8.4Hz,2H,CH2) ,2.57-2.46(m,2H,CH2),1.29(t,J=7.1Hz,2H,CH2),1.10-1.05(m,6H,CH3). Compound K8 1 The results of the carbon NMR spectrum are: 13C NMR (151MHz, CDCl3) δ (ppm): 191.65,172.84,164.84,163.89,156.26,151.15,150.99,149.40 ,135.27,133.59,132.43,132.00,131.68,129.58,129.39,128.99,127.38,127.28,127.20,1 27.03,126.85,126.37,126.07,125.33,125.07,124.03,123.82,120.40,112.07,62.75,60.51,50.65,41.80,40.00,38.68,35.35,33.39,30.21,30.08,28.39,23.41,23.25,21.17,14.32.

[0171] 9) Synthesis of compound SLD1

[0172] The synthetic route is shown below:

[0173]

[0174] In a nitrogen atmosphere, add the above compound K8 into a two-necked flask. 1 (0.53 g, 6.05 mmol), compound f 1 (Specifically 2-(3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H))-ethylidene)malononitrile, 6.65mmol), and dissolved with 5-6mL of ethanol, and then stirred and refluxed at 65°C for 6h. After the reaction is completed, the reaction solution is concentrated to obtain a crude product. The crude product is purified twice by column chromatography using petroleum ether and ethyl acetate (1:4 to 1:1) as eluents to obtain a green solid, which is the organic chromophore SLD1, with a yield of 67.8% (0.48g, 4.10mmol).

[0175] The mass spectrometry characterization results of SLD1 are as follows: HRMS (ESI) ([M+H]+, C 69 H 57 F3N4O9S): calculated value: 1175.3877; measured value: 1175.3876. The results of the H NMR spectrum of SLD1 are: 1H NMR (600MHz, CDCl3) δ (ppm): 8.40-8.29 (m, 2H, ArH), 8.17 (t, J = 7.2Hz, 3H, ArH), 7.99 (d d,J=13.1,5.6Hz,4H,CH),7.47-7.46(m,5H,ArH),7.43(dd,J=8.8,3.1Hz,2H,ArH),7.4 0(d,J=8.9Hz,3H,ArH),7.37-7.28(m,2H,ArH),7.11(dt,J=17.8,8.9Hz,1H,CH),7.01- 6.88(m,2H,ArH),6.84(t,J=2.2Hz,1H,ArH),6.59-6.55(m,3H,CH),6.56-6.45(m,2H,CH ),6.31-6.24(m,1H,ArH),6.01(dd,J=10.5,1.0Hz,1H,CH),4.36(t,J=5.7Hz,2H,OCH2) ,4.16(dd,J=12.2,5.6Hz,2H,OCH2),4.15-4.10(m,2H,NCH2),3.89(t,J=7.5Hz,2H,SCH 2),3.62(t,J=5.7Hz,2H,CH2),2.92(d,J=4.0Hz,3H,CH3),2.78(t,J=6.6Hz,2H,CH2),2.75-2.73(m,2H,CH2),2.56-2.48(m,2H,CH2),1.01-0.97(m,3H,CH3),0.90(s,3H,CH3). The results of the carbon NMR spectrum of SLD1 are: 13 C NMR (151MHz, CDCl3) δ (ppm): 175.69, 173.33, 171.43, 165.53, 164.29, 156.95, 151.43, 150.54, 147. 34,138.11,133.31,132.12,131.89,131.68,131.48,129.82,129.51,129.21,128.40,127.66,126. 85,126.60,126.22,125.12,123.87,117.38,115.05,114.36,114.09,112.46,110.79,63.30,62.36,60.59,58.38,50.64,41.87,41.27,38.46,35.39,33.98,30.55,28.66,27.98,23.36,21.20,14.32.

[0176] Among them, the compound SLD1 provided in Example 1 of the present application can undergo a self-crosslinking reaction at a certain temperature, specifically a Diels-Alder cycloaddition crosslinking reaction between the anthracene group and the acrylate group. Specific examples are as follows:

[0177]

[0178] Example 2

[0179] An organic compound SLD2, whose structural formula is shown below:

[0180]

[0181] The main difference between the synthesis method of the organic compound SLD2 and the above-mentioned SLD1 is that: the carboxylic acid compound e used in step (8) is 1 Replaced with the following carboxylic acid compound e 2 (Specifically 3,5-bis(anthracen-9-ylmethoxy)benzoic acid, 9.46 mmol).

[0182]

[0183] The synthetic route involved in step (8) is shown below:

[0184]

[0185] In step (8), the obtained compound K8 2 The yield was 73.8% (6.79 g, 5.85 mmol). 2 The reaction of step (9) was carried out to obtain the green solid chromophore SLD2 with a yield of 63.8% (0.56 g, 3.85 mmol).

[0186] Compound K8 2 The mass spectrometry characterization results are: MS (MALDI) (M+, C 73 H 63 NO 11 S): calculated value: 1162.4200; measured value: 1162.4211. Compound K8 2 The results of the H NMR spectrum are: 1H NMR (600MHz, CDCl3) δ (ppm): 10.19 (dd, J = 7.9, 3.3Hz, 1H, CHO), 8.64-8.54 (m, 2H,ArH),8.50-8.43(m,3H,CH),8.33-8.26(m,9H,ArH),8.23-7.98(m,4H,ArH) ,7.87-7.74(m,2H,ArH),7.69-7.63(m,12H,ArH),7.61-7.69(m,2H,ArH),6.8 7-6.82(m,2H,CH),6.82-6.772(m,3H,ArH),6.56-6.50(m,2H,CH),6.39-6.25( m,2H,CH),4.41(t,J=6.3Hz,2H,OCH2),4.33(dd,J=11.1,4.5Hz,2H,OCH2),4. 24(ddd,J=22.6,14.6,7.7Hz,2H,NCH2),3.97(dt,J=11.6,4.2Hz,2H,SCH2),3. 79(t,J=6.0Hz,2H,CH2),2.93(d,J=2.5Hz,3H,CH3),2.92(dd,J=15.0,8.4Hz, 2H, CH2), 2.77-2.56 (m, 2H, CH2), 1.39 (t, J = 7.1Hz, 2H, CH2), 1.10 (s, 6H, CH3). Compound K8 2 The results of the carbon NMR spectrum are: 13 C NMR (151MHz, CDCl3) δ (ppm): 191.65, 172.33, 164.47, 163.99, 156.47, 151.35, 150.88, 149.56, 135.57 ,133.71,132.56,132.55,131.77,129.68,129.51,129.49,129.13,128.89,128.66,128.33,127.43,1 27.34,127.35,127.23,126.75,126.35,126.27,125.34,125.37,124.45,123.78,122.44,113.47,62.85,60.81,52.77,40.99,40.12,39.77,37.35,34.29,31.33,30.28,29.39,24.43,24.35,22.27,14.12.

[0187] The mass spectrometry characterization results of SLD2 are as follows: HRMS (ESI) ([M+H]+, C 89 H 69F3N4O 11 S): calculated value: 1459.4714; measured value: 1459.4721. The results of the nuclear magnetic resonance hydrogen spectrum of SLD2 are: 1H NMR (500MHz, CDCl3) δ (ppm): 8.43 (d, J = 7.1Hz, 2H, ArH), 8.14 (d, J = 8.7Hz, 4H, ArH), 7.95 (d, J = 8.2Hz, 4H, ArH), 7.55 (d, J = 1.7Hz, 2H, ArH), 7.47 ( dd,J=12.7,5.6Hz,10H,CH),7.43-7.38(m,9H,CH,ArH),7.28(d,J=12.2Hz,1H,ArH),7.15(d,J=17.4Hz,1H,CH),6.93(s,1H,CH),6.65(d,J=8.8Hz ,2H,ArH),6.52(d,J=17.3Hz,2H,CH),6.39(d,J=14.5Hz,1H,CH),6.20(dd,J=17.3,10.5Hz,2H,CH),5.95(d,J=10.5Hz,2H,ArH),5.78(s,4H,CH2),4.46(d,J=5.4Hz,2H,NCH2),4.16(t,J=6.2Hz,2H,SCH2),3.82-3.69(m,4H,OCH2),3.03(s,3H,NCH3),2.76-2.52(m,4H,CH2),0.82(s,6H,CH3). The results of the carbon NMR spectrum of SLD2 are: 13 C NMR (151MHz, CDCl3) δ (ppm): 174.29, 173.23, 170.44, 166.51, 163.29, 156.85, 150.33, 151.54, 146.24, 137.19, 13 4.31,131.12,131.99,131.77,131.29,129.96,129.66,129.31,129.21,128.56,128.44,128.31,127.78,127.61, 127.55,127.34,126.89,126.77,126.58,126.33,125.22,123.97,117.4,115.35,114.26,114.19,112.56,110.79,63.41,62.33,60.78,58.68,50.75,42.89,43.67,39.57,36.49,34.98,32.53,29.55,28.89,24.21,21.30,14.33.

[0188] Example 3

[0189] An organic compound SLD3, whose structural formula is shown below:

[0190]

[0191] The main difference between the synthesis method of the organic compound SLD3 and the synthesis method of SLD1 is that the hydroxyl compound used in step (1) is different.

[0192] Example 4

[0193] An organic compound SLD4, whose structural formula is shown below:

[0194]

[0195] The main difference between the synthesis method of the organic compound SLD4 and the above-mentioned SLD2 is that the hydroxyl compound used in step (1) is different.

[0196] Example 5

[0197] An organic compound SLD5, whose structural formula is shown below:

[0198]

[0199] The main difference between the synthesis method of the organic compound SLD5 and the above-mentioned SLD1 is that the hydroxyl compound used in step (1) is different.

[0200] Example 6

[0201] An organic compound SLD6, whose structural formula is shown below:

[0202]

[0203] The main difference between the synthesis method of the organic compound SLD6 and the above-mentioned SLD2 is that the hydroxyl compound used in step (1) is different.

[0204] Example 7

[0205] An organic compound SLD7, whose structural formula is shown below:

[0206]

[0207] The main difference between the synthesis method of the organic compound SLD7 and the above-mentioned SLD1 is that the hydroxyl compound used in step (1) is different.

[0208] Example 8

[0209] An organic compound SLD8, whose structural formula is shown below:

[0210]

[0211] The main difference between the synthesis method of the organic compound SLD8 and the above-mentioned SLD2 is that the hydroxyl compound used in step (1) is different.

[0212] Example 9

[0213] An organic compound SLD9, whose structural formula is shown below:

[0214]

[0215] The main difference between the synthesis method of the organic compound SLD9 and the above-mentioned SLD1 is that the hydroxyl compound used in step (1) is different.

[0216] Example 10

[0217] An organic compound SLD10, whose structural formula is shown below:

[0218]

[0219] The main difference between the synthesis method of the organic compound SLD10 and the synthesis method of SLD2 is that the hydroxyl compound used in step (1) is different.

[0220] Embodiment 11

[0221] An organic compound SLD11, whose structural formula is shown below:

[0222]

[0223] The main difference between the synthesis method of the organic compound SLD11 and the synthesis method of the organic compound SLD1 is that the hydroxyl compound used in step (1) is different.

[0224] Example 12

[0225] An organic compound SLD12, whose structural formula is shown below:

[0226]

[0227] The main difference between the synthesis method of the organic compound SLD12 and the synthesis method of SLD2 is that the hydroxyl compound used in step (1) is different.

[0228] Embodiment 13

[0229] An organic compound SLD13, whose structural formula is shown below:

[0230]

[0231] The main difference between the synthesis method of the organic compound SLD13 and the above-mentioned SLD1 is that the hydroxyl compound used in step (1) is different.

[0232] Embodiment 14

[0233] An organic compound SLD14, whose structural formula is shown below:

[0234]

[0235] The main difference between the synthesis method of the organic compound SLD14 and the synthesis method of SLD2 is that the hydroxyl compound used in step (1) is different.

[0236] Results characterization:

[0237] (1) DFT theory simulation calculation

[0238] In order to compare the microscopic nonlinearity, charge transfer and stereo configuration of different chromophores, the chromophore SLD1-14 provided in the embodiment of the present application was subjected to structural optimization and theoretical calculation of the first-order hyperpolarizability. The theoretical calculation was performed using the Gaussian 09 software package, based on the B3LYP method of the density functional method (DFT) combined with the 6-31g (d) basis set. During the calculation, we assumed that all molecules were in the trans configuration, the chromophore was structurally optimized, and the energy level, dipole moment, electron cloud density and microscopic first-order hyperpolarizability β of the ground state and excited state of the chromophore were calculated. The results are shown in Table 1 below.

[0239] Table 1 DFT calculation data of various organic compounds

[0240]

[0241] It can be seen from Table 1 that the first-order hyperpolarizability β of SLD1 to SLD14 increases with the increase of donor strength (specifically reflected by the decrease of ΔE). Among them, although the number of cross-linkable groups contained in SLD1 and SLD2 is different, the donors in both are common aniline donors, and their first-order hyperpolarizabilities are close.

[0242] (2) Thermal stability and spectral absorption characteristics

[0243] The spectral absorption characteristics and thermal stability of each chromophore were tested, wherein the test results of chromophores SLD1, SLD2, SLD3, and SLD4 are summarized in Table 2 below. The thermal stability of the chromophores can be characterized by their thermogravimetric curves, wherein the thermogravimetric curve of chromophore SLD1 is shown in FIG. Figure 2AAs shown, the thermogravimetric curve of the chromophore SLD2 is as follows Figure 2B The UV-visible spectra of the chromophore SLD1 in different solvents and films are shown in Figure 3 The UV-visible spectra of the chromophore SLD2 in different solvents and films are shown in Figure 4 shown.

[0244] Table 2

[0245] Compound <![CDATA[Glass transition temperature T g (°C)]]> <![CDATA[Thermal decomposition temperature T d (°C)]]> <![CDATA[λ max a (nm)]]> <![CDATA[λ max b (nm)]]> SLD1 158 239 749 788 SLD2 200 267 753 793 SLD3 184 270 798 833 SLD4 199 Untested 798 842

[0246] Note: T in Table 2 d and T g It can be obtained from the thermogravimetric curve and differential scanning calorimetry curve of each chromophore; max a is the maximum absorption wavelength of each chromophore in chloroform solvent, λ max b It is the maximum absorption wavelength of each chromophore in the cross-linked film (specifically, cross-linking is achieved by heating at 150°C for 30 minutes).

[0247] It can be seen from Table 2 that the chromophores SLD1 to SLD4 provided in the examples of the present application have high thermal stability (T g Above 150°C), which is conducive to the preparation of electro-optically active and stable thin films. Among them, SLD2 has better thermal stability than SLD1 with similar structure. g As high as 200℃, its thermal decomposition temperature T d The maximum absorption wavelength of SLD2, which has an additional anthracene group compared to SLD1, in chloroform is 753 nm, which is close to 749 nm of SLD1, proving that the crosslinkable group (specifically the anthracene group) does not affect the light absorption performance of the main structure of the chromophore too much. The larger λ max a This means that the chromophore has a large first-order hyperpolarizability; and the maximum absorption wavelength of the film containing SLD2 after cross-linking is basically close to that of SLD1. In addition, the anthracene absorption peak of each film containing chromophore after cross-linking is lower than that of the film before cross-linking, which can indicate that the anthracene group participates in the cross-linking reaction. In addition, the comparison between SLD4 and SLD3 also has a similar rule as that between SLD1 and SLD2.

[0248] (3) Electro-optical performance of assembled devices

[0249] In order to illustrate the conversion of the microscopic hyperpolarizability β of the organic compound provided in the embodiment of the present application into the macroscopic r 33The ability of the value is first made into an electro-optically active film. Different chromophores are dissolved in freshly distilled dibromomethane, and the obtained solution is filtered through a 0.2mm polytetrafluoroethylene (abbreviated as PTFE) filter and spin-coated on an indium oxide (ITO) glass substrate. After heating at 50°C to remove the solvent dibromomethane, a dry film layer is obtained. The upper surface of the dry film layer is connected to a metal electrode (such as a gold electrode), and the gold electrode is electrically connected to the ITO electrode to apply an electric field to polarize the film layer and then cross-link to obtain a stable film exhibiting electro-optical activity. The specific operation process is: 1) First, a polarizing electric field with an intensity of 10V / μm is applied between the gold electrode and the ITO electrode, and the temperature is raised to 100°C at a rate of 10°C / min. 2) Then, the electric field strength was gradually increased to 100-130 V / μm with a step voltage of 1 V / min. At the same time, the film was heated at 100°C for 5 minutes, 110°C for 5 minutes, 120°C for 5 minutes, 130°C for 5 minutes, 140°C for 5 minutes, and 150°C for 10 minutes. After that, each film sample was cooled to room temperature, and the polarization performance of the obtained electro-optically active film at a wavelength of 1310 nm was tested using the Teng-Man simple reflection method. The relevant results are summarized in Table 3.

[0250] Among them, the experimental device for measuring the electro-optic coefficient using a simple reflection method is as follows Figure 5 As shown. The signal light source used is a 1310nm laser in the communication band. The two polarizers are perpendicular to each other, and the incident angle θ is 45°. After passing through the ITO glass and the electro-optically active film, the incident light is reflected and emitted from the surface of the metal electrode, interferes with the polarizer 2, and is detected by the phase-locked amplifier and the detector. Among them, different modulation voltages are applied to both sides of the electro-optically active film, and the refractive index of the film changes, causing the optical path and phase state of the incident light to change. After the reflected light interferes with the polarizer 2, polarized light in different phase states exhibits different extinction phenomena. The light intensity detected by the detector will have a certain relationship with the modulation voltage, so that the electro-optic coefficient r of the polarization film at a wavelength of 1310nm can be calculated. 33 Among them, thin ITO electrodes with low reflectivity and good transparency are used to minimize multiple reflections.

[0251] Table 3 Relevant test data of electro-optical devices assembled by various chromophores

[0252]

[0253] Note: In Table 3, ρ N represents the number density of the polarizable compound (assuming the mass density is 1 g / cm 3 ). 33 / E p It is also called the average polarization efficiency, which is based on the r measured for each film under different polarization field strengths.33 The polarization curve obtained by linear least squares regression is also the slope of the polarization curve, which is the average value of multiple polarization experiments. 33 / (E p ρ N ) represents the polarization efficiency per number density, which can better reflect the polarization of the compound.

[0254] Figure 6 The polarization curve of the film SLD1 after self-crosslinking of the embodiment of the present application is shown. Figure 7 The polarization curve of the SLD2 film after cross-linking of the embodiment of the present application is shown, the horizontal axis is the polarization field strength, and the vertical axis is the r of the film at each polarization field strength. 33 The relevant performance indicators are summarized in Table 3. Among them, Figure 6 , Figure 7 The process of obtaining each data point is as follows: after the electric field strength applied between the gold electrode and the ITO electrode in the above step 2) reaches the electric field strength corresponding to each data point, the heating operation of the above step 2) is performed to achieve self-crosslinking, and the electro-optically active film is obtained after cooling, and then its related properties are tested.

[0255] From Table 3 and Figure 6-Figure 7 It can be seen that the average polarization efficiency of the electro-optically active film formed by polarization and cross-linking of the dry film containing SLD1 is about 2.03nm 2 / V 2 , the maximum electro-optic coefficient r obtained under the polarization field 33 The average polarization efficiency of SLD2 after cross-linking is about 1.58nm 2 / V 2 , maximum electro-optic coefficient r 33 It is about 198pm / V. Among them, the average polarization efficiency and maximum electro-optic coefficient of chromophore SLD1 after cross-linking are higher than those of chromophore SLD2. This is mainly because the bisanthracene structure of chromophore SLD2 leads to an increase in the molecular weight of the chromophore, resulting in a decrease in the number density of the chromophore. The difference in electro-optic coefficient is mainly affected by the number density and polarization efficiency of the chromophore, while the first-order hyperpolarizability is less affected by this. However, it should be noted that although the electro-optic coefficient of chromophore SLD1 is larger, its glass transition temperature Tg is not as high as that of chromophore SLD2. In general, the use of these two chromophores SLD1 and SLD2 can obtain electro-optically active films with good comprehensive performance, which can take into account a higher T g And higher electro-optic coefficient max.r 33 wait.

[0256] The above only expresses several exemplary embodiments of the present application, and the description is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent of the present application. It should be pointed out that for ordinary technicians in this field, several modifications and improvements can be made without departing from the concept of the present application, which all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application shall be based on the attached claims.

[0257] It should be understood that the first, second and various digital numbers involved in this article are only distinguished for the convenience of description and are not used to limit the scope of this application. In various embodiments of this application, the size of the sequence number of each process does not mean the order of execution, some or all of the steps can be executed in parallel or in sequence, and the execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.

[0258] In this application, "and / or" describes the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone, where A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0259] In this application, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.

Claims

1. An organic compound, characterized in that The organic compound has the general structural formula shown in formula (I): In formula (I), A represents an electron acceptor, D represents an electron donor, Z represents a sulfur atom, an oxygen atom or NH, and R1 is selected from substituted or unsubstituted C1-C 10 Alkylene; n is an integer selected from 0-2; X1 includes at least one first crosslinkable group, X2 includes at least one second crosslinkable group, and a cycloaddition crosslinking reaction can occur between the first crosslinkable group and the second crosslinkable group.

2. The organic compound according to claim 1, characterized in that The first crosslinkable group and the second crosslinkable group are independently selected from one or more of anthracene group, acrylate group, maleamide group, furan group, aryl azide group and alkynyloxy group.

3. The organic compound according to claim 1 or 2, characterized in that Said X1 and X2 are independently selected from One or more of; the position marked with * is the connection position.

4. The organic compound according to any one of claims 1 to 3, characterized in that The Z is a sulfur atom, and R1 is -CH2-CH2.

5. The organic compound according to any one of claims 1 to 4, characterized in that The D independently comprises an aromatic amine structure or a heteroaromatic amine structure containing a tertiary amino nitrogen atom.

6. The organic compound according to claim 5, characterized in that The D comprises any structure represented by formula (d-1) to formula (d-6) which is substituted or unsubstituted: in,*, The marked position is the connection position, the position marked with * is connected to -OCO-X2, each a is independently selected from an integer of 1-3, each b is independently selected from an integer of 0-3, and R2, R3, and R4 are independently selected from substituted or unsubstituted alkyl groups.

7. The organic compound according to any one of claims 1 to 6, characterized in that The A comprises a structure shown in formula (A-1) or formula (A-2): in, The marked position is the connection position, X is independently selected from oxygen atom, sulfur atom, N(R8) or CH2, R7 is independently selected from at least one of cyano, nitro, trihalomethyl, fluorine atom, sulfonic acid, trifluoromethanesulfonyl each time it appears, R5 and R6 are independently selected from one of substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and R8 is a hydrogen atom, or a substituted or unsubstituted alkyl.

8. The organic compound according to claim 7, characterized in that A is a structure represented by formula (A-1), and each R7 is a cyano group, one of R5 and R6 is a trifluoromethyl group, and the other is a phenyl group; X is an oxygen atom, a sulfur atom, NH or CH2.

9. A film, characterized in that: The film comprises a cross-linked product of the organic compound according to any one of claims 1 to 8.

10. The film according to claim 9, characterized in that The glass transition temperature of the film is greater than or equal to 150°C.

11. The film according to claim 9 or 10, characterized in that The film is an electro-optically active film, and the maximum electro-optic coefficient of the electro-optically active film is greater than or equal to 190 pm / V.

12. A method for preparing an electro-optically active film, characterized in that: The following steps are involved: Applying a solution containing the organic compound according to any one of claims 1 to 8 on a substrate and drying to form a film layer; Applying an electric field to the film layer and heating it at a first temperature to polarize the organic compound; The polarized film layer is further heated to a second temperature to allow the organic compound in the film layer to self-crosslink, and then the temperature is lowered to obtain an electro-optically active film.

13. Use of the organic compound according to any one of claims 1 to 8, the thin film according to any one of claims 9 to 11, and the electro-optically active thin film prepared by the preparation method according to claim 12 in components of optical communication systems, solar cells, organic electroluminescent devices, and organic photoluminescent devices.

14. The use according to claim 13, characterized in that The components of the optical communication system include one or more of electro-optical devices, optical switches, straight waveguides, bent waveguides, single-mode optical splitters, routers, filters, optical interconnectors, and resonators.

15. An electro-optical device, characterized in that: It comprises a film as described in any one of claims 9 to 11, or an electro-optically active film prepared by the preparation method as described in claim 12.

16. The electro-optical device according to claim 15, characterized in that The electro-optical device includes one or more of an electro-optic modulator, a coupler, a terahertz detector, an electro-optic frequency shifter, and a frequency comb source.

17. An optical communication system, characterized in that: At least some of the components of the optical communication system include a film as claimed in any one of claims 9 to 11, or an electro-optically active film made by the preparation method as claimed in claim 12.

18. A phased array laser radar system, characterized in that: It comprises a film as described in any one of claims 9 to 11, or an electro-optically active film prepared by the preparation method as described in claim 12.

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