Organic photoelectric compound and organic photoelectric component using same

Abstract

The invention relates to an organic photoelectric compound, which comprises a structure shown in a formula I: (formula I) # imgabs0 #, has a pyrazine core structure, provides an additional conjugate plane for molecules, strengthens an intermolecular interaction force, enables carrier flow to be smoother, reduces energy loss, and improves thermal stability. In addition, arrangement and energy level of the material can be changed by changing functional groups and structural symmetry. The invention also provides an active layer material containing the compound and an organic photoelectric component. The active layer material and the organic photoelectric component have good thermal stability.

Description

Technical Field

[0001] The invention relates to an organic photoelectric compound applied to an organic photoelectric component, in particular to an organic photoelectric compound with a pyrazine core structure and an organic photoelectric component containing the compound. Background Art

[0002] In recent years, due to the vigorous development of solar energy and sensor-related industries, the main application areas cover general livelihood and industry to medical testing and other purposes. In the sensor part, as the dependence of electronic payment and other applications in mobile phones and other consumer electronic products gradually increases, coupled with the increase in the application scope of biometric features such as full-screen fingerprint recognition or vein texture recognition, the demand for this type of technology has also directly or indirectly increased. At this stage, many manufacturers have stepped up their layout of sensor-related technologies, and the future is promising.

[0003] As mentioned above, image sensors have become one of the fastest growing semiconductor product categories in recent years. Its applications can be mainly classified according to the photosensitive band. For example, lenses, optical communications, biochips or fingerprint scanning all rely on visible light band optical sensing technology. The current mainstream technology in the market is photosensitive components composed of single crystal silicon. However, in the foreseeable future, since the visible light band area is far less than the invisible light band, the application demand for invisible light has a trend of increasing significantly in the near future, such as vein scanning recognition (vein scanner), iris recognition (iris sensor), and facial recognition (facial recognition) and other biometric technologies, as well as pulse oximetry measurement of physiological vital signs monitoring technology, or current self-driving car demand for LiDAR (LiDAR), time of flight range sensor (Time of Fight Sensor) and other machine vision applications. Therefore, how to provide an organic light sensor with high performance and low cost in the light absorption range of near infrared light or short wave infrared light corresponding to the above applications is a very important issue at present.

[0004] Active layer materials play an important role in organic light sensors and directly affect the performance of components. Active layer materials are divided into two parts: donors and acceptors. For donor materials, the development of DA-type conjugated polymers is the mainstream. The push-pull electron effect performed by the multi-electron unit and the electron-deficient unit in the conjugated polymer can be used to regulate the energy level and energy gap of the polymer. The matching acceptor material is usually a fullerene derivative with high conductivity, and its absorption range is about 400-600nm. However, fullerene derivatives are not easy to adjust in structure, and their absorption and energy level are limited to a certain range, which limits the matching of the overall donor and acceptor materials. With the development of the market, the demand for materials in the near-infrared region is gradually increasing. Even if the absorption range of the conjugated polymer used as the donor material can be adjusted to the near-infrared region, it may not be well matched due to the limitation of the fullerene acceptor. Therefore, it is necessary to develop non-fullerene acceptors to replace traditional fullerene acceptors. The development of non-fullerene acceptor materials mainly forms ADA ladder molecules with multi-electron centers and electron-deficient units on both sides. D is usually a ladder molecule composed of a benzene ring and thiophene, and A is usually an indanone-cyano (IC) derivative. ITIC is a representative non-fullerene acceptor, which absorbs light at about 600-750nm and has good performance in organic light sensors. In addition to the ADA ladder molecule, in 2019, Yang's team formed a ladder molecule such as Y6 (BTP-4F) with an AD-A'-DA structure, which has an absorption range of 600-900nm, further expanding the absorption spectrum of non-fullerene acceptors to the near-infrared region. However, the non-fullerene acceptors with the Y6 architecture as the core currently have the problem of insufficient thermal stability. For example, the glass transition temperature of Y6, which performs better in the BTP series, is only 102°C and the pyrolysis temperature is only 318°C. For its application in mass production and introduction into commercial products, the service life and stability of the product are a major challenge. Therefore, how to develop an organic photoelectric compound that is a light-absorbing material covering near-infrared light and has good thermal stability is a very important topic at present. Summary of the invention

[0005] Therefore, one scope of the present invention is to provide an organic photoelectric compound having a structure as shown in Formula 1: Wherein, R1 is selected from the following groups and one of their derivatives: C1-C30 alkyl, C6-C30 aryl, C3-C30 heteroaryl, C1-C8 haloalkyl, C4-C30 aralkyl, C4-C30 alkoxy and polymer chain. R2 and R1 may be the same or different, and R2 is selected from the following groups and one of their derivatives: C1-C30 alkyl, C6-C30 aryl, C3-C30 heteroaryl, C1-C8 haloalkyl, C4-C30 aralkyl, C4-C30 alkoxy, hydrogen, fluorine, chlorine and bromine. Ar1 and Ar2 may be the same or different, and are independently selected from the following groups and one of their derivatives: C6-C30 carbon chain, C6-C30 cycloalkyl, C6-C30 aryl, C2-C30 heteroaryl, C1-C30 alkoxy and C7-C30 phenolic alkyl. Ar3 to Ar6 may be the same or different and independently selected from the following groups and their derivatives: C6-C30 aryl, C2-C30 heteroaryl and C2-C8 spiro. Ar7 and Ar8 may be the same or different electron withdrawing groups, the electron withdrawing group being a polycyclic structure with or without substitution including at least one five-membered ring and at least one six-membered ring, a polycyclic structure with or without substitution including at least two five-membered rings, or a polycyclic structure with or without substitution including at least two six-membered rings, and X is selected from nitrogen, oxygen, sulfur and selenium. Wherein, when X is nitrogen, k≧0, l is an integer from 1 to 10, and m is an integer from 0 to 10; when X is oxygen, sulfur or selenium, k and l are 0, and m is an integer from 0 to 10.

[0006] When X is nitrogen and R1 is a non-polymer chain, k is an integer of 0 to 2, l is an integer of 1 to 10, and m is an integer of 0 to 10.

[0007] When X is nitrogen and R1 is a polymer chain, k≧0, l is 1, and m is an integer between 0 and 10.

[0008] Wherein, Ar1 and Ar2 are independently selected from one of the following structures:

[0009]

[0010] Wherein, Z includes halogen. R3 is selected from the following groups and one of their derivatives: C1-C30 straight chain alkyl, C1-C30 branched chain alkyl and C1-C30 alkoxy. R3' is selected from the following groups and one of their derivatives: C1-C30 straight chain alkyl, C1-C30 branched chain alkyl, C6-C30 aryl, C2-C30 heterocyclic, C1-C30 alkoxy and C7-C30 phenolic alkyl.

[0011] Wherein, Ar3 and Ar4 are independently selected from one of the following structures:

[0012]

[0013] Among them, R4 is selected from the following groups and their derivatives: C1-C30 alkyl, C2-C30 heterocycle, C1-C30 alkoxy, and C7-C30 phenalkyl.

[0014] Among them, Ar5 and Ar6 are independently selected from one of the following structures:

[0015]

[0016] Among them, R5 is selected from one of the following groups and their derivatives: C1-C30 alkyl, C6-C30 aryl, C2-C30 heterocycle, C1-C30 alkoxy, C7-C30 phenalkyl, hydrogen, fluorine, and chlorine.

[0017] Among them, the polycyclic structure of Ar7 and Ar8 contains at least one of the following two: at least one five-membered ring containing at least one of cyano and C=O, and at least one six-membered ring containing at least one of hydrogen, halogen, and C=O as substituents.

[0018] Another aspect of the present invention is to provide an active layer material, which includes: a receptor material and a donor material. The receptor material includes the organic optoelectronic compound as described above. The donor material includes at least one organic conjugated polymer.

[0019] Among them, the organic conjugated polymer includes at least one of the following structures:

[0020]

[0021]

[0022]

[0023]

[0024] Among them, 0 < x < 1, 0 < y < 1, and x + y = 1; and n is a positive integer greater than 1.

[0025] Another aspect of the present invention is to provide an organic optoelectronic device, which includes a first electrode, an active layer, and a second electrode. The active layer includes at least one of the organic optoelectronic compounds as described above and at least one of the aforementioned active layer materials. Among them, the active layer is located between the first electrode and the second electrode, and at least one of the first electrode and the second electrode is a transparent or semi-transparent electrode.

[0026] The organic photoelectric component further comprises a first carrier transfer layer and a second carrier transfer layer. The first carrier transfer layer is disposed between the first electrode and the active layer, and the first carrier transfer layer is used to transfer carriers in the first electrode and the active layer. The second carrier transfer layer is disposed between the active layer and the second electrode, and the second carrier transfer layer is used to transfer carriers in the active layer and the second electrode.

[0027] Compared with the prior art, the organic optoelectronic component of the present invention has good thermal stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 A structural schematic diagram of a specific embodiment of an organic optoelectronic component of the present invention is depicted.

[0029] Figure 2 The film surface thermal stability test results of comparative examples Ref., N01 and N15 are shown.

[0030] Figure 3 The thermal stability test results of the membrane surface of D01 and P01 are shown.

[0031] Description of reference numerals:

[0032] 1: Organic optoelectronic components

[0033] 10: Substrate

[0034] 11: First electrode

[0035] 12: First carrier transfer layer

[0036] 13: Active layer

[0037] 14: Second carrier transfer layer

[0038] 15: Second electrode DETAILED DESCRIPTION

[0039] In order to make the advantages, spirit and features of the present invention easier and more clearly understood, the following will be described and discussed in detail with reference to the accompanying drawings and embodiments. It is worth noting that these embodiments are only representative embodiments of the present invention. However, they can be implemented in many different forms and are not limited to the embodiments described in this specification. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thorough and comprehensive.

[0040] The terms used in the various embodiments disclosed in the present invention are only used for the purpose of describing specific embodiments, and are not intended to limit the various embodiments disclosed in the present invention. As used herein, the singular form also includes the plural form, unless the context clearly indicates otherwise. Unless otherwise specified, all terms used in this specification (including technical terms and scientific terms) have the same meanings as those commonly understood by ordinary technicians in the field to which the various embodiments disclosed in the present invention belong. The above terms (such as those defined in generally used dictionaries) will be interpreted as having the same meanings as the contextual meanings in the same technical field, and will not be interpreted as having idealized meanings or overly formal meanings, unless clearly defined in the various embodiments disclosed in the present invention.

[0041] In the description of this specification, the description with reference to the terms "one embodiment", "a specific embodiment", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment are included in at least one embodiment of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments in a suitable manner.

[0042] definition:

[0043] As used herein, a "donor" material or a "p-type" material refers to a semiconductor material, such as an organic semiconductor material, that has holes as the primary current or charge carriers. In certain embodiments, when a p-type semiconductor material is deposited on a substrate, it can provide more than about 10 -5 cm 2 / Vs hole mobility.

[0044] As used herein, an "acceptor" material, an "n-type" material, refers to a semiconductor material, such as an organic semiconductor material, that has electrons as the primary current or charge carrier. In certain embodiments, when an n-type semiconductor material is deposited on a substrate, it can provide more than about 10 -5 cm 2 / Vs electron mobility.

[0045] The "electron-withdrawing group" used in this article is a group or atom that has a stronger electron-withdrawing ability than hydrogen, that is, it has an electron-withdrawing inductive effect. The "electron-pushing group" used in this article is a group or atom that has a stronger electron-pushing ability than hydrogen, that is, it has an electron-pushing inductive effect. The inductive effect is the effect that the bonding electron cloud moves in a certain direction on the atomic bond due to the different polarity (electron negativity) of atoms or groups in the molecule. The electron cloud tends to move toward the group or atom with stronger electronegativity.

[0046] The structures listed in this article “*” or “*” represents the positions of the structure that can be bonded, but is not limited thereto.

[0047] The terms "polymer" and "macromolecule" as used herein refer to a very large molecule consisting of thousands or more covalently bonded atoms. A polymer is composed of many repeating units, i.e. monomers (composed of one or more atoms) bonded together by covalent bonds. From a physical property point of view, the number of repeating units should be so large that adding more repeating units will not significantly change the physical properties. Polymers are further divided into copolymers and homopolymers. Homopolymers are formed by the polymerization of only one monomer. Copolymers are formed by the polymerization of two or more monomers. Copolymers are divided into alternating copolymers, random copolymers, block copolymers, and graft copolymers.

[0048] As used herein, a component (eg, a thin film layer) may be considered "photoactive" if it includes one or more compounds that can absorb photons to generate excitons for generating photocurrent.

[0049] As used herein, "solution processing" refers to processes in which compounds (e.g., polymers), materials or compositions can be used in solution-state processes, such as spin coating, printing (e.g., inkjet printing, gravure printing, lithography, etc.), spraying, electrospraying, drop casting, dip coating and doctor blade coating.

[0050] As used herein, "annealing" refers to a post-deposition heat treatment of a semi-crystalline polymer film for a certain duration in an ambient or under reduced or increased pressure, and "annealing temperature" refers to a temperature at which the polymer film or a mixed film of the polymer and other molecules can undergo small-scale molecular motion and rearrangement during the annealing process. Without being bound by any particular theory, it is said that annealing can, if possible, lead to an increase in crystallinity in the polymer film, improve the material carrier mobility of the polymer film or the mixed film of the polymer and other molecules, and form an interactive molecular arrangement to achieve an effect of independent transfer paths for effective electrons and holes.

[0051] The external quantum efficiency (EQE) used in this article is the quantum efficiency obtained by substituting the spectral response unit Amp / Watt, converting ampere A into the number of electrons per unit time (electron / sec), and watt Watt into the number of photons per unit time (Photons / sec) into the above formula. Generally speaking, quantum efficiency (QE) refers to external quantum efficiency (EQE), also known as incident photon-electron conversion efficiency (IPCE).

[0052] Due to the existing technology, the ladder-shaped molecules formed by the AD-A'-DA structure, such as Y6 (BTP-4F), have the problem of insufficient thermal stability. Therefore, the present invention redesigns the core structure of the AD-A'-DA structure type on the premise of increasing the thermal stability of the non-fullerene acceptor and maintaining the high efficiency of the material, hoping to increase the breadth and depth of its application in related fields after it becomes a commercial product.

[0053] In one embodiment, an organic photoelectric compound of the present invention comprises a structure of Formula 1:

[0054]

[0055] Wherein, R1 is selected from the following groups and one of their derivatives: a C1-C30 alkyl group with or without a substitution group, a C6-C30 aryl group with or without a substitution group, a C3-C30 heteroaryl group with or without a substitution group, a C1-C8 haloalkyl group with or without a substitution group, a C4-C30 aralkyl group with or without a substitution group, a C4-C30 alkoxy group with or without a substitution group, and a polymer chain with or without a substitution group. R2 and R1 may be the same or different, and R2 is selected from the following groups and one of their derivatives: substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C1-C8 haloalkyl, substituted or unsubstituted C4-C30 aralkyl, substituted or unsubstituted C4-C30 alkoxy, hydrogen, fluorine, chlorine and bromine. Ar1 and Ar2 may be the same or different and are independently selected from the following groups and their derivatives: a substituted or unsubstituted C6-C30 carbon chain, a substituted or unsubstituted C6-C30 cycloalkyl, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted C2-C30 heteroaryl, a substituted or unsubstituted C1-C30 alkoxy, and a substituted or unsubstituted C7-C30 phenolalkyl. Ar3 to Ar6 may be the same or different and are independently selected from the following groups and their derivatives: a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted C2-C30 heteroaryl, and a substituted or unsubstituted C2-C8 spirocycle. Ar7 and Ar8 may be the same or different electron withdrawing groups, which are polycyclic structures with or without substitutions including at least one five-membered ring and at least one six-membered ring, polycyclic structures with or without substitutions including at least two five-membered rings, or polycyclic structures with or without substitutions including at least two six-membered rings. X is selected from nitrogen, oxygen, sulfur, and selenium. When X is nitrogen, k≧0, l is an integer from 1 to 10, and m is an integer from 0 to 10; and when X is oxygen, sulfur, or selenium, k and l are 0, and m is an integer from 0 to 10.

[0056] The organic photoelectric compound of the present invention introduces pyrazine groups and additional conjugated planes to effectively improve the stability of the material and increase the carrier transmission channel. Among them, the R1 and R2 groups have the following characteristics: 1. By modifying the R1 and R2 groups, the material energy level and energy gap can be fine-tuned, which is beneficial for matching different P-type materials and increasing the breadth of applications; 2. The R1 and R2 groups can effectively change the intermolecular forces to change the material arrangement and solubility, and maintain the breadth of application. 3. R1 and R2 are used as bridges between molecules to connect two or more molecules to extend the conjugated system and strengthen the network constructed by the intermolecular forces.

[0057] In practical applications, Ar1 and Ar2 are independently selected from one of the following structures:

[0058]

[0059] wherein Z contains halogen. R3 is selected from the following groups and their derivatives: a C1-C30 straight chain alkyl group with or without a substituent, a C1-C30 branched chain alkyl group with or without a substituent, and a C1-C30 alkoxy group with or without a substituent; and R3' is selected from the following groups and their derivatives: a C1-C30 straight chain alkyl group with or without a substituent, a C1-C30 branched chain alkyl group with or without a substituent, a C6-C30 aryl group with or without a substituent, a C2-C30 heterocyclic ring with or without a substituent, a C1-C30 alkoxy group with or without a substituent, and a C7-C30 phenolic alkyl group with or without a substituent.

[0060] In practical applications, Ar3 and Ar4 are independently selected from one of the following structures:

[0061]

[0062] Wherein, R4 is selected from the following groups and one of their derivatives: a C1-C30 alkyl group with or without a substitution group, a C2-C30 heterocycle with or without a substitution group, a C1-C30 alkoxy group with or without a substitution group, and a C7-C30 phenolic alkyl group with or without a substitution group.

[0063] In practical applications, Ar5 and Ar6 are independently selected from one of the following structures:

[0064]

[0065] Among them, R5 is selected from the following groups and one of their derivatives: C1-C30 alkyl with or without substitution, C6-C30 aryl with or without substitution, C2-C30 heterocycle with or without substitution, C1-C30 alkoxy with or without substitution, C7-C30 phenolic alkyl with or without substitution, hydrogen, fluorine and chlorine.

[0066] Furthermore, the polycyclic structures of Ar7 and Ar8 contain at least one of the following two: at least one of the five-membered ring contains at least one of cyano and C=O, and at least one of the six-membered ring contains at least one of hydrogen, halogen and C=O as a substituent.

[0067] In practical applications, Ar7 and Ar8 are independently selected from one of the following structures:

[0068]

[0069] Wherein, Z1 and Z2 may be the same or different, and are independently selected from at least one of a hydrogen atom and a halogen.

[0070] The substituents mentioned above can be independently selected from the following groups and their derivatives: C1-C30 alkyl, C3-C30 branched alkyl, C1-C30 silyl, C2-C30 ester, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 haloalkyl, C2-C30 olefin, C2-C30 alkyne, C2-C30 carbon chain containing cyano, C1-C30 carbon chain containing nitro, C1-C30 carbon chain containing hydroxyl, C3-C30 carbon chain containing keto, halogen, cyano and hydrogen. The aryl and heteroaryl groups mentioned above can contain monocyclic or polycyclic structures.

[0071] Specifically, X is selected from nitrogen, oxygen, sulfur, and selenium. When X is oxygen, sulfur, or selenium, k and l are 0, and m is an integer from 0 to 10. The organic photoelectric compound of the present invention may include the following embodiments:

[0072]

[0073] Wherein, when X is nitrogen and R1 is a non-polymer chain, k is an integer of 0 to 2, l is an integer of 1 to 10, and m is an integer of 0 to 10. In detail, the organic photoelectric compound of the present invention may include the following embodiments:

[0074]

[0075]

[0076]

[0077] The following will take D01 to D04 as examples of the structure of dimers, and D05 as an example of the structure of trimers, but not limited thereto.

[0078]

[0079]

[0080] Among them, when X is nitrogen and R1 is a polymer chain, k≥0, l is 1, and m is an integer from 0 to 10. Specifically, the organic optoelectronic compound of the present invention may include the following embodiments:

[0081]

[0082] It should be understood that the above embodiments are representative examples for those of ordinary skill in the art to more clearly understand the structural composition of the present invention, but not limited thereto.

[0083] In practical applications, the present invention also provides an active layer material, which includes a receptor material and a donor material. Among them, the receptor material includes the aforementioned organic optoelectronic compound. The donor material includes at least one organic conjugated polymer.

[0084] Specifically, the organic conjugated polymer may include at least one of the following embodiments:

[0085]

[0086]

[0087]

[0088]

[0089] Among them, 0 < x < 1, 0 < y < 1, and x + y = 1, where x and y are the molar ratios, and n is a positive integer greater than 1. It should be understood that the above embodiments are representative examples for those of ordinary skill in the art to more clearly understand the structural composition of the present invention, but not limited thereto.

[0090] Please refer to Figure 1 , Figure 1 is a schematic structural diagram showing an embodiment of the organic optoelectronic component 1 of the present invention. As Figure 1As shown, in an embodiment, the present invention provides an organic photoelectric device 1, which includes a first electrode 11, a second electrode 15 and an active layer 13. The active layer 13 is located between the first electrode 11 and the second electrode 15. In one embodiment, the active layer 13 includes at least one of the organic photoelectric compound having a structure of Formula 1 and the active layer material. The organic photoelectric device 1 can be a stacked structure, further including a first carrier transfer layer 12 and a second carrier transfer layer 14, and is stacked in sequence with a substrate 10, a first electrode 11 (transparent or semi-transparent electrode), a first carrier transfer layer 12, an active layer 13, a second carrier transfer layer 14 and a second electrode 15. The first carrier transfer layer 12 is used to transfer carriers in the first electrode 11 and the active layer 13, and the second carrier transfer layer 14 is used to transfer carriers in the active layer 13 and the second electrode 15. In detail, the first carrier transfer layer 12 is one of an electron transport layer and a hole transport layer, and the second carrier transfer layer 14 is the other. Specifically, when the first carrier transport layer 12 is an electron transport layer, the second carrier transport layer 14 is a hole transport layer, which is a reverse stack structure; when the first carrier transport layer 12 is a hole transport layer, the second carrier transport layer 14 is an electron transport layer, which is a regular stack structure. In practice, the organic optoelectronic component 1 may include an organic photovoltaic component, an organic light sensing component, and an organic light emitting diode.

[0091] In order to more clearly illustrate the organic photoelectric compound of the present invention, the following experiment will be conducted using the comparative example Ref. and the aforementioned embodiments N01, N03, N05, N14, N15, D01, S01 and P01 of the present invention to illustrate the difference in efficacy, and further use them as receptor materials to prepare active layer materials and organic photoelectric components for material testing and component testing.

[0092] For the optical physical property quality measurement part of material testing and component testing, the UV absorption spectrum measurement instrument model is Hitachi UH5700, and the oxidation potential is measured using cyclic voltammetry with CH Instrument 611E.

[0093] Synthesis of N01-A0:

[0094]

[0095] N01-A0 was prepared by the synthesis method according to Adv. Mater. 2019, 31, 1807577.

[0096] Synthesis of N01-A1:

[0097]

[0098] N01-A0 (1.50 g, 1.34 mmol) and potassium hydroxide (0.90 g, 10.71 mmol) were placed in a 500 ml double-necked flask, and 75 ml of dimethyl sulfoxide and 75 ml of toluene were added under nitrogen. The reactants were heated to 80°C for 30 minutes. 7-(iodomethyl)pentadecane (2.10 g, 4.02 mmol) was slowly added dropwise to the reaction. After 3 hours of reaction, potassium hydroxide (0.90 g, 10.71 mmol) was added again, and after half an hour, 7-(iodomethyl)pentadecane (2.10 g, 4.02 mmol) was added for the second time. The temperature was kept at 80°C and the reaction was continued for 24 hours, and then the reaction was terminated with deionized water and extracted with heptane. After dehydration with magnesium sulfate, the mixture was concentrated under reduced pressure to a brown oily viscous substance. The crude product was purified by silica gel column chromatography (the eluent was dichloromethane / heptane = 1 / 19) to obtain the product N01-A1. 1 H NMR (500MHz, CDCl3) δ7.03 (s, 2H), 4.72 (d, J = 7.5Hz, 4H), 2.99 (t, J = 7.5Hz, 4H), 2.19-2.21 (m, 2H), 1.99-2.03 (m, 4H), 0.65-1.52 (m, 98H).

[0099] Synthesis of N01-I1:

[0100]

[0101] Dissolve isotonic acid (2.00 g, 13.59 mmol) in 10 ml of dimethylacetamide under nitrogen. Add potassium carbonate (K2CO3, 2.44 g, 17.67 mmol) to the reactant and stir at room temperature for 30 minutes. Slowly add 3-(bromomethyl)hexane (2.89 g, 14.95 mmol) and 10 ml of dimethylacetamide. Heat the reactant to 50°C for 18 hours, cool it down, inject 20 ml of deionized water to terminate the reaction and extract with dichloromethane. Dehydrate with magnesium sulfate and concentrate to obtain a crude product. The crude product is purified by silica gel column (eluent is dichloromethane) to obtain product N01-I1 (3.32 g, yield 94%). 1 H NMR (600MHz, CDCl3) δ7.60(d,J=7.2Hz,1H),7.58(dt,J=7.8,1.2Hz,1H),7.11(t,J=7.8Hz,1H),6.87(d,J=7.8 Hz, 1H), 3.57-3.64 (m, 2H), 1.79-1.83 (m, 1H), 1.25-1.43 (m, 8H), 0.93 (t, J = 7.2Hz, 3H), 0.89 (t, J = 7.2Hz, 3H).

[0102] Synthesis of N01-A3:

[0103]

[0104] N01-A1 (2.00 g, 1.67 mmol) was placed in a double-necked flask and the gas was replaced with argon. 40 ml of tetrahydrofuran was injected at room temperature to dissolve. The reactants were cooled to 5°C and lithium aluminum hydride (0.32 g, 8.43 mmol) was added. After slowly warming to room temperature, the mixture was stirred under argon for 16 hours. The reaction was cooled to 5°C again and 1.00 ml of deionized water was slowly added to terminate the reaction. After stirring for 30 minutes, the mixture was dehydrated with magnesium sulfate. The brown-black oil was purified by silica gel column to obtain 1.68 g of crude N01-A2. The dried crude N01-A2 was directly subjected to the next cyclization reaction without purification. 1.68 g of crude N01-A2 and N01-I1 (0.65 g, 2.51 mmol) were placed in a 100 ml reaction flask and 35 ml of glacial acetic acid were added. Under nitrogen, the mixture was heated to 120°C for 2 hours and then injected with 50 ml of deionized water. The extract was extracted with dichloromethane and heptane in a volume ratio of 1:3 to obtain an extract. The extract was neutralized with a saturated potassium carbonate aqueous solution to a pH value between 6 and 7, and the organic layer was washed with 50 ml of deionized water. After dehydration and concentration, it was purified with a silica gel column (the eluent was dichloromethane / heptane = 1 / 1) to obtain N01-A3 (0.62 g, 31% yield after two-step reaction). 1 H NMR (500MHz, CDCl3) δ8.78 (dd, J=8.0, 1.5Hz, 1H), 7.59 (dt, J=7.0, 1.5Hz, 1H), 7.37-7.42 (m, 2H), 7.01 (s, 1H), 6.97(s,1H),4.41-4.67(m,6H),2.81-2.87(m,4H),2.17-2.23(m,2H),1.87-1.93(m,6H),0.67-1.66(m,112H).

[0105] Synthesis of N01-A4:

[0106]

[0107] N01-A3 (0.22 g, 0.16 mmol) was placed in a double-necked flask and injected with 8.0 ml of 1,2-dichloroethane under argon. Dimethylformamide (0.15 ml, 1.90 mmol) and phosphorus oxychloride (0.14 ml, 1.48 mmol) were prepared into a Vilsmayer-Hack reagent. The Vilsmayer-Hack reagent was slowly added to the reactants and heated to 70°C for 4 hours. The mixture was cooled to room temperature and stirred with a 2% potassium carbonate aqueous solution for more than 1 hour. The mixture was extracted with heptane and dichloromethane, and the obtained extract was quenched with deionized water, dehydrated and concentrated. The crude product was purified by silica gel column chromatography (eluents were dichloromethane and heptane) to obtain N01-A4 (0.21 g, yield 91%). 1 H NMR (500MHz, CDCl3) δ10.15(s,1H),10.14(s,1H),8.78(dd,J=9.5,1.5Hz,1H),7.66(dt,J=7.0,1.5Hz,1H),7.42-7.47(m, 2H),4.41-4.64(m,6H),3.23-3.21(m,4H),2.14-2.17(m,2H),1.96-1.98(m,4H),1.82-1.87(m,2H),0.67-1.61(m,112H).

[0108] Synthesis of N01:

[0109]

[0110] N01-A4 (0.17 g, 0.12 mmol) and 5,6-difluoro-1,3-hydroindanedione (0.11 g, 0.48 mmol) were placed in a double-necked flask, and 8.8 ml of chloroform was injected under argon. Pyridine (0.17 ml, 2.11 mmol) was added at room temperature and heated to 65°C for 4 hours. After cooling to room temperature, 17 ml of methanol was injected into the reaction flask to precipitate the product. The solid was collected by filtration and purified with a silica gel column (the eluents were chloroform and heptane), and then the solid was precipitated with isopropanol to obtain N01 (0.17 g, yield 75%). 1H NMR(600MHz, CDCl3)δ9.19(s,1H),9.18(s,1H),8.78(dd,J=7.8,1.2Hz,1H),8.55-8.59(m,2H),7.67-7.70(m,3H),7.45-7.49(m,2H),4.7 6(d,J=7.8Hz,1H),4.72(d,J=7.2Hz,1H),4.40-4.56(m,2H),3.25-3.27(m,4H),2.14-2.17(m,2H),1.89-1.93(m,6H),0.51-1.6(m,112H).

[0111] Synthesis of N14:

[0112] Synthesis of N14-IB1:

[0113]

[0114] N01-I1 (1.06 g, 4.09 mmol) was placed in a 100 ml double-necked reaction bottle, and 40 ml of tetrahydrofuran was added under nitrogen. 800 mg of N-bromosuccinimide (4.50 mmol) was added at room temperature and stirred for 18 hours. The reaction was terminated with a saturated aqueous potassium carbonate solution. The product was extracted with dichloromethane, and the organic layer solution was then washed with deionized water. After dehydration with magnesium sulfate, the product was purified by silica gel column chromatography (the eluent was dichloromethane and heptane), and N14-IB1 (1.12 g, yield 81%) was obtained after concentration. 1 H NMR (500MHz, CDCl3) δ7.70(d,J=2.0Hz,1H),7.68(dd,J=7.0,1.5Hz,1H),6.78(d,J=7.5Hz,1H),3.5 6-3.63(m,2H),1.76-1.80(m,1H),1.22-1.39(m,8H),0.93(t,J=6.5Hz,3H),0.88(t,J=6.0Hz,3H).

[0115] Synthesis of N14-A1:

[0116]

[0117] The crude product of N01-A2 (0.57 g, 0.49 mmol) and N14-IB1 (0.17 g, 0.51 mmol) were reacted and purified using the same steps as N01-A3 to obtain N14-A1 (0.35 g, 48% yield). 1H NMR (500MHz, CDCl3) δ8.89(d,J=2.0Hz,1H),7.65(t,J=7.0Hz,1H),7.25(t,J=7.0Hz,1H),7.02(s,1H),6.98(s,1H), 4.59-4.63(m,4H),4.38-4.50(m,2H),2.85-2.88(m,4H),2.09-2.11(m,2H),1.89-1.95(m,6H),0.67-1.60(m,112H).

[0118] Synthesis of N14-A2:

[0119]

[0120] N14-A1 (0.30 g, 0.21 mmol), 2-tributylstannylthiophene (0.17 g, 0.45 mmol), tri(dibenzylideneacetone)dipalladium (0.01 g, 0.01 mmol), tri(o-methylphenyl)phosphine (0.013 g, 0.04 mmol) were placed in a 100 ml double-necked flask, and 30 ml of deoxygenated toluene was injected under argon and stirred. The reactants were placed in a 90°C oil bath and heated for 18 hours. After cooling to room temperature, the reactants were filtered with diatomaceous earth and concentrated to obtain a brown crude product. The crude product was purified by silica gel column chromatography (eluting solvents were heptane and dichloromethane) to obtain N14-A2 (0.26 g, yield 84%). 1 H NMR (500MHz, CDCl3) δ8.99(d,J=2.5Hz,1H),7.84(dd,J=9.0,2.0Hz,1H),7.56(s,1H),7.37(d,J=2.5Hz,1H),7.36(d,J=1.0Hz,1H),7.18(d,J=1.0Hz ,1H),7.01(s,1H),6.97(s,1H),4.57-4.61(m,4H),4.42-4.59(m,2H),2.8 4-2.88(m,4H),2.37-2.15(m,2H),1.89-1.91(m,6H),0.79-1.61(m,112H).

[0121] Synthesis of N14-A3:

[0122]

[0123] Place N14-A2 (0.18 g, 0.12 mmol) in a 50 ml double-necked flask and replace the gas with argon. Inject 7.0 ml of 1,2-dichloroethane at room temperature to dissolve. Prepare dimethylformamide (0.51 ml, 6.58 mmol) and phosphorus oxychloride (0.17 ml, 1.77 mmol) to form a Vilsmeier-Hack reagent and slowly add it to the reactants. Heat to 70°C and react for 4 hours. Cool to room temperature and stir with 2% potassium carbonate aqueous solution for more than 1 hour. Extract with heptane and dichloromethane, and the obtained extract is quenched with deionized water, then dehydrated and concentrated. Purify with silica gel column chromatography (eluents are dichloromethane and heptane) to obtain an orange solid product N14-A3 (0.18 g, yield 95%). 1 H NMR (500MHz, CDCl3) δ10.18(s,1H),10.16(s,1H),8.91(s,1H),8.10(s,1H),7.73(dd,J=9.0,2.5Hz,1H),7.29(d,J=9.0Hz ,1H),4.70-4.62(m,4H),4.60-4.36(m,2H),3.28-3.18(m,4H),2.17-2.10(m,2H),1.97-1.95(m,6H),0.66-1.73(m,112H).

[0124] Synthesis of N14:

[0125]

[0126] N14-A3 (0.18 g, 0.11 mmol) and 5,6-difluoro-1,3-hydroindanedione (0.17 g, 0.74 mmol) were placed in a double-necked flask and injected with 12 ml of chloroform under argon. 0.18 ml of pyridine was added at room temperature and heated to 65°C for 5 hours. After cooling to room temperature, 40 ml of methanol was injected into the reaction flask to precipitate the product, and the solid was collected by filtration. Purification was performed by silica gel column chromatography (the eluents were chloroform and heptane), and the solid was precipitated with isopropanol to obtain N14 (0.22 g, yield 89%). 1 H NMR(600MHz, CDCl3)δ9.20(s,1H),9.15(s,1H),9.01(br,1H),8.85(br,1H),8.61-8.58(m,2H),8.50(br,1H),7.99(br,1H),7.81(s,1H) ,7.77-7.67(m,4H),4.84-4.79(m,4H),4.42-4.60(m,2H),3.25-3.30(m,4H),2.10-2.07(m,2H),1.89-1.95(m,6H),0.66-1.59(m,112H).

[0127] Synthesis of N15:

[0128] Synthesis of N15-A0:

[0129]

[0130] N01-A0 (1.5 g, 1.34 mmol) and 1-iodo-2-decyltetradecane (5.6 g, 4.12 mmol) were used to synthesize N15-A0 under the reaction conditions of N01-A1 to obtain a bright orange solid N15-A0 (2.65 g, 92% yield). 1 H NMR (500MHz, CDCl3) δ7.02 (s, 2H), 4.71 (d, J = 7.5Hz, 4H), 3.00 (t, J = 7.5Hz, 4H), 2.19-2.21 (m, 2H), 1.99-2.03 (m, 4H), 0.63-1.60 (m, 134H).

[0131] Synthesis of N15-A2:

[0132]

[0133] Take 380 mg of N15-A0 and react it under the reaction conditions of N01-A2 and N14-A2 to obtain N15-A2 (134 mg, yield 40%). 1 H NMR (600MHz, CDCl3) δ8.88(d,J=2.4Hz,1H),8.10(s,1H),7.67(dd,J=9.0,2.4Hz,1H),7.56(s,1H),7.25(d,J=2.4Hz,1H),7 .00(s,1H),6.96(s,1H),4.56-4.60(m,4H),4.38-4.48(m,2H),2.84-2.88(m,4H),2.08-2.10(m,4H),0.79-1.60(m,146H).

[0134] Synthesis of N15-A3:

[0135]

[0136] Take 120 mg of N15-A2 and react it under the reaction conditions of N14-A3 to obtain N15-A3 (74 mg, yield 62%). 1HNMR (600MHz, CDCl3) δ8.98(d,J=1.8Hz,1H),7.84(dd,J=9.0,2.4Hz,1H),7.56(d,J=3.0Hz,1H),7.40(d,J=8.4Hz,1H),7.37(d,J=7.2Hz,1H),7.18 (dd,J=3.6,1.8Hz,1H),7.00(s,1H),6.97(s,1H),4.61-4.58(m,4H),4.53 -4.42(m,2H),2.84-2.88(m,4H),2.16-2.14(m,2H),1.64-0.83(m,146H).

[0137] Synthesis of N15-A4:

[0138]

[0139] 112 mg of N15-A3 was reacted under the reaction conditions of N14-A4 to obtain N15-A4 (47 mg, yield 40%). 1 HNMR(500MHz, CDCl3)δ10.16(s,1H),10.15(s,1H),9.98(s,1H),9.05(d,J= 1.5Hz,1H),7.94(dd,J=7.0,1.5Hz,1H),7.85(d,J=3.0Hz,1H),7.67(d,J=3 .0Hz,1H),7.50(d,J=7.5Hz,1H),4.63-4.42(m,6H),3.27-3.22(m,4H),2.1 7-2.13(m,2H),2.00-1.96(m,4H),1.89-1.82(m,2H),0.66-1.64(m,142H).

[0140] Synthesis of N15:

[0141]

[0142] 47 mg of N15-A4 was reacted under the reaction conditions of N14 to obtain N15 (51 mg, yield 80%). 1H NMR(600MHz, CDCl3)δ9.20(s,2H),9.14(s,1H),8.99(br,1H),8.84(br,1H),8.61-8.57(m,2H),8.50(br,1H),7.99(br,1H),7.81(s,1H) ,7.77-7.67(m,4H),4.87-4.74(m,4H),4.64-4.41(m,2H),3.23-3.30(m,4H),2.11-2.06(m,2H),1.96-1.87(m,6H),0.66-1.59(m,142H).

[0143] Synthesis of N03:

[0144] Synthesis of N03-A1:

[0145]

[0146] Place N14-A1 (0.20 g, 0.14 mmol) in a 50 ml double-necked flask and inject 8.0 ml of 1,2-dichloroethane under argon. Prepare the Vilsmeier-Hack reagent with 0.25 ml of dimethylformamide and 0.25 ml of phosphorus oxychloride and slowly add it to the reaction system, and heat to 55°C for 2 hours. Cool to room temperature and stir with 2% potassium carbonate aqueous solution for more than 1 hour. Extract with heptane and dichloromethane, and the obtained extract is quenched with deionized water, dehydrated and concentrated. Purify by silica gel column chromatography (eluents are dichloromethane and heptane) to obtain N03-A1 (0.12 g, yield 56%). 1 H NMR (500MHz, CDCl3) δ10.16 (s, 1H), 10.15 (s, 1H), 8.88 (d, J = 2.0Hz 1H),8.10(s,1H),7.73(dd,J=9.0,2.0Hz,1H),7.29(d,J=9.0Hz,1H),4.64-4.56(m,4H),4.53 -4.37(m,2H),3.25-3.21(m,4H),2.10-2.07(m,2H),1.97-1.93(m,6H),0.66-1.73(m,112H).

[0147] Synthesis of N03:

[0148]

[0149] Place N03-A1 (0.10 g, 0.06 mmol) and 5,6-difluoro-1,3-hydroindanedione (0.06 g, 0.25 mmol) in a double-necked flask and inject 7 ml of chloroform under argon. Add 0.10 ml of pyridine at room temperature and heat to 65°C for 2 hours. After cooling to room temperature, inject 20 ml of methanol into the reaction flask to precipitate the product, and collect the solid by filtration. Purify with silica gel column chromatography (eluents are chloroform and heptane), and then precipitate the solid with isopropanol to obtain a black solid product N03 (0.09 g, yield 71%). 1 H NMR (600MHz, CDCl3) δ9.19 (s, 1H), 9.18 (s, 1H), 8.89 (d, J = 2.4Hz, 1H), 8.59 -8.56(m,2H),7.77(dd,J=9.0,2.4Hz,1H),7.71-7.68(m,2H),7.36(d,J=9.0 Hz,1H),4.76(d,J=7.8Hz,2H),4.72(d,J=7.2Hz,2H),4.35-4.60(m,2H),3. 26-3.30(m,4H),2.14-2.09(m,2H),1.86-1.95(m,6H),0.64-1.58(m,112H).

[0150] Synthesis of N05:

[0151] Synthesis of N05-A1:

[0152]

[0153] 112 mg of N15-A3 was reacted under the reaction conditions of N03-A1 to obtain N05-A1 (35 mg, yield 30%). 1 HNMR (500MHz, CDCl3) δ10.15 (s, 1H), 10.14 (s, 1H), 8.97 (d, J = 1.5Hz, 1H), 7.8 9(dd,J=7.0,1.5Hz,1H),7.56(d,J=2.5Hz,1H),7.45(d,J=7.5Hz,1H),7.39(d ,J=4.0Hz,1H),7.20(t,J=3.5Hz,1H),4.63-4.40(m,6H),3.25-3.21(m,4H),2 .17-2.15(m,2H),2.01-1.94(m,4H),1.89-1.82(m,2H),0.82-1.63(m,142H).

[0154] Synthesis of N05:

[0155]

[0156] 35 mg of N05-A1 was reacted under N14 reaction conditions to obtain N05 (35 mg, yield 80%). 1 H NMR (500MHz, CDCl3) δ9.20 (s, 1H), 9.19 (s, 1H), 8.96 (d, J = 2.0Hz, 1H), 8.60-8.56 (m, 2H), 7 .92(dd,J=8.5,2.0Hz,1H),7.72-7.68(m,2H),7.57(dd,J=3.5,1.0Hz,1H),7.46(d,J=9.0H z,1H),7.41(dd,J=5.5,1.0Hz,1H),7.21(dd,J=5.0,3.5Hz,1H),4.77-4.73(m,4H),4.59-4 .39(m,2H),3.31-3.27(m,4H),2.15-2.17(m,2H),1.96-1.88(m,6H),0.64-1.81(m,142H).

[0157] Synthesis of D01:

[0158] Synthesis of D01-I1:

[0159]

[0160] Dissolve isotonic acid (1.51 g, 10.26 mmol) in 20 ml of dimethylacetamide under nitrogen, add potassium carbonate (7.09 g, 51.32 mmol) and stir at room temperature for 30 minutes. Slowly add 1,6-dibromohexane (0.79 ml, 5.13 mmol) and 10 ml of dimethylacetamide. Heat the reactants to 60 ° C for 24 hours. After cooling, inject 150 ml of deionized water to terminate the reaction. Filter and collect the solid, and wash the solid with deionized water and methanol. After drying, an orange-red solid product D01-I1 (1.60 g, yield 83%) is obtained. 1 H NMR (600MHz, CDCl3) δ7.57-7.61 (m, 4H), 7.11 (dt, J = 7.8, 1.2Hz, 2H), 6.88 (d ,J=8.4Hz,2H),3.72(t,J=7.2Hz,4H),1.72-1.70(m,4H),1.45-1.43(m,4H).

[0161] Synthesis of D01-A1:

[0162] The crude product N01-A2 (0.59 g, 0.50 mmol) and D01-I1 (0.1 g, 0.25 mmol) were reacted and purified using the same steps as N01-A3 to obtain an orange paste product D01-A1 (0.20 g, 30% yield). 1 H NMR(500MHz, CDCl3)δ8.76(d,J=8.0Hz,2H),7.46(t,J=7.0Hz,2H),7.38-7.34(m,4H),7.01(s,2H),6.96(s ,2H),4.71-4.58(m,12H),2.90-2.83(m,8H),2.00-2.10(m,4H),1.89-1.87(m,16H),0.67-1.42(m,196H).

[0163] Synthesis of D01-A2:

[0164]

[0165] D01-A1 (0.20 g, 0.08 mmol) was placed in a 50 ml double-necked flask and injected with 8.0 ml of 1,2-dichloroethane under argon. 1.42 ml of dimethylformamide and 1.43 ml of phosphorus oxychloride were prepared into a Vilsmayer-Hack reagent. The Vilsmayer-Hack reagent was slowly added to the reactants and heated to 70°C for 24 hours. The mixture was cooled to room temperature and stirred with a 2% potassium carbonate aqueous solution for more than 1 hour. The mixture was extracted with heptane and dichloromethane, and the obtained extract was quenched with deionized water, dehydrated and concentrated. The product D01-A2 (0.20 g, yield 94%) was obtained by purification by silica gel column chromatography (eluting solvents were ethyl acetate and heptane) to obtain an orange solid product. 1 H NMR (600MHz, CDCl3) δ10.15(s,2H),10.12(s,2H),8.77(dd,J=7.8,1.2Hz,2H),7.54(td,J=8.4,1.2Hz,2H),7.41 -7.39(m,4H),4.64-4.60(m,8H),3.24-3.18(m,8H),2.06-2.04(m,4H),1.97-1.82(m,16H),0.66-1.73(m,200H).

[0166] Synthesis of D01:

[0167]

[0168] D01-A2 (0.11 g, 0.04 mmol) and 5,6-difluoro-1,3-hydroindanedione (0.08 g, 0.34 mmol) were placed in a double-necked flask and injected with 7.0 ml of chloroform under argon. 0.1 ml of pyridine was added at room temperature and heated to 65°C for 5 hours. After cooling to room temperature, 30 ml of methanol was injected into the reaction flask to precipitate the product. The solid was collected by filtration and purified by silica gel column chromatography (the eluents were chloroform and heptane). The solid was precipitated with isopropanol to obtain a blue-black solid product D01 (0.10 g, yield 75%). 1 H NMR(500MHz, CDCl3)δ9.17(s,2H),9.07(s,2H),8.74-8.73(m,2H),8.60-8.53(m,4H),7.71(t,J=8.0Hz,2H),7.62-7.58(m, 4H),7.44-7.40(m,4H),4.81-4.74(m,8H),3.28-3.25(m,8H),2.10-2.07(m,4H),1.81-1.97(m,16H),0.66-1.59(m,200H).

[0169] Synthesis of S01:

[0170] Synthesis of S01-A1:

[0171]

[0172] The crude product N01-A2 (0.42 g, 0.36 mmol) and 1-benzothiophene-2,3-dione (0.06 g, 0.37 mmol) were reacted and purified using the N01-A3 steps to obtain a brown oily paste product S01-A1 (0.27 g, 59% yield). 1 HNMR(500MHz, CDCl3)δ8.24(d,J=8.5Hz,1H),8.13(d,J=7.5Hz,1H),7.44(d t,J=7.0,1.0Hz,1H),7.30(dt,J=8.0,1.0Hz,1H),7.05(s,1H),6.97(s,1H) ,4.61(d,J=7.5Hz,2H),4.55(d,J=7.5Hz,2H),4.38-4.50(m,2H),2.82(t,J =7.5Hz,2H),2.18(t,J=7.5Hz,2H),2.01-2.11(m,4H),0.66-1.87(m,98H).

[0173] Synthesis of S01-A2:

[0174]

[0175] S01-A1 (0.28 g, 0.19 mmol) was subjected to the reaction and purification steps of N01-A4 to obtain a yellow-brown oily paste product S01-A2 (0.16 g, yield 62%). 1 H NMR (500MHz, CDCl3) δ10.16(s,1H),10.09(s,1H),8.14(d,J=8.0Hz,1H),8.09(d,J=7.0Hz,1H),7.39(t,J=7.0Hz,1H),7.30(t,J=7.0Hz, 1H), 4.64 (d, J = 7.5Hz, 2H), 4.58 (d, J = 7.5Hz, 2H), 3.21 (t, J = 8.0Hz, 2H), 3.04 (t, J = 7.5Hz, 2H), 2.07-1.98 (m, 2H), 1.96-0.66 (m, 102H).

[0176] Synthesis of S01:

[0177]

[0178] S01-A2 (0.16 g, 0.12 mmol) was reacted with N01 and purified to obtain a black solid product S01 (0.05 g, yield 24%). 1 H NMR (500MHz, CDCl3) δ9.18 (s, 1H), 9.16 (s, 1H), 8.57 (m, 2H), 8.10 (d, J = 8.0Hz, 1H), 8.02(m,1H),7.69(m,2H),7.32(m,1H),7.08(m,1H),4.78-4.65(m,4H),3.29-3.25(m 4H),2.17-0.66(m,104H).

[0179] Synthesis of P01:

[0180] Synthesis of P01-I0:

[0181]

[0182] P01-I0 was prepared by the synthetic method according to J. Mater. Chem. 2011, 21, 2733-2739.

[0183] Synthesis of P01-I1:

[0184]

[0185] Dissolve isotonic acid (0.50 g, 3.40 mmol) in 10 ml of dimethylacetamide under nitrogen. Add potassium carbonate (1.88 g, 13.59 mmol) and stir at room temperature for 30 minutes. Slowly add P01-I0 (1.51 g, 3.74 mmol) and 10 ml of methylacetamide, and heat the reactants to 85°C for 20 hours. After cooling, inject 20 ml of deionized water to terminate the reaction and extract with dichloromethane. Dehydrate with magnesium sulfate and concentrate to obtain a crude product. The crude product is purified by silica gel column chromatography (eluent is dichloromethane) to obtain P01-I1 (1.24 g, yield 78%). 1 H NMR (600MHz, CDCl3) δ7.61-7.57(m,2H),7.11(t,J=7.8Hz,1H),6.88(d,J=7.8Hz,1H),6.75(s,1H),3 .71(t,J=7.2Hz,2H),2.50(t,J=7.2Hz,2H),1.73-1.68(m,2H),1.57-1.52(m,2H),1.42-1.35(m,4H).

[0186] Synthesis of P01-A1:

[0187]

[0188] The crude product N01-A2 (0.90 g, 0.77 mmol) and P01-I1 (0.38 g, 0.81 mmol) were reacted and purified using the same steps as N01-A3 to obtain P01-A1 (0.52 g, 42% yield). 1 H NMR (600MHz, CDCl3) δ8.79(d,J=7.2Hz,1H),7.61(dt,J=7.8,1.0Hz,1H),7.42(t,J=7.2Hz,1H),7.38(d,J=8.4Hz,1H),7.00(s,1H),6.97(s,1 H), 6.75 (s, 1H), 4.61-4.52 (m, 6H), 4.55 (d, J = 7.5Hz, 2H), 2.87-2.83 (m, 4H), 2.56 (t, J = 7.2Hz, 2H), 1.98-1.87 (m, 8H), 1.67-0.67 (m, 102H).

[0189] Synthesis of P01-A2:

[0190]

[0191] P01-A1 (0.52 g, 0.32 mmol) was reacted and purified using N01-A4 to obtain P01-A2 (0.49 g, 91% yield). 1 H NMR (500MHz, CDCl3) δ10.15(s,1H),10.14(s,1H),8.79(dd,J=6.5,1.0Hz,1H),7.67(dt,J=6.5,1.0Hz,1H),7.46(t,J=6.5Hz,1H),7.42(d,J=8.0 Hz,1H),6.75(s,1H),4.64-4.53(m,6H),3.23(t,J=6.5Hz,4H),2.55(t,J =6.5Hz,2H),2.00-1.93(m,6H),1.87-1.81(m,2H),1.96-0.66(m,102H).

[0192] Synthesis of P01-A3:

[0193]

[0194] P01-A2 (0.49 g, 0.29 mmol) was reacted with N01 and purified to obtain P01-A3 (0.56 g, 92% yield). 1 H NMR(600MHz, CDCl3)δ9.18(s,2H),8.79(d,J=7.8Hz,2H),8.59-8.56(m,2H),7.72-7.67(m,2H),7.49(t,J=8.4Hz,1H), 7.42(d,J=8.4Hz,1H),6.75(s,1H),4.77-4.54(m,6H),3.30-3.27(m,4H),2.55(t,J=9.0Hz,2H),1.99-0.65(m,112H).

[0195] Synthesis of P01:

[0196]

[0197] P01-A3 (0.21 g, 0.10 mmol), 2,5-trimethyltinthiophene (0.10 mmol), tri(dibenzylideneacetone)dipalladium (0.01 g, 0.001 mmol) and tri(o-methylphenyl)phosphine (0.012 g, 0.004 mmol) were placed in a 100 ml double-necked flask, and 6 ml of deoxygenated toluene was injected under argon and stirred. The reactants were heated in a 90°C oil bath for 45 minutes. The reaction was terminated with 2-bromothiophene. After cooling to room temperature, the reactants were filtered through diatomaceous earth and precipitated in methanol to obtain a black crude product. The crude product was purified by Soxhlet extraction with methanol and acetone to obtain a black solid product P01 (0.13 g, yield 64%).

[0198] Characteristic test of organic photoelectric compounds:

[0199] Please refer to Table 1, which shows the examples N01, N03, N05, N14, N15, D01, S01,

[0200] The test results of P01 and comparative example Ref.

[0201] Table 1: Test results of Examples N01, N03, N05, N14, N15, D01, S01, P01 and Comparative Example Ref.

[0202]

[0203] Among them, the structure of comparative example Ref. is:

[0204]

[0205] The embodiment and comparative example are ladder-shaped molecules formed by AD-A'-DA structure, but the difference is that the organic photoelectric compound of the present invention has a pyrazine core structure. The embodiment and comparative example Ref. listed in the table are measured by cyclic voltammetry for oxidation properties. After calculation (HOMO = -|4.71 + E ox -E ferroncene |) to obtain the highest occupied molecular orbital (HOMO), and then the absorption onset position (λ film onset ), we can know the optical energy gap (E g =1241 / λ film onset ) and the lowest unoccupied molecular orbital (LUMO, LUMO = HOMO + E g). As shown in Table 1, the maximum absorption value and absorption coefficient in the absorption spectra of the energy level, HOMO, LUMO, film state and solution state are recorded.

[0206] See also Figure 2 and Figure 3 , Figure 2 The thermal stability test results of the membrane surface of the comparative examples Ref., N01 and N15 are shown. Figure 3 The thermal stability test results of the film surface of D01 and P01 are shown. In order to test the thermal stability performance of the examples and compare with the comparative example Ref., the comparative example Ref., the examples N01, N15, D01 and P01 were coated into thin film samples, and the initial film surface before heating and the film surface after heating at 220°C for 1 hour in the atmosphere were observed. Figure 2 and Figure 3 As shown, the film surface of the comparative example Ref. aggregates after heating, while the film surfaces of the examples remain unchanged. It can be seen that the thermal stability of the organic photoelectric compound of the present invention is better than that of the comparative example Ref.

[0207] Preparation and thermal stability performance test of organic photosensitive components of organic optoelectronic components:

[0208] Pre-patterned indium tin oxide (ITO) coated glass with a sheet resistance of ~15Ω / sq was used as a substrate. Ultrasonic shock treatment was carried out in deionized water containing soap, deionized water, acetone and isopropanol in sequence, and cleaning was carried out for 15 minutes in each step. The washed substrate was further treated with a UV-ozone cleaner for 15 minutes. A top coating of aluminum doped zinc oxide nanoparticles (AZO) was spin-coated on the ITO substrate at a rotation rate of 2000 rpm for 40 seconds, and then baked at 120°C in air for 5 minutes to form an electron transporting layer (ETL). An active layer solution (donor material: acceptor material weight ratio of 1:1~2) was prepared in o-xylene. The donor material includes DO-01~DO-34 materials, and the acceptor material includes at least one of the organic photoelectric compound and the active layer material of the present invention. In order to completely dissolve the active layer material, the active layer solution needs to be stirred at 100°C on a hot plate for at least 3 hours. After the active layer material is completely dissolved, it is filtered with a PTFE filter membrane (pore size 0.45-1.2μm), and the active layer solution is heated for 1 hour. The active layer material is then cooled to room temperature for spin coating, and the coating speed is used to control the film thickness range to around 100-1000nm. Finally, the film formed by the coated active layer material is thermally annealed at 100°C for 5 minutes and then transferred to a thermal evaporator. At 3×10 -6 A thin layer (8 nm) of molybdenum trioxide (MoO3) was deposited as a hole transporting layer (HTL) under a vacuum of 1000 Torr. TM The 2400 source meter instrument records the dark current (J) in the absence of light. dark , bias voltage is 0.5~-6.0V). External quantum efficiency (EQE) uses an external quantum efficiency meter with a measurement range of 300~1100nm (bias voltage is 0~-0.5V), and silicon (300~1100nm) is used for light source calibration. The component heat resistance test is to place the organic optoelectronic component on a 160℃ heating plate for 1 hour, and then return it to room temperature for efficiency measurement.

[0209] It should be noted here that in practical applications, the first electrode preferably has good light transmittance. The first electrode is often made of a transparent conductive material, preferably selected from one of the following conductive material groups: indium oxide, tin oxide, fluorine-doped tin oxide (Fluorine Doped Tin Oxide, FTO), or a composite metal oxide, such as indium tin oxide (Indium Tin Oxide, ITO) and indium zinc oxide (Indium Zinc Oxide, IZO). The material of the second electrode is a conductive metal, preferably silver or aluminum, more preferably silver. Suitable and preferred materials for the electron transport layer include but are not limited to metal oxides, such as ZnO x , aluminum-doped ZnO (AZO), TiO x or nanoparticles thereof, salts (e.g., LiF, NaF, CsF, Cs2CO3), amines (e.g., primary amines, secondary amines, or tertiary amines), conjugated polymer electrolytes (e.g., polyethyleneimine), conjugated polymers (e.g., poly[3-(6-trimethylammoniumhexyl)thiophene], poly(9,9)-bis(2-ethylhexyl-fluorene)-b-poly[3-(6-trimethylammoniumhexyl)thiophene], or poly[(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)], and organic compounds (e.g., tris(8-quinolyl)-aluminum(III) (Alq3), 4,7-diphenyl-1,10-phenanthroline), or combinations of one or more of the above substances. Suitable and preferred materials for the hole transport layer include, but are not limited to, metal oxides, such as ZTO (Zinc Tin Oxide), MoO x , WO x 、NiO x SnO x Or its nanoparticles, containing metal salts, such as copper sulfide, cuprous thiocyanate, copper iodide, copper indium sulfide, lead sulfide, cobalt acetate, tungsten disulfide, etc., conjugated polymer electrolytes, such as PEDOT:PSS, polymer acids, such as polyacrylates, conjugated polymers, such as polytriarylamine (PTAA), insulating polymers, such as Nafion films, polyethyleneimine or polystyrene sulfonate, organic compounds, such as N,N'-diphenyl-N,N'-bis(1-naphthyl)(1,1'-biphenyl)-4,4'-diamine (NPB), N,N'-diphenyl-N,N'-(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), or a combination of one or more of the above materials.

[0210] Please refer to Table 2, which shows the thermal stability test results of organic optoelectronic component embodiments 1 to 4 and comparative example Ref. Among them, the donor material of the organic optoelectronic component is DO-34, and the acceptor materials are organic optoelectronic compounds N14, N15, D01, P01 and Ref. respectively. It should be understood that although the following tests use DO-34 as the donor material, it is not limited to this. This is only an exemplary description, and the aforementioned DO-01 to DO-33 can also have similar test results. In addition, the following tests respectively select N14 and N15 to represent small molecules, D01 to represent dimers, and P01 to represent polymers, but it is not limited to this. This is only an exemplary description, and the aforementioned embodiments can also have similar test results.

[0211] Table 2. Thermal stability test results of organic optoelectronic components Examples 1 to 4 and Comparative Example Ref.

[0212]

[0213] As shown in Table 2, this is the EQE of the tested organic optoelectronic component when it is not heated and after being heated to 160°C for 1 hour. The EQE tested when not heated is taken as 1, and the result of the EQE tested after heating is compared. It can be seen from Table 2 that the EQE of the organic optoelectronic component of the present invention after heating is roughly between ±0.2 and the EQE without heating. Even though the thermal stability of Example 3 is worse than that of Examples 1 to 4, it can still maintain about 70% of the EQE efficiency. In contrast, the comparative example Ref. only has 20% of the EQE efficiency left. The organic optoelectronic component of the present invention has good thermal stability. The thermal stability test in this Table 2 is consistent with the aforementioned Figures 2 to 3 The results of the film surface thermal stability test show that the organic photoelectric compound of formula 1 and the organic photoelectric component using the compound have good thermal stability.

[0214] Based on the above experimental results, the organic photoelectric compound of the present invention has a pyrazine core structure and can be used as a non-fullerene receptor material. Among them, the structure of formula 1 has the following characteristics: 1. It provides an additional conjugated plane for the molecule, strengthens the interaction force between molecules, makes the carrier flow smoother and reduces energy loss. In addition, the arrangement and energy level of the material can be changed by changing the functional group and the structural symmetry, and the asymmetric structure has the effect of reducing energy loss by non-radiation; 2. The added structure can extend the conjugation and increase the structural rigidity to strengthen the thermal stability of the material. In addition, the added heteroaromatic ring can be used to synthesize dimers or trimers to further improve the thermal stability and have the opportunity to extend the material stacking network; 3. After increasing the conjugated plane, the solubility of the material may decrease. The material modified in this way can modify the functional group in a simpler way, and the solubility and clustering mode of the material can be changed without affecting the overall conjugated system too much.

[0215] Through the detailed description of the above specific embodiments, it is hoped that the features and spirit of the present invention can be more clearly described, and the scope of the present invention is not limited by the above disclosed specific embodiments. On the contrary, its purpose is to cover various changes and arrangements with equivalents within the scope of the patent that the present invention hopes to apply for.

Claims

1. An organic photoelectric compound comprising a structure of formula 1: in, R1 is selected from the following groups and one of their derivatives: C1-C30 alkyl, C6-C30 aryl, C3-C30 heteroaryl, C1-C8 haloalkyl, C4-C30 aralkyl, C4-C30 alkoxy and polymer chain; R2 and R1 may be the same or different, and R2 is selected from one of the following groups and their derivatives: C1-C30 alkyl, C6-C30 aryl, C3-C30 heteroaryl, C1-C8 haloalkyl, C4-C30 aralkyl, C4-C30 alkoxy, hydrogen, fluorine, chlorine and bromine; Ar1 and Ar2 may be the same or different and are independently selected from the following groups and their derivatives: C6-C30 carbon chain, C6-C30 cycloalkyl, C6-C30 aryl, C2-C30 heteroaryl, C1-C30 alkoxy and C7-C30 phenolic alkyl; Ar3 to Ar6 may be the same or different and are independently selected from the following groups and their derivatives: C6-C30 aryl, C2-C30 heteroaryl and C2-C8 spiro; Ar7 and Ar8 may be the same or different electron withdrawing groups, which are substituted or unsubstituted polycyclic structures comprising at least one five-membered ring and at least one six-membered ring, substituted or unsubstituted polycyclic structures comprising at least two five-membered rings, or substituted or unsubstituted polycyclic structures comprising at least two six-membered rings; and X is selected from nitrogen, oxygen, sulfur and selenium; Wherein, when X is nitrogen, k≧0, l is an integer from 1 to 10, and m is an integer from 0 to 10; and When X is oxygen, sulfur or selenium, k and l are 0, and m is an integer between 0 and 10.

2. The organic photoelectric compound according to claim 1, wherein When X is nitrogen and R1 is a non-polymer chain, k is an integer of 0 to 2, l is an integer of 1 to 10, and m is an integer of 0 to 10.

3. The organic photoelectric compound according to claim 1, wherein When X is nitrogen and R1 is a polymer chain, k≧0, l is 1, and m is an integer between 0 and 10.

4. The organic photoelectric compound according to claim 1, wherein Ar1 and Ar2 are independently selected from one of the following structures: in, Z comprises halogen; R3 is selected from one of the following groups and their derivatives: C1-C30 straight chain alkyl, C1-C30 branched chain alkyl and C1-C30 alkoxy; and R3' is selected from the following groups and one of their derivatives: C1-C30 straight chain alkyl, C1-C30 branched chain alkyl, C6-C30 aryl, C2-C30 heterocycle, C1-C30 alkoxy and C7-C30 phenolic alkyl.

5. The organic photoelectric compound according to claim 1, wherein Ar3 and Ar4 are independently selected from one of the following structures: in, R4 is selected from the following groups and one of their derivatives: C1-C30 alkyl, C2-C30 heterocycle, C1-C30 alkoxy and C7-C30 phenolic alkyl.

6. The organic photoelectric compound according to claim 1, wherein Ar5 and Ar6 are independently selected from one of the following structures: in, R5 is selected from one of the following groups and their derivatives: C1-C30 alkyl, C6-C30 aryl, C2-C30 heterocycle, C1-C30 alkoxy, C7-C30 phenalkyl, hydrogen, fluorine, and chlorine.

7. The organic optoelectronic compound according to claim 1, wherein the polycyclic structure of Ar7 and Ar8 contains at least one of the following: at least one of the five-membered rings contains at least one of a cyano group and C=O, and at least one of the six-membered rings contains at least one of hydrogen, a halogen, and C=O as substituents.

8. An active layer material, comprising: A receptor material, comprising the organic optoelectronic compound according to claim 1; and A donor material, comprising at least one organic conjugated polymer.

9. The active layer material according to claim 8, wherein the organic conjugated polymer contains at least one of the following structures: in, 0 < x < 1, 0 < y < 1, and x + y = 1; and n is a positive integer greater than 1.

10. An organic optoelectronic device, comprising: A first electrode; An active layer, comprising at least one of the organic optoelectronic compound according to claim 1 and the active layer material according to claim 8; and A second electrode, wherein the active layer is located between the first electrode and the second electrode, and at least one of the first electrode and the second electrode is a transparent or semi-transparent electrode.

11. The organic optoelectronic device according to claim 10, wherein the organic optoelectronic device further comprises a first charge transport layer and a second charge transport layer. The first charge transport layer is disposed between the first electrode and the active layer and is used to transport charges in the first electrode and the active layer; the second charge transport layer is disposed between the active layer and the second electrode and is used to transport charges in the active layer and the second electrode.

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