N-containing hybrid organic compound and application thereof

Abstract

The invention relates to a novel N-containing hybrid organic compound, the organic compound has three phosphoric acid anchoring sites, a plurality of phosphoric acid anchoring sites can effectively enhance the anchoring capability of the organic compound with the surface of an ITO-containing substrate, and meanwhile, the N-containing hybrid organic compound has relatively large steric hindrance, can effectively inhibit excessive aggregation of molecules, and can improve the stability of the organic compound. When the compound is used as a hole transport material to be applied to organic electronic devices, the photoelectric property of the devices can be improved.

Description

Technical Field

[0001] The invention relates to the field of organic semiconductor materials, in particular to an organic compound containing N impurities and applications thereof. Background Art

[0002] Organic photovoltaic cells (OPV) have attracted much attention due to their flexibility, light weight, and ability to print large-area devices. At present, the energy conversion efficiency of OPV single-junction devices has reached 20%, showing its huge application potential. OPV devices adopt a "sandwich" layer-by-layer stacking structure, with a hole transport layer and an electron transport layer on both sides of the active layer to modify the work function of the electrode, reduce the recombination of charges at the interface, and thus improve device performance.

[0003] At present, the most widely used hole transport material is poly (3,4-ethylenedioxythiophene) - polystyrene sulfonic acid (PEDOT:PSS). However, the hydrophilicity and strong acidity of PEDOT:PSS cause a significant decrease in the stability of the device. In addition, PEDOT:PSS has absorption in the near-ultraviolet and near-infrared regions, and the HOMO energy level is relatively high, which limits the short-circuit current density (J SC ) and open circuit voltage (V OC ) enhancement.

[0004] In response to these problems, new self-assembled small molecule organic compound hole transport materials (SAMs) have been successfully developed in recent years. Self-assembled small molecule hole transport materials have the advantages of simple synthesis, low material consumption, adjustable band gap, and green solvent processability, which are of great significance for reducing costs and improving device efficiency. Self-assembled small molecule organic compounds contain anchoring groups (such as phosphoric acid, carboxylic acid, etc.), which can react with the surface hydroxyl groups of the substrate through the anchoring groups, and can further adjust the work function (WF) of the substrate to better align the interface energy level. More importantly, they are able to chemically self-absorb on the substrate surface. These unique advantages, combined with reasonable molecular design, are expected to be industrially applied in organic solar cell devices.

[0005] Currently, the design of self-assembling small molecule materials is mostly based on the research of monophosphate carbazole and its derivatives. This type of self-assembling small molecule materials faces the problem of single material structure and the need to further improve the photoelectric performance of solar cell devices. Therefore, it is necessary to develop new high-performance self-assembling materials to promote the diversified development of self-assembling materials in organic solar devices. Summary of the invention

[0006] The purpose of the present invention is to provide a novel N-containing organic compound, which can be used as a hole transport material in an organic solar cell device, thereby improving the photoelectric performance of the device.

[0007] To achieve the purpose of the present invention, the technical solution is as follows:

[0008] A N-containing miscellaneous organic compound having a structure as shown in the general formula (I):

[0009]

[0010] in,

[0011] -Z-, at each occurrence, is independently selected from a single bond, -CH2-, -O-, or -S-;

[0012] Each occurrence of A is independently selected from the group (A-1) or (A-2):

[0013]

[0014] Each occurrence of L is independently selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a A substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or R a a substituted or unsubstituted heteroaromatic group having 5 to 10 carbon atoms;

[0015] Ar1, Ar2, Ar3 are independently selected from b A substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or R b a substituted or unsubstituted heteroaromatic group having 5 to 20 carbon atoms;

[0016] R a , R b Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, hydroxy, nitro, amino, alkyl having 1-20 carbon atoms, alkoxy having 1-20 carbon atoms, alkylthio having 1-20 carbon atoms, aryl having 6-10 carbon atoms, or heteroaromatic having 5-10 ring atoms, or a group formed by a combination of the foregoing groups;

[0017] * indicates the attachment site.

[0018] Correspondingly, the present invention also provides a hole transport material, wherein the hole transport material is selected from the N-containing miscellaneous organic compounds as described above.

[0019] Correspondingly, the present invention also provides a composition, which comprises at least one N-containing miscellaneous organic compound as described above, and at least one organic solvent.

[0020] Correspondingly, the present invention also provides an organic electronic device, which comprises an anode, a cathode, a photoactive layer located between the anode and the cathode, and a hole transport layer located between the photoactive layer and the anode, wherein the hole transport layer material is selected from the N-containing organic compounds as described above.

[0021] Compared with the prior art, the present invention has the following significant advantages: the present invention provides a novel N-containing organic compound, the organic compound has three phosphate anchoring sites, and the multiple phosphate anchoring sites can effectively enhance the anchoring ability with the surface of the ITO substrate; at the same time, the N-containing organic compound has a large steric hindrance, which can effectively inhibit excessive molecular aggregation, thereby forming an ideal molecular morphology, thereby enhancing the extraction and transmission of holes, and improving the photoelectric performance of the device when used as a hole transport material in an organic electronic device. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 It is a schematic structural diagram of a device embodiment of the present invention. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical solution and advantages of the present application more clear, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described here are only used to explain the present application and are not used to limit the present application.

[0024] In the description of the present invention, it is to be understood that the terms "upper", "lower", "between layers", etc. indicate orientations or positional relationships that are conventionally placed when organic electronic devices are used, or are orientations or positional relationships conventionally understood by those skilled in the art. These are merely for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present invention.

[0025] The terms "and / or", "or / and", and "and / or" used in this article include any one of two or more related listed items, and also include any and all combinations of related listed items, and the arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and / or", "or / and", and "and / or", it should be understood that in this application, the technical solution undoubtedly includes technical solutions that are all connected by "logical and", and undoubtedly includes technical solutions that are all connected by "logical or". For example, "A and / or B" includes three parallel solutions of A, B and A+B. For example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, the technical solution that is all connected by "logical OR"), and also includes any and all combinations of A, B, C, and D, that is, the combination of any two or any three of A, B, C, and D, and also includes the combination of four of A, B, C, and D (that is, the technical solution that is all connected by "logical AND").

[0026] In the present invention, organic photovoltaic device, organic solar cell, OPV and OSC have the same meaning and can be interchangeable.

[0027] In the present invention, photoactive layer and active layer have the same meaning and can be interchanged.

[0028] In the present invention, when a group contains multiple substituents with the same symbol, the substituents may be the same or different from each other. The six Rs on the benzene ring may be the same as or different from each other.

[0029] In the present invention, "substituted" means that one or more hydrogen atoms in a substituted group are replaced by a substituent.

[0030] In the present invention, when the same substituent appears multiple times, it can be independently selected from different groups. If the general formula contains multiple R, then R can be independently selected from different groups.

[0031] In the present invention, the "number of ring atoms" refers to the number of atoms in the atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) formed by atoms bonding to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, the number of ring atoms of a thienyl ring is 5, and the number of ring atoms of a phenanthrene ring is 14.

[0032] "Aryl or aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing a hydrogen atom, which may be a monocyclic aromatic group, a condensed aromatic group, or a polycyclic aromatic group. For polycyclic rings, at least one is an aromatic ring system. Suitable examples include, but are not limited to, phenyl, naphthyl, anthracenyl, phenanthrenyl, and their derivatives.

[0033] "Heteroaryl or heteroaromatic group" means that at least one carbon atom on the basis of an aromatic group is replaced by a non-carbon atom, and the non-carbon atom may be a N atom, an O atom, a S atom, etc. Suitable examples include, but are not limited to, thienyl, furanyl, pyrrolyl, oxadiazolyl, triazolyl, imidazolyl, pyridinyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothiophenyl, benzothiadiazolyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothiphenyl, furopyrrolyl, furanofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, o-naphthyl, phenanthridinyl, primary pyridinyl, quinazolinonyl, dibenzothiophenyl, dibenzofuranyl, carbazolyl, and derivatives thereof.

[0034] In the present invention, "alkyl" may mean a straight chain alkyl, a branched chain alkyl or a cyclic alkyl. The carbon number of the straight chain alkyl may be 1 to 20, 1 to 16, 1 to 10 or 1 to 6; the carbon number of the branched chain alkyl may be 3 to 20, 3 to 16, 3 to 10 or 3 to 6; the carbon number of the cyclic alkyl may be 3 to 20, 3 to 16, 3 to 10 or 3 to 6. Non-limiting examples of alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl , 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3,7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, etc.

[0035] The term "alkoxy" refers to a group with the structure "-O-alkyl", i.e., an alkyl group as defined above is connected to other groups via an oxygen atom. The straight-chain alkoxy group means that the alkyl group in "-O-alkyl" is selected from a straight-chain alkyl group, wherein the carbon atoms of the straight-chain alkyl group may be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the branched-chain alkoxy group means that the alkyl group in "-O-alkyl" is selected from a branched-chain alkyl group, wherein the carbon number of the branched-chain alkyl group may be 3 to 20, 3 to 16, 3 to 10, or 3 to 6; the cyclic alkoxy group means that the alkyl group in "-O-alkyl" is selected from a cyclic alkyl group, wherein the carbon number of the cyclic alkyl group may be 3 to 20, 3 to 16, 3 to 10, or 3 to 6. Suitable examples of phrases containing this term include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, pentoxy, 2-pentoxy, isopentoxy, neopentoxy, hexoxy, 2-hexoxy, 3-hexoxy, 3-methylpentoxy.

[0036] The term "alkylthio" refers to a group having the structure "-S-alkyl", i.e., an alkyl group as defined above connected to another group via a sulfur atom. The straight-chain alkylthio group means that the alkyl group in the "-S-alkyl" is selected from a straight-chain alkyl group, wherein the carbon atoms of the straight-chain alkyl group may be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the branched-chain alkylthio group means that the alkyl group in the "-S-alkyl" is selected from a branched-chain alkyl group, wherein the carbon number of the branched-chain alkyl group may be 3 to 20, 3 to 16, 3 to 10, or 3 to 6; the cyclic alkylthio group means that the alkyl group in the "-S-alkyl" is selected from a cyclic alkyl group, wherein the carbon number of the branched-chain alkyl group may be 3 to 20, 3 to 16, 3 to 10, or 3 to 6. Suitable examples of phrases containing this term include, but are not limited to, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio, pentylthio, 2-pentylthio, isopentylthio, neopentylthio, hexylthio, 2-hexylthio, 3-hexylthio, 3-methylpentylthio.

[0037] In the present invention, the single bond to which the substituent is connected runs through the corresponding ring, indicating that the substituent can be connected to any position of the ring, for example R is connected to any substitutable position of the benzene ring.

[0038] The “combination thereof”, “any combination thereof”, “combination of groups”, “combination” and the like used in the present invention include all suitable combinations of any two or more items in the listed groups.

[0039] In the present invention, “further”, “furthermore”, “particularly”, etc. are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of protection of the present invention.

[0040] In the present invention, "optionally", "optional", and "optional" mean optional, that is, any one of the two parallel solutions of "yes" or "no". If multiple "options" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent.

[0041] In the present invention, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0042] A N-containing miscellaneous organic compound having a structure as shown in the general formula (I):

[0043]

[0044] in:

[0045] -Z-, at each occurrence, is independently selected from a single bond, -CH2-, -O-, or -S-;

[0046] Each occurrence of A is independently selected from the group (A-1) or (A-2):

[0047]

[0048] Each occurrence of L is independently selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a A substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or R a a substituted or unsubstituted heteroaromatic group having 5 to 10 carbon atoms;

[0049] Ar1, Ar2, Ar3 are independently selected from b A substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or R b a substituted or unsubstituted heteroaromatic group having 5 to 20 carbon atoms;

[0050] R a , R b Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, hydroxy, nitro, amino, alkyl having 1-20 carbon atoms, alkoxy having 1-20 carbon atoms, alkylthio having 1-20 carbon atoms, aryl having 6-10 carbon atoms, or heteroaromatic having 5-10 ring atoms, or a group formed by a combination of the foregoing groups;

[0051] * indicates the attachment site.

[0052] Furthermore, the N-containing organic compound of the present invention is selected from any one of the structures shown in general formula (II-1) to (II-4):

[0053]

[0054] In one embodiment, Ar1, Ar2, Ar3 are independently selected from b A substituted or unsubstituted aromatic group having 6 to 14 carbon atoms, or R b A substituted or unsubstituted heteroaromatic group having 5 to 14 carbon atoms.

[0055] Furthermore, Ar1, Ar2, and Ar3 are independently selected from the following groups:

[0056]

[0057] in,

[0058] Each occurrence of X is independently selected from CR1 or N;

[0059] Each occurrence of R1 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, hydroxy, nitro, amino, alkyl having 1-20 carbon atoms, alkoxy having 1-20 carbon atoms, alkylthio having 1-20 carbon atoms, aryl having 6-10 carbon atoms, or heteroaromatic group having 5-10 ring atoms, or a group formed by a combination of the above groups;

[0060] # represents a fusion site, and the fusion site is selected from a C atom. Further, the N-containing miscellaneous organic compound is selected from any structure shown in (III-1)-(III-16):

[0061]

[0062]

[0063] In one embodiment, according to the N-containing miscellaneous organic compound of the present invention, Selected from

[0064] In one embodiment, according to the N-containing miscellaneous organic compound of the present invention, Selected from

[0065] In one embodiment, according to the N-containing miscellaneous organic compound of the present invention, Selected from

[0066] Furthermore, when the Selected from When Selected from , Selected from

[0067] When the Selected from When Selected from Said Selected from

[0068] Further, each occurrence of R1 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, hydroxyl, nitro, amino, alkyl having 1-10 carbon atoms, alkoxy having 3-10 carbon atoms, alkylthio having 1-10 carbon atoms, aryl having 6-10 carbon atoms, or heteroaromatic group having 5-10 ring atoms, or a group formed by a combination of the above groups.

[0069] In a specific embodiment, each occurrence of R1 is independently selected from -H, -D, -F, -CF3, -Cl, -Br, -I, -CN, hydroxyl, nitro, amino, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, cyclohexyl, methoxy, methylthio, phenyl, pyridyl, pyrimidinyl, thienyl, furanyl, or a group formed by a combination of the above groups.

[0070] In one embodiment, each occurrence of L is independently selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkylthio group having 1 to 10 carbon atoms, a Substituted or unsubstituted phenyl, or R a Substituted or unsubstituted biphenyl.

[0071] Preferably, the R a Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, hydroxy, nitro, amino, alkyl having 1-6 carbon atoms, alkoxy having 1-6 carbon atoms, alkylthio having 1-6 carbon atoms, aryl having 6-10 carbon atoms, or a heteroaromatic group having 5-10 ring atoms, or a group formed by a combination of the above groups.

[0072] Further, each occurrence of L is independently selected from -(CH2)-, -(CH2)-(CH2)-, -(CH2)-(CH2)-(CH2)-, -(CH2)-(CH2)-(CH2)-(CH2)-, -(CH2)-(CH2)-(CH2)-(CH2)-, -(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-, -(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-, -(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-, -(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-, -(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)- CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-、-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-、-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-, phenyl, pyridyl, pyrimidinyl, triazine, thienyl, furanyl, benzothiadiazolyl, biphenyl, thiophenebiphenyl, thiophenebithiphenyl, or a group formed by a combination of the above groups.

[0073] In a specific embodiment, according to the N-containing organic compound as described above, the *-LA is selected from any of the following groups:

[0074]

[0075] Wherein: n is selected from 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0076] Furthermore, each occurrence of *-LA in the general formula (I) is selected from the same group.

[0077] Furthermore, the N-containing organic compound provided by the present invention is selected from the following structures but not limited thereto:

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084] The present invention also relates to a hole transport material, wherein the hole transport material is selected from the N-containing organic compounds as described above.

[0085] The present invention further relates to a composition comprising at least one N-containing organic compound as described above, and at least one organic solvent.

[0086] In one embodiment, the organic solvent is selected from one or more of alcohols or DMF; preferably, the organic solvent is selected from one or more of methanol, ethanol, isopropanol, ethylene glycol, DMF, etc.; more preferably, the organic solvent is selected from one or more of methanol, ethanol or DMF.

[0087] Correspondingly, the present invention also relates to an organic electronic device, which comprises an anode, a cathode, a photoactive layer located between the anode and the cathode, and a hole transport layer located between the photoactive layer and the anode, wherein the hole transport layer material is selected from the N-containing organic compounds as described above.

[0088] Furthermore, the organic electronic device further comprises an electron transport layer, and the electron transport layer is located between the cathode and the photoactive layer.

[0089] It should be noted that, in order to improve the performance of the organic electronic device, the organic electronic device may further include other functional layers, including but not limited to charge injection layers and / or charge blocking layers, and the charges include holes and electrons.

[0090] Preferably, the organic electronic device is an organic solar cell or a perovskite solar cell.

[0091] In a specific embodiment, the organic electronic device is an organic solar cell.

[0092] Furthermore, the organic solar cell comprises an anode, a hole transport layer, a photoactive layer, an electron transport layer and a cathode stacked in sequence from bottom to top, and the hole transport layer material is selected from the N-containing organic compounds described above.

[0093] Furthermore, the anode layer is preferably selected from metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), and the like.

[0094] Further, the photoactive layer material comprises a photoactive layer donor material and a photoactive layer acceptor material; preferably, the photoactive layer acceptor material can be selected from a non-fullerene acceptor material or a fullerene derivative acceptor material, and the non-fullerene acceptor material can be selected from an acceptor material based on a Y6 skeleton, such as Y6, BTP-4Cl-8, L8-BO, BO-4Cl, N3, BTP-eC9 and its derivatives; or a non-condensed ring small molecule acceptor material, or a dimer, trimer or polymer based on a Y6 skeleton, but not limited thereto; the fullerene derivative acceptor material is selected from a C60 derivative or a C70 derivative, and the fullerene derivative acceptor material includes but is not limited to: PC61BM ([6,6]-phenyl C61 butyric acid methyl ester), PC71BM ([6,6]-phenyl C71 butyric acid methyl ester), indene-containing fullerene, etc. The photoactive layer donor material is selected from polymer donor materials, including but not limited to: one or more of PBDB-T, PM6, PM7, D18, D18-Cl, PTO2, PB2, PB2F, PTVT-BT, PTQ10, PTQ11, PBQx-TCl, PQM-Cl, or small molecule donor materials.

[0095] Furthermore, the material of the electron transport layer can be selected from metal complexes, metal oxides, metal salts, etc. with low work function, such as metal complexes of 8-hydroxyquinoline, complexes containing Alq3, metal complexes containing Liq, LiF, Ca, titanium oxide (TiO x ), zinc oxide (ZnO), cesium carbonate (Cs2CO3), etc.; it can also be a polymer material, such as PFN-Br or PFN or PDINN or PDINO or PNDIT-F3N-Br or PNDIT-F3N, etc., but not limited to this.

[0096] The cathode material can be selected from metals, such as vanadium (V), chromium (Cr), zinc (Zn), silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), palladium (Pd), or alloys of the above metals; conductive nanomaterials, such as metal nanowires, nanoparticle slurries, graphene, carbon nanotubes, etc.; combinations of metals and oxides, such as ZnO:Al or SnO2:Sb, etc.; and conductive polymers, such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole and polyaniline, etc.; or materials with a multilayer structure, such as LiF / Al, LiO2 / Al, LiF / Fe, MoO3 / Al, Al:Li, Al:BaF2 and Al:BaF2:Ba, etc., but are not limited to these.

[0097] Further, the organic electronic device (including organic solar cells and perovskite solar cells) of the present invention also includes a substrate, and the substrate uses a substrate with excellent transparency, surface smoothness, ease of operation and waterproofness. Specifically, a glass substrate, a thin film glass substrate or a transparent plastic substrate can be used. The plastic substrate may include a film in a single or multilayer form, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK) and polyimide (PI), but is not limited thereto.

[0098] The present invention also relates to the application of the above-mentioned organic electronic devices in various equipment, including, but not limited to, automobiles and building integrated photovoltaics (BIPV), electronic price tags, indoor photovoltaics, the Internet of Things, smart agriculture, etc.

[0099] Compound Synthesis Examples

[0100] Synthesis Example 1: Synthesis of (SAM-1)

[0101]

[0102] Synthesis of compound 1-2: accurately weigh compound 1-1 (11.48 g, 20 mmol) and add it to a 500 mL three-necked flask, add 1,4-dibromobutane (19.4 g, 90 mmol) to the 500 mL three-necked flask in turn, add about 100 mL of NaOH aqueous solution (50%), 100 mL of dioxane, and tetrabutylammonium bromide (1.6 g, 5 mmol), replace nitrogen three times, heat to 70 ° C and react for 4 hours, cool to room temperature after the raw materials react completely, add water to quench, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent, mix with silica gel column chromatography, eluent is PE:EA=5:1 (volume ratio), and obtain about 14.2 g of compound 1-2, yield: 72.8%. MALDI-TOF-MS: 978.54.

[0103] Synthesis of compound 1-3: Accurately weigh compound 1-2 (13.6 g, 14 mmol) and add it to a 250 mL three-necked flask, add 150 mL of triethyl phosphite, replace nitrogen three times, heat to 160 ° C and react for 4 hours. Cool to room temperature and remove excess solvent by vacuum distillation. The crude product is purified by column chromatography (PE: EA == 1: 1 (volume ratio)) to obtain about 14.3 g of compound 1-3, yield: 88.9%. MALDI-TOF-MS: = 1150.98.

[0104] Synthesis of compound (SAM-1): Accurately weigh compound 1-3 (11.50 g, 10 mmol) and add it to a 250 mL three-necked flask, dissolve it with 100 mL of dichloromethane, replace nitrogen three times, and add trimethylsilyl bromide (45.9 g, 300 mmol) under nitrogen protection. React at room temperature for 12 hours, and add 30 mL of methanol. Remove the solvent by vacuum distillation, then add methanol and water to precipitate the solid, filter it, and beat the filter cake with ethyl acetate to obtain about 7.43 g of compound (SAM-1), with a yield of 75.8%, and MALDI-TOF-MS: 981.67.

[0105] Synthesis Example 2: Synthesis of (SAM-2)

[0106]

[0107] Synthesis of compound 2-3: Accurately weigh compound 2-1 (45.30 g, 150 mmol), compound 2-2 (22.80 g, 50 mmol), potassium carbonate (41.40 g, 300 mmol), tetrakis(triphenylphosphine)palladium (1.73 g, 1.5 mmol) and add them to a 1000 mL three-necked flask in sequence, add 500 mL tetrahydrofuran and 250 mL water, replace nitrogen three times and heat to reflux, react for 16 hours. Cool to room temperature, wash with water, extract with ethyl acetate, and remove excess solvent from the organic phase by reduced pressure distillation. The crude product is purified by column chromatography (PE: DCM = 7: 1 (volume ratio)) to obtain about 23.63 g of compound 2-3, yield: 63.8%. MS: 741.57.

[0108] Synthesis of compound 2-4: accurately weigh compound 2-3 (14.84 g, 20 mmol) and add it to a 500 mL three-necked flask, add 1,4-dibromobutane (19.4 g, 90 mmol) to the 500 mL three-necked flask in turn, add about 100 mL of NaOH aqueous solution (50%), 100 mL of dioxane, and tetrabutylammonium bromide (1.6 g, 5 mmol), replace nitrogen three times, and heat to 70 ° C for 4 hours. After the raw materials react completely, cool to room temperature, add water to quench, and extract with ethyl acetate. Combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent. Silica gel mixed sample column chromatography, eluent PE: EA = 5: 1 (volume ratio), to obtain about 20.3 g of compound 2-4, yield: 88.7%. MALDI-TOF-MS: 1146.25.

[0109] Synthesis of compound 2-5: Accurately weigh compound 2-4 (16 g, 14 mmol) and add it to a 250 mL three-necked flask, add 150 mL of triethyl phosphite, replace nitrogen three times, heat to 160 ° C and react for 4 hours. Cool to room temperature and remove excess solvent by vacuum distillation. The crude product is purified by column chromatography (PE: EA = 5: 1 (volume ratio)) to obtain about 16.7 g of compound 2-5, yield: 90.7%. MALDI-TOF-MS: 1318.41.

[0110] Synthesis of compound (SAM-2): Accurately weigh compound 2-5 (13.19 g, 10 mmol) and add it to a 250 mL three-necked flask, dissolve it with 100 mL of dichloromethane, replace nitrogen three times, and add trimethylsilyl bromide (45.9 g, 300 mmol) under nitrogen protection. React at room temperature for 12 hours, and add 30 mL of methanol. Remove the solvent by vacuum distillation, then add methanol and water to precipitate the solid, filter it, and beat the filter cake with ethyl acetate to obtain about 6.16 g of compound (SAM-2), with a yield of 53.6%, MALDI-TOF-MS: 1149.70.

[0111] Synthesis Example 3: Synthesis of (SAM-3)

[0112]

[0113] Synthesis of compound 3-2: Accurately weigh compound 3-1 (55.8 g, 150 mmol), compound 2-2 (22.80 g, 50 mmol), cesium carbonate (97.50 g, 300 mmol), palladium acetate (0.34 g, 1.5 mmol) and add them to a 1000 mL three-necked flask in turn, add 300 mL acetonitrile and 300 mL methanol, replace nitrogen three times and heat to reflux, react for 12 hours. Cool to room temperature, remove the solvent by vacuum distillation, add water and EA to extract and separate the liquid, and concentrate and dry the organic phase. The crude product is purified by column chromatography (PE: EA = 20: 1 (volume ratio)) to obtain about 23.74 g of compound 3-2, yield: 58.6%. MS: 809.84.

[0114] Synthesis of compound 3-3: accurately weigh compound 3-2 (16.20 g, 20 mmol) and add it to a 500 mL three-necked flask, add 1,4-dibromobutane (19.4 g, 90 mmol) to a 500 mL three-necked flask, add about 100 mL of NaOH aqueous solution (50%), 100 mL of dioxane, and tetrabutylammonium bromide (1.6 g, 5 mmol), replace nitrogen three times, and heat to 70 ° C for 4 hours. After the raw materials react completely, cool to room temperature, add water to quench, and extract with ethyl acetate. Combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Silica gel mixed sample column chromatography, eluent PE: EA = 5: 1 (volume ratio). Get about 18.7 g of compound 3-3, yield: 76.9%. MALDI-TOF-MS: 1215.85.

[0115] Synthesis of compound 3-4: Accurately weigh compound 3-3 (17 g, 14 mmol) and add it to a 250 mL three-necked flask, add 150 mL of triethyl phosphite, replace nitrogen three times, heat to 160 ° C and react for 4 hours. Cool to room temperature and remove excess solvent by vacuum distillation. The crude product is purified by column chromatography (PE: EA = 2: 1 (volume ratio)) to obtain about 15.8 g of compound 3-4, yield: 81.7%. MALDI-TOF-MS: 1386.57.

[0116] Synthesis of compound (SAM-3): Accurately weigh compound 3-4 (13.87 g, 10 mmol) and add it to a 250 mL three-necked flask, dissolve it with 100 mL of dichloromethane, replace nitrogen three times, and add trimethylsilyl bromide (45.9 g, 300 mmol) under nitrogen protection. React at room temperature for 12 hours, and add 30 mL of methanol. Remove the solvent by vacuum distillation, then add methanol and water to precipitate the solid, filter it, and beat the filter cake with ethyl acetate to obtain about 9.95 g of compound (SAM-3), yield: 81.6%, MALDI-TOF-MS: 1218.33.

[0117] Synthesis Example 4: Synthesis of (SAM-5)

[0118]

[0119] Synthesis of compound 4-2: Accurately weigh compound 4-1 (36.92g, 150mmol), compound 2-2 (22.80g, 50mmol), potassium carbonate (41.40g, 300mmol), tetrakis(triphenylphosphine)palladium (1.73g, 1.5mmol) and add them to a 1000mL three-necked flask in sequence, add 500mL tetrahydrofuran and 250mL water, replace nitrogen three times and heat to reflux, react for 16h. Cool to room temperature, wash with water, extract with ethyl acetate, and remove excess solvent from the organic phase by reduced pressure distillation. The crude product is purified by column chromatography (PE:DCM=10:1 (volume ratio)) to obtain about 22.60g of compound 4-2, yield: 78.8%. MS: 574.18.

[0120] Synthesis of compound 4-3: accurately weigh compound 4-2 (11.48 g, 20 mmol) and add it to a 500 mL three-necked flask, add 1,4-dibromobutane (19.4 g, 90 mmol) to the 500 mL three-necked flask in turn, add about 100 mL of NaOH aqueous solution (50%), 100 mL of dioxane, and tetrabutylammonium bromide (1.6 g, 5 mmol), replace nitrogen three times, heat to 70 ° C and react for 4 hours, cool to room temperature after the raw materials react completely, add water to quench, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent, mix with silica gel and column chromatography, eluent is PE:EA=5:1 (volume ratio) to obtain about 16.7 g of compound 4-3, yield: 85.7%. MS: 979.25.

[0121] Synthesis of compound 4-4: Accurately weigh compound 4-3 (13.7 g, 14 mmol) and add it to a 250 mL three-necked flask, add 150 mL of triethyl phosphite, replace nitrogen three times, heat to 160 ° C and react for 4 hours. Cool to room temperature and remove excess solvent by vacuum distillation. The crude product is purified by column chromatography (PE: EA = 2: 1 (volume ratio)) to obtain about 11.8 g of compound 4-4, yield: 73.9%. MALDI-TOF-MS: 1150.74.

[0122] Synthesis of compound (SAM-5): Accurately weigh compound 4-4 (11.51 g, 10 mmol) and add it to a 250 mL three-necked flask, dissolve it with 100 mL of dichloromethane, replace nitrogen three times, and add trimethylsilyl bromide (45.9 g, 300 mmol) under nitrogen protection. React at room temperature for 12 hours, and add 30 mL of methanol. Remove the solvent by vacuum distillation, then add methanol and water to precipitate the solid, filter it, and beat the filter cake with ethyl acetate to obtain about 8.62 g of compound (SAM-5), with a yield of 87.8%, and MALDI-TOF-MS: 981.50.

[0123] Synthesis Example 5: Synthesis of (SAM-12)

[0124]

[0125] Synthesis of compound 5-2: Accurately weigh compound 5-1 (41.40 g, 150 mmol), compound 2-2 (22.80 g, 50 mmol), potassium carbonate (41.40 g, 300 mmol), tetrakis(triphenylphosphine)palladium (1.73 g, 1.5 mmol) and add them to a 1000 mL three-necked flask in sequence, add 500 mL tetrahydrofuran and 250 mL water, replace nitrogen three times and then heat to reflux and react for 16 hours. Cool to room temperature, wash with water, extract with ethyl acetate, and remove excess solvent from the organic phase by reduced pressure distillation. The crude product is purified by column chromatography (PE: EA = 30: 1 (volume ratio)) to obtain about 25.15 g of compound 5-2, with a yield of 75.8%. MS: 664.12.

[0126] Synthesis of compound 5-4: Accurately weigh compound 5-2 (13.28 g, 20 mmol) and 5-3 (29.40 g, 120 mmol), add to a 500 mL three-necked flask, add 120 mL of dimethyl sulfoxide to dissolve, blow nitrogen, add sodium hydride (2.88 g, 120 mmol) in batches, heat to 70 ° C and react for 12 hours. Cool to room temperature, acidify with 1M hydrochloric acid, extract with ethyl acetate, wash with water, and remove excess solvent from the organic phase by reduced pressure distillation. The crude product is purified by column chromatography (PE: EA = 15: 1 (volume ratio)) to obtain about 17.03 g of compound 5-4, yield: 73.6%. MALDI-TOF-MS: 1155.88.

[0127] Synthesis of compound (SAM-12): Accurately weigh compound 5-4 (11.56 g, 10 mmol) and add it to a 250 mL three-necked flask, dissolve it with 100 mL of dichloromethane, replace nitrogen three times, and add trimethylsilyl bromide (45.9 g, 300 mmol) under nitrogen protection. React at room temperature for 12 hours, and add 30 mL of methanol. Remove the solvent by vacuum distillation, then add methanol and water to precipitate the solid, filter it, and beat the filter cake with ethyl acetate to obtain about 5.06 g of compound (SAM-12), with a yield of 51.2%, and MALDI-TOF-MS: 987.62.

[0128] Synthesis Example 6: Synthesis of (SAM-22)

[0129]

[0130] Synthesis of compound 6-2: Accurately weigh compound 1-1 (28.68g, 50mmol), compound 6-1 (27.75g, 150mmol), sodium tert-butoxide (28.8g, 300mmol), (dibenzylideneacetone) palladium (0.85g, 1.5mmol), Xantphos (1.73g, 3mmol) and add them to a 1000mL three-necked flask in sequence, add 600mL toluene, replace nitrogen three times, then heat to reflux and react for 12h. Cool to room temperature, wash with water, extract with ethyl acetate, and remove excess solvent from the organic phase by reduced pressure distillation. The crude product is purified by column chromatography (PE: EA = 20: 1 (volume ratio)) to obtain about 33.52g of compound 6-2, with a yield of 75.7%. MS: 885.42.

[0131] Synthesis of compound 6-4: Accurately weigh compound 6-2 (17.72g, 20mmol), compound 6-3 (15.94g, 90mmol), add 200ml toluene, 15ml piperidine in a 500mL three-necked flask, replace nitrogen three times and heat to 110℃ for 12h. After cooling to room temperature, remove the organic solvent by rotary evaporation, dissolve the remaining product in dichloromethane, wash with water, collect the organic phase and dry it with anhydrous sodium sulfate. Remove the excess solvent by vacuum distillation. The crude product is purified by column chromatography (PE:DCM=1:1 (volume ratio)) to obtain about 17.23g of compound 6-4, with a yield of 63.2%. MALDI-TOF-MS: 1362.87.

[0132] Synthesis of compound (SAM-22): Accurately weigh compound 6-4 (13.63 g, 10 mmol) and add it to a 250 mL three-necked flask, dissolve it with 100 mL of dichloromethane, replace nitrogen three times, and add trimethylsilyl bromide (45.9 g, 300 mmol) under nitrogen protection. React at room temperature for 12 hours, and add 30 mL of methanol. Remove the solvent by vacuum distillation, then add methanol and water to precipitate the solid, filter it, and beat the filter cake with ethyl acetate to obtain about 7.86 g of compound (SAM-22), with a yield of 65.8%, and MALDI-TOF-MS: 1195.35.

[0133] Synthesis Example 7: Synthesis of (SAM-25)

[0134]

[0135] Synthesis of compound 7-2: Accurately weigh compound 7-1 (37.07g, 150mmol), compound 2-2 (22.80g, 50mmol), potassium carbonate (41.40g, 300mmol), tetrakis(triphenylphosphine)palladium (1.73g, 1.5mmol) and add them to a 1000mL three-necked flask in sequence, add 500mL tetrahydrofuran and 250mL water, replace nitrogen three times and then heat to reflux and react for 16h. Cool to room temperature, wash with water, extract with ethyl acetate, and remove excess solvent from the organic phase by reduced pressure distillation. The crude product is purified by column chromatography (PE:EA=15:1 (volume ratio)) to obtain about 25.02g of compound 7-2, with a yield of 86.8%. MS: 576.24.

[0136] Synthesis of compound 7-4: Accurately weigh compound 7-2 (23.05g, 40mmol), compound 7-3 (28.31g, 120mmol), sodium tert-butoxide (23.04g, 240mmol), (dibenzylideneacetone) palladium (0.68g, 1.2mmol), Xantphos (1.38g, 2.4mmol) and add them to a 500mL three-necked flask in sequence, add 250mL toluene, replace nitrogen three times, and then heat to 80°C and react for 12h. Cool to room temperature, wash with water, and then extract with ethyl acetate. The organic phase is distilled under reduced pressure to remove excess solvent. The crude product is purified by column chromatography (PE: DCM = 20: 1 (volume ratio)) to obtain about 27.45g of compound 7-4, with a yield of 65.9%. MS: 1041.19.

[0137] Synthesis of compound 7-5: Accurately weigh compound 7-4 (26g, 25mmol) and 780mL triethyl phosphite into a 1000mL three-necked flask, replace nitrogen three times, add palladium acetate (0.19g, 0.75mol), DPPF (0.83g, 1.5mmol), then heat to 160°C and react for 12h. Cool to room temperature and remove excess solvent by vacuum distillation. The crude product is purified by column chromatography (PE: EA = 5: 1 (volume ratio)) to obtain about 22.07g of compound 7-5, with a yield of 72.7%. MALDI-TOF-MS: 1213.67.

[0138] Synthesis of compound (SMA-25): Accurately weigh compound 7-5 (12.14 g, 10 mmol) and add it to a 250 mL three-necked flask, dissolve it with 100 mL of dichloromethane, replace nitrogen three times, and add trimethylsilyl bromide (45.9 g, 300 mmol) under nitrogen protection. React at room temperature for 12 hours, and add 30 mL of methanol. Remove the solvent by vacuum distillation, then add methanol and water to precipitate the solid, filter it, and beat the filter cake with ethyl acetate to obtain about 8.25 g of compound (SAM-25), with a yield of 78.9%, MALDI-TOF-MS: 1045.08.

[0139] Synthesis Example 8: Synthesis of (SAM-34)

[0140]

[0141] Synthesis of compound 8-2: Accurately weigh compound 8-1 (44.43 g, 150 mmol), compound 2-2 (22.80 g, 50 mmol), potassium carbonate (41.40 g, 300 mmol), tetrakis(triphenylphosphine)palladium (1.73 g, 1.5 mmol) and add them to a 1000 mL three-necked flask in sequence, add 500 mL tetrahydrofuran and 250 mL water, replace nitrogen three times and heat to reflux, react for 16 hours. Cool to room temperature, wash with water, extract with ethyl acetate, and remove excess solvent from the organic phase by reduced pressure distillation. The crude product is purified by column chromatography (PE: DCM = 7: 1 (volume ratio)) to obtain about 27.82 g of compound 8-2, yield: 76.9%. MS: 723.25.

[0142] Synthesis of compound 8-3: accurately weigh compound 8-2 (14.48 g, 20 mmol) and add it to a 500 mL three-necked flask, add 1,4-dibromobutane (19.4 g, 90 mmol) to the 500 mL three-necked flask in turn, add about 100 mL of NaOH aqueous solution (50%), 100 mL of dioxane, and tetrabutylammonium bromide (1.6 g, 5 mmol), replace nitrogen three times, and heat to 70 ° C for 4 hours. After the raw materials react completely, cool to room temperature, add water to quench, and extract with ethyl acetate. Combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent. Silica gel mixed sample column chromatography, eluent PE: EA = 5: 1 (volume ratio) to obtain about 20 g of compound 8-3, yield: 88.9%. MALDI-TOF-MS: 1128.64.

[0143] Synthesis of compound 8-4: Accurately weigh compound 8-3 (15.7 g, 14 mmol) and add it to a 250 mL three-necked flask, add 150 mL of triethyl phosphite, replace nitrogen three times, heat to 160 ° C and react for 4 hours. Cool to room temperature and remove excess solvent by vacuum distillation. The crude product is purified by column chromatography (PE: EA = 1: 1 (volume ratio)) to obtain about 15.4 g of compound 8-4, yield: 84.9%. MALDI-TOF-MS: 1300.81.

[0144] Synthesis of compound (SAM-34): Accurately weigh compound 8-4 (13.0 g, 10 mmol) and add it to a 250 mL three-necked flask, dissolve it with 100 mL of dichloromethane, replace nitrogen three times, and add trimethylsilyl bromide (45.9 g, 300 mmol) under nitrogen protection. React at room temperature for 12 hours, and add 30 mL of methanol. Remove the solvent by vacuum distillation, then add methanol and water to precipitate the solid, filter it, and slurry the filter cake with ethyl acetate to obtain about 9.51 g of compound (SAM-34), with a yield of 84.1%, and MALDI-TOF-MS: 1131.58.

[0145] Synthesis Example 9: Synthesis of (SAM-37)

[0146]

[0147] Synthesis of compound 9-2: Accurately weigh compound 9-1 (44.42 g, 150 mmol), compound 2-2 (22.80 g, 50 mmol), potassium carbonate (41.40 g, 300 mmol), tetrakis(triphenylphosphine)palladium (1.73 g, 1.5 mmol) and add them to a 1000 mL three-necked flask in sequence, add 500 mL tetrahydrofuran and 250 mL water, replace nitrogen three times and heat to reflux, react for 16 hours. Cool to room temperature, wash with water, extract with ethyl acetate, and remove excess solvent from the organic phase by reduced pressure distillation. The crude product is purified by column chromatography (PE: DCM = 5: 1 (volume ratio)) to obtain about 29.96 g of compound 9-2, with a yield of 82.8%. MS: 723.65.

[0148] Synthesis of compound 9-3: accurately weigh compound 9-2 (14.48 g, 20 mmol) and add it to a 500 mL three-necked flask, add 1,4-dibromobutane (19.4 g, 90 mmol) to the 500 mL three-necked flask in turn, add about 100 mL of NaOH aqueous solution (50%), 100 mL of dioxane, and tetrabutylammonium bromide (1.6 g, 5 mmol), replace nitrogen three times, and heat to 70 ° C for 4 hours. After the raw materials react completely, cool to room temperature, add water to quench, and extract with ethyl acetate. Combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Mix the sample with silica gel and perform column chromatography. The eluent is PE:EA=5:1 (volume ratio) to obtain about 18.2 g of compound 9-3, with a yield of 81.1%. MALDI-TOF-MS: 1128.26.

[0149] Synthesis of compound 9-4: Accurately weigh compound 9-3 (15.8 g, 14 mmol) and add it to a 250 mL three-necked flask, add 150 mL of triethyl phosphite, replace nitrogen three times, heat to 160 ° C and react for 4 hours. Cool to room temperature and remove excess solvent by vacuum distillation. The crude product is purified by column chromatography (PE: EA = 1: 1 (volume ratio)) to obtain about 15 g of compound 9-4, yield: 82.8%. MALDI-TOF-MS: 1300.07.

[0150] Synthesis of compound (SAM-37): Accurately weigh compound 9-4 (13.0 g, 10 mmol) and add it to a 250 mL three-necked flask, dissolve it with 100 mL of dichloromethane, replace nitrogen three times, and add trimethylsilyl bromide (45.9 g, 300 mmol) under nitrogen protection. React at room temperature for 12 hours, and add 30 mL of methanol. Remove the solvent by vacuum distillation, then add methanol and water to precipitate the solid, filter it, and beat the filter cake with ethyl acetate to obtain about 8.0 g of compound (SAM-37), yield: 70.7%, MALDI-TOF-MS: 1131.52.

[0151] Synthesis Example 10: Synthesis of (SAM-45)

[0152]

[0153] Synthesis of compound 10-2: Accurately weigh compound 10-1 (56.25g, 150mmol), compound 2-2 (22.80g, 50mmol), potassium carbonate (41.40g, 300mmol), tetrakis(triphenylphosphine)palladium (1.73g, 1.5mmol) and add them to a 1000mL three-necked flask in sequence, add 500mL tetrahydrofuran and 250mL water, replace nitrogen three times and then heat to reflux and react for 16h. Cool to room temperature, wash with water, extract with ethyl acetate, and remove excess solvent from the organic phase by reduced pressure distillation. The crude product is purified by column chromatography (PE:DCM=5:1 (volume ratio)) to obtain about 23.49g of compound 10-2, with a yield of 48.9%. MS: 961.45.

[0154] Synthesis of compound 10-3: accurately weigh compound 10-2 (19.22 g, 20 mmol) and add it to a 500 mL three-necked flask, add 1,4-dibromobutane (19.4 g, 90 mmol) to the 500 mL three-necked flask in turn, add about 100 mL of NaOH aqueous solution (50%), 100 mL of dioxane, and tetrabutylammonium bromide (1.6 g, 5 mmol), replace nitrogen three times, and heat to 70 ° C for 4 hours. After the raw materials react completely, cool to room temperature, add water to quench, and extract with ethyl acetate. Combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Mix the sample with silica gel and perform column chromatography. The eluent is PE:EA=5:1 (volume ratio) to obtain about 23.2 g of compound 10-3, with a yield of 85.4%. MALDI-TOF-MS: 1364.94.

[0155] Synthesis of compound 10-4: Accurately weigh compound 10-3 (19 g, 14 mmol) and add it to a 250 mL three-necked flask, add 150 mL of triethyl phosphite, replace nitrogen three times, heat to 160 ° C and react for 4 hours. Cool to room temperature and remove excess solvent by vacuum distillation. The crude product is purified by column chromatography (PE: EA = 1: 1 (volume ratio)) to obtain about 15.8 g of compound 10-4, yield: 73.8%. MALDI-TOF-MS: 1536.73.

[0156] Synthesis of compound (SAM-45): Accurately weigh compound 10-4 (15.37 g, 10 mmol) and add it to a 250 mL three-necked flask, dissolve it with 100 mL of dichloromethane, replace nitrogen three times, and add trimethylsilyl bromide (45.9 g, 300 mmol) under nitrogen protection. React at room temperature for 12 hours, and add 30 mL of methanol. Remove the solvent by vacuum distillation, then add methanol and water to precipitate the solid, filter it, and beat the filter cake with ethyl acetate to obtain about 7.36 g of compound (SAM-45), with a yield of 53.8%, and MALDI-TOF-MS: 1368.46.

[0157] Synthesis Example 11: Synthesis of (SAM-46)

[0158]

[0159] Synthesis of compound 11-3: Accurately weigh compound 11-1 (60.6 g, 300 mmol), compound 11-2 (98.4 g, 300 mmol), potassium carbonate (82.80 g, 600 mmol), palladium acetate (0.68 g, 3 mmol), triphenylphosphine (1.57 g, 6 mmol) and add them to a 5000 mL three-necked flask in sequence, add 1000 mL acetonitrile and 1000 mL methanol, replace nitrogen three times and then heat to reflux and react for 16 hours. Cool to room temperature, wash with water, extract with ethyl acetate, and remove excess solvent from the organic phase by reduced pressure distillation. The crude product is purified by column chromatography (PE: EA = 5: 1 (volume ratio)) to obtain about 81.44 g of compound 11-3, with a yield of 75.7%. MS: 358.81.

[0160] Synthesis of compound 11-4: Accurately weigh compound 11-3 (71.7 g, 200 mmol) and triethyl phosphite (99.6 g, 600 mmol) and add them to a 1000 mL three-necked flask in sequence, add 700 mL of o-dichlorobenzene, replace nitrogen three times, and heat to 150 ° C. React for 16 hours. Cool to room temperature, and remove excess solvent from the organic phase by vacuum distillation. The crude product is purified by column chromatography (PE: EA = 3: 1 (volume ratio)) to obtain about 53.17 g of compound 11-4, with a yield of 81.4%. MS: 326.65.

[0161] Synthesis of compound 11-5: Accurately weigh compound 11-4 (48.93 g, 150 mmol), compound 2-2 (22.80 g, 50 mmol), potassium carbonate (41.40 g, 300 mmol), tetrakis(triphenylphosphine)palladium (1.73 g, 1.5 mmol) and add them to a 1000 mL three-necked flask in sequence, add 500 mL tetrahydrofuran and 250 mL water, replace nitrogen three times and heat to reflux, react for 16 hours. Cool to room temperature, wash with water, extract with ethyl acetate, and remove excess solvent from the organic phase by reduced pressure distillation. The crude product is purified by column chromatography (PE: DCM = 3: 1 (volume ratio)) to obtain about 27.75 g of compound 11-5, yield: 68.2%. MS: 813.49.

[0162] Synthesis of compound 11-6: accurately weigh compound 11-5 (16.28 g, 20 mmol) and add it to a 500 mL three-necked flask, add 1,4-dibromobutane (19.4 g, 90 mmol) to the 500 mL three-necked flask in turn, add about 100 mL of NaOH aqueous solution (50%), 100 mL of dioxane, and tetrabutylammonium bromide (1.6 g, 5 mmol), replace nitrogen three times, and heat to 70 ° C for 4 hours. After the raw materials react completely, cool to room temperature, add water to quench, and extract with ethyl acetate. Combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent. Silica gel mixed sample column chromatography, eluent PE: EA = 5: 1 (volume ratio) to obtain about 17.2 g of compound 11-6, yield: 70.9%. MALDI-TOF-MS: 1219.29.

[0163] Synthesis of compound 11-7: Accurately weigh compound 11-6 (17 g, 14 mmol) and add it to a 250 mL three-necked flask, add 150 mL of triethyl phosphite, replace nitrogen three times, heat to 160 ° C and react for 4 hours. Cool to room temperature and remove excess solvent by vacuum distillation. The crude product is purified by column chromatography (PE: DCM = 2: 1 (volume ratio)) to obtain about 16 g of compound 11-7, yield: 82.7%. MALDI-TOF-MS: 1390.87.

[0164] Synthesis of compound (SAM-46): Accurately weigh compound 11-7 (13.91 g, 10 mmol) and add it to a 250 mL three-necked flask, dissolve it with 100 mL of dichloromethane, replace nitrogen three times, and add trimethylsilyl bromide (45.9 g, 300 mmol) under nitrogen protection. React at room temperature for 12 hours, and add 30 mL of methanol. Remove the solvent by vacuum distillation, then add methanol and water to precipitate the solid, filter it, and beat the filter cake with ethyl acetate to obtain about 7.12 g of compound (SAM-46), with a yield of 58.2%, MALDI-TOF-MS: 1222.80.

[0165] Synthesis Example 12: Synthesis of (SAM-50)

[0166]

[0167] Synthesis of compound 12-2: Accurately weigh compound 12-1 (44.43 g, 150 mmol), compound 2-2 (22.80 g, 50 mmol), potassium carbonate (41.40 g, 300 mmol), tetrakis(triphenylphosphine)palladium (1.73 g, 1.5 mmol) and add them to a 1000 mL three-necked flask in sequence, add 500 mL tetrahydrofuran and 250 mL water, replace nitrogen three times and heat to reflux, react for 16 hours. Cool to room temperature, wash with water, extract with ethyl acetate, and remove excess solvent from the organic phase by reduced pressure distillation. The crude product is purified by column chromatography (PE: EA = 20: 1 (volume ratio)) to obtain about 30.64 g of compound 12-2, yield: 84.6%. MS: 723.68.

[0168] Synthesis of compound 12-3: accurately weigh compound 12-2 (14.48 g, 20 mmol) and add it to a 500 mL three-necked flask, add 1,4-dibromobutane (19.4 g, 90 mmol) to the 500 mL three-necked flask in turn, add about 100 mL of NaOH aqueous solution (50%), 100 mL of dioxane, and tetrabutylammonium bromide (1.6 g, 5 mmol), replace nitrogen three times, and heat to 70 ° C for 4 hours. After the raw materials react completely, cool to room temperature, add water to quench, and extract with ethyl acetate. Combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent. Silica gel mixed sample column chromatography, eluent PE: EA = 5: 1 (volume ratio) to obtain about 19.3 g of compound 12-3, yield: 85.9%. MALDI-TOF-MS: 1129.34.

[0169] Synthesis of compound 12-4: Accurately weigh compound 12-3 (15.7 g, 14 mmol) and add it to a 250 mL three-necked flask, add 150 mL of triethyl phosphite, replace nitrogen three times, heat to 160 ° C and react for 4 hours. Cool to room temperature and remove excess solvent by vacuum distillation. The crude product is purified by column chromatography (PE: DCM = 1: 1 (volume ratio)) to obtain about 13.7 g of compound 12-4, yield: 75.8%. MALDI-TOF-MS: 1300.29.

[0170] Synthesis of compound (SAM-50): Accurately weigh compound 12-4 (13.0 g, 10 mmol) and add it to a 250 mL three-necked flask, dissolve it with 100 mL of dichloromethane, replace nitrogen three times, and add trimethylsilyl bromide (45.9 g, 300 mmol) under nitrogen protection. React at room temperature for 12 hours, and add 30 mL of methanol. Remove the solvent by vacuum distillation, then add methanol and water to precipitate the solid, filter it, and beat the filter cake with ethyl acetate to obtain about 7.32 g of compound (SAM-50), with a yield of 64.7%, MALDI-TOF-MS: 1131.78.

[0171] Synthesis Example 13: Synthesis of (SAM-65)

[0172]

[0173] Synthesis of compound 13-2: Accurately weigh compound 13-1 (51.93 g, 150 mmol), compound 2-2 (22.80 g, 50 mmol), potassium carbonate (41.40 g, 300 mmol), tetrakis(triphenylphosphine)palladium (1.73 g, 1.5 mmol) and add them to a 1000 mL three-necked flask in sequence, add 500 mL tetrahydrofuran and 250 mL water, replace nitrogen three times and heat to reflux, react for 16 hours. Cool to room temperature, wash with water, extract with ethyl acetate, and remove excess solvent from the organic phase by reduced pressure distillation. The crude product is purified by column chromatography (PE: DCM = 3: 1 (volume ratio)) to obtain about 31.25 g of compound 13-2, yield: 71.6%. MS: 873.45.

[0174] Synthesis of compound 13-3: accurately weigh compound 13-2 (17.48 g, 20 mmol) and add it to a 500 mL three-necked flask, add 1,4-dibromobutane (19.4 g, 90 mmol) to the 500 mL three-necked flask in turn, add about 100 mL of NaOH aqueous solution (50%), 100 mL of dioxane, and tetrabutylammonium bromide (1.6 g, 5 mmol), replace nitrogen three times, heat to 70 ° C and react for 4 hours, cool to room temperature after the raw materials react completely, add water to quench, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent, mix with silica gel column chromatography, eluent is PE:EA=5:1 (volume ratio) to obtain about 20.9 g of compound 13-3, yield: 81.7%. MALDI-TOF-MS: 1279.49.

[0175] Synthesis of compound 13-4: Accurately weigh compound 13-3 (18.1 g, 14 mmol) and add it to a 250 mL three-necked flask, add 150 mL of triethyl phosphite, replace nitrogen three times, heat to 160 ° C and react for 4 hours. Cool to room temperature and remove excess solvent by vacuum distillation. The crude product is purified by column chromatography (PE: EA = 1: 1 (volume ratio)) to obtain about 17.4 g of compound 13-4, yield: 86.2%. MALDI-TOF-MS: 1450.86.

[0176] Synthesis of compound (SAM-65): Accurately weigh compound 13-4 (14.50 g, 10 mmol) and add it to a 250 mL three-necked flask, dissolve it with 100 mL of dichloromethane, replace nitrogen three times, and add trimethylsilyl bromide (45.9 g, 300 mmol) under nitrogen protection. React at room temperature for 12 hours, and add 30 mL of methanol. Remove the solvent by vacuum distillation, then add methanol and water to precipitate the solid, filter it, and beat the filter cake with ethyl acetate to obtain about 9.14 g of compound (SAM-65), with a yield of 71.3%, and MALDI-TOF-MS: 1282.25.

[0177] Synthesis Example 14: Synthesis of (SAM-79)

[0178]

[0179] Synthesis of compound 14-3: Accurately weigh compound 14-1 (17.84g, 50mmol), compound 14-2 (43.98g, 150mmol), potassium carbonate (41.40g, 300mmol), tetrakis(triphenylphosphine)palladium (1.73g, 1.5mmol) and add them to a 1000mL three-necked flask in sequence, add 500mL tetrahydrofuran and 250mL water, replace nitrogen three times and then heat to reflux and react for 16h. Cool to room temperature, wash with water, extract with ethyl acetate, and remove excess solvent from the organic phase by reduced pressure distillation. The crude product is purified by column chromatography (PE:EA=10:1 (volume ratio)) to obtain about 23.79g of compound 14-3, yield: 77.2%. MS: 616.32.

[0180] Synthesis of compound 14-4: Accurately weigh compound 14-3 (12.31 g, 20 mmol) and compound 5-3 (29.40 g, 120 mmol), add to a 500 mL three-necked flask, add 120 mL of dimethyl sulfoxide to dissolve, blow nitrogen, add sodium hydride (2.88 g, 120 mmol) in batches, heat to 70 ° C and react for 12 hours. Cool to room temperature, acidify with 1M hydrochloric acid, extract with ethyl acetate, wash with water, and remove excess solvent from the organic phase by reduced pressure distillation. The crude product is purified by column chromatography (PE: EA = 1: 1 (volume ratio)) to obtain about 14.22 g of compound 14-4, yield: 64.2%. MALDI-TOF-MS: 1107.68.

[0181] Synthesis of compound (SAM-79): Accurately weigh compound 14-4 (11.08 g, 10 mmol) and add it to a 250 mL three-necked flask, dissolve it with 100 mL of dichloromethane, replace nitrogen three times, and add trimethylsilyl bromide (45.9 g, 300 mmol) under nitrogen protection. React at room temperature for 12 hours, and add 30 mL of methanol. Remove the solvent by vacuum distillation, then add methanol and water to precipitate the solid, filter it, and beat the filter cake with ethyl acetate to obtain about 7.74 g of compound (SAM-79), with a yield of 82.4%, and MALDI-TOF-MS: 939.56.

[0182] Synthesis Example 15: Synthesis of (SAM-80)

[0183]

[0184] Synthesis of compound 15-2: Accurately weigh compound 14-1 (17.84g, 50mmol), compound 15-1 (52.40g, 150mmol), potassium carbonate (41.40g, 300mmol), tetrakis(triphenylphosphine)palladium (1.73g, 1.5mmol) and add them to a 1000mL three-necked flask in sequence, add 500mL tetrahydrofuran and 250mL water, replace nitrogen three times and then heat to reflux and react for 16h. Cool to room temperature, wash with water, extract with ethyl acetate, and remove excess solvent from the organic phase by reduced pressure distillation. The crude product is purified by column chromatography (PE:EA=3:1 (volume ratio)) to obtain about 33.36g of compound 15-2, with a yield of 85.1%. MS: 783.56.

[0185] Synthesis of compound 15-3: Accurately weigh compound 15-2 (31.35 g, 40 mmol), compound 7-3 (28.30 g, 120 mmol), sodium tert-butoxide (23.04 g, 240 mmol), (dibenzylideneacetone) palladium (0.68 g, 1.2 mmol), Xantphos (1.38 g, 2.4 mmol) and add them into a 500 mL three-necked flask in sequence, add 250 mL of toluene, replace nitrogen three times, and then heat to 80 ° C and react for 12 hours. Cool to room temperature, wash with water, and then extract with ethyl acetate. The organic phase is distilled under reduced pressure to remove excess solvent. The crude product is purified by column chromatography (PE: EA = 5: 1 (volume ratio)) to obtain about 34.87 g of compound 15-3, with a yield of 69.8%. MALDI-TOF-MS: 1248.95.

[0186] Synthesis of compound 15-4: Accurately weigh compound 15-3 (31.20 g, 25 mmol) and 780 mL of triethyl phosphite and add them to a 1000 mL three-necked flask. After replacing nitrogen three times, add palladium acetate (0.19 g, 0.75 mol) and DPPF (0.83 g, 1.5 mmol), then heat to 160 ° C and react for 12 hours. Cool to room temperature and remove excess solvent by vacuum distillation. The crude product is purified by column chromatography (PE: EA = 3: 1 (volume ratio)) to obtain about 25.35 g of compound 15-4, with a yield of 71.4%. MALDI-TOF-MS: 1420.97.

[0187] Synthesis of compound (SAM-80): Accurately weigh compound 15-4 (14.21 g, 10 mmol) and add it to a 250 mL three-necked flask, dissolve it with 100 mL of dichloromethane, replace nitrogen three times, and add trimethylsilyl bromide (45.9 g, 300 mmol) under nitrogen protection. React at room temperature for 12 hours, and add 30 mL of methanol. Remove the solvent by vacuum distillation, then add methanol and water to precipitate the solid, filter it, and beat the filter cake with ethyl acetate to obtain about 10.0 g of compound (SAM-80), with a yield of 79.9%, MALDI-TOF-MS: 1252.14.

[0188] Synthesis Example 16: Synthesis of (SAM-82)

[0189]

[0190] Synthesis of compound 16-2: Accurately weigh compound 14-1 (17.84g, 50mmol), compound 16-1 (51.48g, 150mmol), potassium carbonate (41.40g, 300mmol), tetrakis(triphenylphosphine)palladium (1.73g, 1.5mmol) and add them to a 1000mL three-necked flask in sequence, add 500mL tetrahydrofuran and 250mL water, replace nitrogen three times and then heat to reflux and react for 16h. Cool to room temperature, wash with water, extract with ethyl acetate, and remove excess solvent from the organic phase by reduced pressure distillation. The crude product is purified by column chromatography (PE:DCM=20:1 (volume ratio)) to obtain about 26.12g of compound 16-2, with a yield of 68.2%. MS: 765.59.

[0191] Synthesis of compound 16-3: accurately weigh compound 16-2 (15.31 g, 20 mmol) and add it to a 500 mL three-necked flask, add 1,4-dibromobutane (19.4 g, 90 mmol) to the 500 mL three-necked flask, add about 100 mL of NaOH aqueous solution (50%), 100 mL of dioxane, and tetrabutylammonium bromide (1.6 g, 5 mmol), replace nitrogen three times, and heat to 70 ° C for 4 hours. After the raw materials react completely, cool to room temperature, add water to quench, and extract with ethyl acetate. Combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent. Silica gel mixed sample column chromatography, eluent PE: EA = 5: 1 (volume ratio) to obtain about 17.9 g of compound 16-3, yield: 76.6%. MALDI-TOF-MS: 1171.24.

[0192] Synthesis of compound 16-4: Accurately weigh compound 16-3 (16.4 g, 14 mmol) and add it to a 250 mL three-necked flask, add 150 mL of triethyl phosphite, replace nitrogen three times, heat to 160 ° C and react for 4 hours. Cool to room temperature and remove excess solvent by vacuum distillation. The crude product is purified by column chromatography (PE: DCM = 5: 1 (volume ratio)) to obtain about 15.7 g of compound 16-4, yield: 83.7%. MALDI-TOF-MS: 1342.55.

[0193] Synthesis of compound (SAM-82): Accurately weigh compound 16-4 (13.43 g, 10 mmol) and add it to a 250 mL three-necked flask, dissolve it with 100 mL of dichloromethane, replace nitrogen three times, and add trimethylsilyl bromide (45.9 g, 300 mmol) under nitrogen protection. React at room temperature for 12 hours, and add 30 mL of methanol. Remove the solvent by vacuum distillation, then add methanol and water to precipitate the solid, filter it, and beat the filter cake with ethyl acetate to obtain about 7.88 g of compound (SAM-82), with a yield of 67.1%, and MALDI-TOF-MS: 1174.68.

[0194] Synthesis Example 17: Synthesis of (SAM-92)

[0195]

[0196] Synthesis of compound 17-2: Accurately weigh compound 17-1 (38.74 g, 180 mmol) and add it to a 1000 mL three-necked flask, dissolve it with 500 mL of acetonitrile, add di-tert-butyl dicarbonate (78.48, 360 mmol) to replace nitrogen three times, and react at room temperature for 4 hours. Remove the solvent by vacuum distillation, and purify the product by column chromatography (PE:EA=10:1 (volume ratio)) to obtain about 56.26 g of compound 17-2, with a yield of 98.8% and MS: 316.25.

[0197] Synthesis of compound 17-4: Accurately weigh compound 17-3 (6.30 g, 50 mmol), compound 17-2 (47.40 g, 150 mmol), cesium carbonate (97.50 g, 300 mmol), and cuprous bromide (2.15 g, 15 mmol) and add them to a 1000 mL three-necked flask in sequence, add 500 mL DMF, replace nitrogen three times, and then heat to 160 ° C and react for 12 hours. Cool to room temperature, wash with water, and then extract with ethyl acetate. The organic phase is distilled under reduced pressure to remove excess solvent. The crude product is purified by column chromatography (PE: EA = 20: 1 (volume ratio)) to obtain about 38.75 g of compound 17-4, with a yield of 76.6%. MS: 1011.98.

[0198] Synthesis of compound 17-5: Accurately weigh compound 17-4 (25.30 g, 25 mmol) and add it to a 500 mL three-necked flask, add 250 mL methanol and 100 ML 1M hydrochloric acid, replace nitrogen three times, heat to reflux, and react for 3 hours. Cool to room temperature, remove excess solvent by vacuum distillation, add water and ethyl acetate to extract the liquid, and concentrate the organic phase. The crude product is purified by column chromatography (PE: EA = 20: 1 (volume ratio)) to obtain about 16.33 g of compound 17-5, yield: 91.7%. MS: 712.54.

[0199] Synthesis of compound 17-6: accurately weigh compound 17-5 (14.24 g, 20 mmol) and add it to a 500 mL three-necked flask, add 1,4-dibromobutane (19.4 g, 90 mmol) to the 500 mL three-necked flask in turn, add about 100 mL of NaOH aqueous solution (50%), 100 mL of dioxane, and tetrabutylammonium bromide (1.6 g, 5 mmol), replace nitrogen three times, heat to 70 ° C and react for 4 hours, cool to room temperature after the raw materials react completely, add water to quench, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent, mix with silica gel column chromatography, eluent is PE:EA=5:1 (volume ratio) to obtain about 16.8 g of compound 17-6, yield: 75.2%. MALDI-TOF-MS: 1117.28.

[0200] Synthesis of compound 17-7: Accurately weigh compound 17-6 (15.6 g, 14 mmol) and add it to a 250 mL three-necked flask, add 150 mL of triethyl phosphite, replace nitrogen three times, heat to 160 ° C and react for 4 hours. Cool to room temperature and remove excess solvent by vacuum distillation. The crude product is purified by column chromatography (PE: DCM = 15: 1 (volume ratio)) to obtain about 15.5 g of compound 17-7, yield: 86.2%. MALDI-TOF-MS: 1288.27.

[0201] Synthesis of compound (SAM-92): Accurately weigh compound 17-7 (12.89 g, 10 mmol) and add it to a 250 mL three-necked flask, dissolve it with 100 mL of dichloromethane, replace nitrogen three times, and add trimethylsilyl bromide (45.9 g, 300 mmol) under nitrogen protection. React at room temperature for 12 hours, and add 30 mL of methanol. Remove the solvent by vacuum distillation, then add methanol and water to precipitate the solid, filter it, and beat the filter cake with ethyl acetate to obtain about 8.32 g of compound (SAM-92), with a yield of 74.3%, and MALDI-TOF-MS: 1119.58.

[0202] Synthesis Example 18: Synthesis of (SAM-101)

[0203]

[0204] Synthesis of compound 18-2: Accurately weigh compound 18-1 (42.35 g, 180 mmol) and add it to a 1000 mL three-necked flask, dissolve it with 500 mL of acetonitrile, add di-tert-butyl dicarbonate (78.48, 360 mmol) to replace nitrogen three times, and react at room temperature for 4 hours. Remove the solvent by vacuum distillation, and purify the product by column chromatography (PE:DCM=10:1 (volume ratio)) to obtain about 58.8 g of compound 18-2, with a yield of 97.2%, MS: 336.21

[0205] Synthesis of compound 18-3: Accurately weigh compound 17-3 (6.30 g, 50 mmol), compound 18-2 (50.30 g, 150 mmol), cesium carbonate (97.50 g, 300 mmol), and cuprous bromide (2.15 g, 15 mmol) and add them to a 1000 mL three-necked flask in sequence, add 500 mL DMF, replace nitrogen three times, and heat to 160 ° C. React for 12 hours. Cool to room temperature, wash with water, and then extract with ethyl acetate. The organic phase is distilled under reduced pressure to remove excess solvent. The crude product is purified by column chromatography (PE: DCM = 20: 1 (volume ratio)) to obtain about 36.89 g of compound 18-3, with a yield of 68.8%. MS: 1071.58.

[0206] Synthesis of compound 18-4: Accurately weigh compound 18-3 (26.80 g, 25 mmol) and add it to a 500 mL three-necked flask, add 250 mL of methanol and 100 mL of 1 M hydrochloric acid, replace nitrogen three times, heat to reflux, and react for 3 hours. Cool to room temperature, remove excess solvent by vacuum distillation, add water and ethyl acetate to extract the liquid, and concentrate the organic phase. The crude product is purified by column chromatography (PE: DCM = 20: 1 (volume ratio)) to obtain about 19.01 g of compound 18-4, yield: 98.4%. MS: 772.59.

[0207] Synthesis of compound 18-5: accurately weigh compound 18-4 (15.44 g, 20 mmol) and add it to a 500 mL three-necked flask, add 1,4-dibromobutane (19.4 g, 90 mmol) to the 500 mL three-necked flask in turn, add about 100 mL of NaOH aqueous solution (50%), 100 mL of dioxane, and tetrabutylammonium bromide (1.6 g, 5 mmol), replace nitrogen three times, and heat to 70 ° C for 4 hours. After the raw materials react completely, cool to room temperature, add water to quench, and then extract with ethyl acetate. Combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent. Silica gel mixed sample column chromatography, eluent PE: EA = 5: 1 (volume ratio), to obtain about 16.7 g of compound 18-5, yield: 71.2%. MALDI-TOF-MS: 1175.94.

[0208] Synthesis of compound 18-6: Accurately weigh compound 18-5 (16.4 g, 14 mmol) and add it to a 250 mL three-necked flask, add 150 mL of triethyl phosphite, replace nitrogen three times, heat to 160 ° C and react for 4 hours. Cool to room temperature and remove excess solvent by vacuum distillation. The crude product is purified by column chromatography (PE: EA = 15: 1 (volume ratio)) to obtain about 16 g of compound 18-6, yield: 84.9%. MALDI-TOF-MS: 1348.25.

[0209] Synthesis of compound (SAM-101): Accurately weigh compound 18-6 (13.48 g, 10 mmol) and add it to a 250 mL three-necked flask, dissolve it with 100 mL of dichloromethane, replace nitrogen three times, and add trimethylsilyl bromide (45.9 g, 300 mmol) under nitrogen protection. React at room temperature for 12 hours, and add 30 mL of methanol. Remove the solvent by vacuum distillation, then add methanol and water to precipitate the solid, filter it, and beat the filter cake with ethyl acetate to obtain about 8.09 g of compound (SAM-101), with a yield of 68.6%, MALDI-TOF-MS: 1179.69.

[0210] Synthesis Example 19: Synthesis of (SAM-104)

[0211]

[0212] Synthesis of compound 19-2: Accurately weigh compound 19-1 (62.32 g, 180 mmol) and add it to a 1000 mL three-necked flask, dissolve it with 500 mL of acetonitrile, add di-tert-butyl dicarbonate (78.48, 360 mmol) to replace nitrogen three times, and react at room temperature for 4 hours. Remove the solvent by vacuum distillation, and purify the product by column chromatography (PE:DCM=20:1 (volume ratio)) to obtain about 79.23 g of compound 19-2, with a yield of 98.7% and MS: 445.75.

[0213] Synthesis of compound 19-3: Accurately weigh compound 17-3 (6.30 g, 50 mmol), compound 19-2 (66.90 g, 150 mmol), cesium carbonate (97.50 g, 300 mmol), cuprous bromide (2.15 g, 15 mmol) and add them to a 1000 mL three-necked flask in sequence, add 500 mL DMF, replace nitrogen three times and heat to 160 ° C, react for 12 hours. Cool to room temperature, wash with water, extract with ethyl acetate, and remove excess solvent from the organic phase by reduced pressure distillation. The crude product is purified by column chromatography (PE: DCM = 20: 1 (volume ratio)) to obtain about 45.11 g of compound 19-3, yield: 73.8%. MALDI-TOF-MS: 1222.58.

[0214] Synthesis of compound 19-4: Accurately weigh compound 19-3 (30.57 g, 25 mmol) and add it to a 500 mL three-necked flask, add 250 mL methanol and 100 mL 1M hydrochloric acid, replace nitrogen three times, heat to reflux, and react for 3 hours. Cool to room temperature, remove excess solvent by vacuum distillation, add water and ethyl acetate to extract the liquid, and concentrate the organic phase. The crude product is purified by column chromatography (PE: DCM = 15: 1 (volume ratio)) to obtain about 22.34 g of compound 19-4, yield: 96.8%. MS: 922.83.

[0215] Synthesis of compound 19-5: accurately weigh compound 19-4 (18.46 g, 20 mmol) and add it to a 500 mL three-necked flask, add 1,4-dibromobutane (19.4 g, 90 mmol) to the 500 mL three-necked flask in turn, add about 100 mL of NaOH aqueous solution (50%), 100 mL of dioxane, and tetrabutylammonium bromide (1.6 g, 5 mmol), replace nitrogen three times, and heat to 70 ° C for 4 hours. After the raw materials react completely, cool to room temperature, add water to quench, and extract with ethyl acetate. Combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent. Silica gel mixed sample column chromatography, eluent PE: EA = 5: 1 (volume ratio), to obtain about 20.3 g of compound 19-5, yield: 76.5%. MALDI-TOF-MS: 1327.48.

[0216] Synthesis of compound 19-6: Accurately weigh compound 19-5 (18.5 g, 14 mmol) and add it to a 250 mL three-necked flask, add 150 mL of triethyl phosphite, replace nitrogen three times, heat to 160 ° C and react for 4 hours. Cool to room temperature and remove excess solvent by vacuum distillation. The crude product is purified by column chromatography (PE: EA = 8: 1 (volume ratio)) to obtain about 17.8 g of compound 19-6, yield: 84.9%. MALDI-TOF-MS: 1498.28.

[0217] Synthesis of compound (SAM-104): Accurately weigh compound 19-6 (14.98 g, 10 mmol) and add it to a 250 mL three-necked flask, dissolve it with 100 mL of dichloromethane, replace nitrogen three times, and add trimethylsilyl bromide (45.9 g, 300 mmol) under nitrogen protection. React at room temperature for 12 hours, and add 30 mL of methanol. Remove the solvent by vacuum distillation, then add methanol and water to precipitate the solid, filter it, and beat the filter cake with ethyl acetate to obtain about 7.81 g of compound (SAM-104), with a yield of 58.7%, and MALDI-TOF-MS: 1330.75.

[0218] Organic solar cell (OPV) device preparation and characterization examples

[0219] This embodiment exemplifies the preparation, implementation and characterization of the OPV device in the organic electronic device provided by the present invention, but the present invention is not limited to the following embodiment.

[0220] like Figure 1 As shown, the OPV device structure is as follows: indium tin oxide ITO / hole transport layer / photoactive layer / PNDIT-F3N / / Ag.

[0221] Device Example 1:

[0222] 1) ITO substrate cleaning:

[0223] The ITO conductive glass was cleaned with detergent, rinsed, and then ultrasonically cleaned with deionized water, acetone, and isopropanol for 15 minutes, then blown dry with nitrogen and treated in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0224] 2) Preparation of hole transport layer

[0225] The hole transport layer solution was evenly spin-coated on the ITO in air at a spin-coating speed of 3000 rpm for 30 seconds, and dried at 110° C. for 10 minutes to obtain the hole transport layer. The hole transport layer solution preparation method is as follows: the hole transport layer material organic compound (SAM-1) was dissolved in an organic solvent DMF at a concentration of 0.3 mg / mL to obtain the hole transport layer solution.

[0226] 3) Preparation of photoactive layer

[0227] In a glove box (inert gas atmosphere), the photoactive layer solution was evenly spin-coated on the hole transport layer at a rotation speed of 1800-4000 rpm to obtain a photoactive layer with a total thickness of about 100 nm.

[0228] The donor material in the photoactive layer solution is selected from PM6, and the acceptor material is selected from L8-BO and BTP-eC9. The polymer PM6 and the acceptor materials L8-BO and BTP-eC9 are dissolved in chloroform, the mass ratio of PM6:L8-BO:BTP-eC9 is 1:0.5:0.7, the total concentration of PM6, L8-BO and BTP-eC9 in chloroform is 16 mg / mL, and 0.5% by volume of DIO is added as an additive to obtain a photoactive layer solution.

[0229]

[0230] 4) Preparation of cathode buffer layer

[0231] After thermal annealing on a hot plate at 100°C for 10 min, the cathode buffer layer material PNDIT-F3N (PNDIT-F3N was dissolved in methanol to prepare a solution with a concentration of 1.0 mg / mL, and 0.4% by volume acetic acid was added to the solution) was evenly spin-coated on the photoactive layer at a spin coating speed of 3000 rpm and a rotation time of 20 s to obtain a cathode buffer layer.

[0232] 5) Cathode layer preparation

[0233] In high vacuum (1×10 -6 Ag was evaporated onto the cathode buffer layer at 400 mbar to form a cathode layer with a thickness of about 100 nm.

[0234] 6) Packaging

[0235] The devices were encapsulated with UV-curable resin in a nitrogen glove box.

[0236] Device Examples 2-14:

[0237] The preparation methods of device embodiments 2-14 refer to the preparation method of device embodiment 1, except that the hole transport layer material is selected differently. Specifically, the hole transport layer material organic compound (SAM-1) in device embodiment 1 is replaced by organic compound (SAM-2), organic compound (SAM-3), organic compound (SAM-5), organic compound (SAM-12), organic compound (SAM-22), organic compound (SAM-34), organic compound (SAM-45), organic compound (SAM-50), organic compound (SAM-65), organic compound (SAM-79), organic compound (SAM-80), organic compound (SAM-92) and organic compound (SAM-104), respectively. See Table 1 for details.

[0238] The prepared organic solar cell device was subjected to a performance test. Under the irradiation of standard light from a solar simulator (AM 1.5G), the cell current-voltage curve was tested and the photoelectric conversion efficiency was calculated. See Table 1 for details.

[0239] Table 1

[0240] Device Embodiment Hole transport layer materials Photoelectric conversion efficiency (%) Device Example 1 Organic compounds (SAM-1) 18.74 Device Example 2 Organic compounds (SAM-2) 18.61 Device Example 3 Organic compounds (SAM-3) 19.32 Device Example 4 Organic compound (SAM-5) 18.5 Device Example 5 Organic compound (SAM-12) 18.16 Device Example 6 Organic compound (SAM-22) 15.46 Device Example 7 Organic compound (SAM-34) 17.88 Device Example 8 Organic compound (SAM-45) 18.27 Device Example 9 Organic compound (SAM-50) 17.95 Device Example 10 Organic compounds (SAM-65) 17.01 Device Example 11 Organic compound (SAM-79) 17.62 Device Example 12 Organic compound (SAM-80) 14.87 Device Example 13 Organic compound (SAM-92) 18.83 Device Example 14 Organic compound (SAM-104) 17.4

[0241] It can be seen from the data in Table 1 that the N-containing miscellaneous organic compound provided by the present invention is applied as a hole transport layer material in an organic solar device and exhibits excellent photoelectric conversion performance. The reason is that: the organic compound has three phosphate anchoring sites, and multiple phosphate anchoring sites can effectively enhance its anchoring ability with the surface of the ITO substrate. At the same time, the N-containing miscellaneous organic compound of the present invention has a large steric hindrance, which can effectively inhibit excessive molecular aggregation, thereby forming an ideal molecular morphology, thereby enhancing the extraction of holes.

[0242] The above examples further illustrate the content of the present application, but should not be construed as limiting the present application. Without departing from the spirit and substance of the present application, modifications and replacements made to the methods, steps or conditions of the present application all fall within the scope of the present application. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.

Claims

1. A N-containing miscellaneous organic compound, characterized in that: The N-containing miscellaneous organic compound has a structure as shown in the general formula (I): in, -Z-, at each occurrence, is independently selected from a single bond, -CH2-, -O-, or -S-; Each occurrence of A is independently selected from the group (A-1) or (A-2): Each occurrence of L is independently selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a A substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or R a a substituted or unsubstituted heteroaromatic group having 5 to 10 carbon atoms; Ar1, Ar2, Ar3 are independently selected from b A substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or R b a substituted or unsubstituted heteroaromatic group having 5 to 20 carbon atoms; R a , R b Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, hydroxy, nitro, amino, alkyl having 1-20 carbon atoms, alkoxy having 1-20 carbon atoms, alkylthio having 1-20 carbon atoms, aryl having 6-10 carbon atoms, or heteroaromatic having 5-10 ring atoms, or a group formed by a combination of the foregoing groups; * indicates the attachment site.

2. The N-containing miscellaneous organic compound according to claim 1, characterized in that: The N-containing miscellaneous organic compound has a structure shown in any one of the general formulas (II-1) to (II-4):

3. The N-containing miscellaneous organic compound according to claim 1 or 2, characterized in that: The Ar1, Ar2, and Ar3 are independently selected from any of the following groups: in, Each occurrence of X is independently selected from CR1 or N; Each occurrence of R1 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, hydroxy, nitro, amino, alkyl having 1-20 carbon atoms, alkoxy having 1-20 carbon atoms, alkylthio having 1-20 carbon atoms, aryl having 6-10 carbon atoms, or heteroaromatic group having 5-10 ring atoms, or a group formed by a combination of the above groups; # indicates a fusion site, which is selected from a C atom.

4. The N-containing miscellaneous organic compound according to claim 3, characterized in that: The N-containing miscellaneous organic compound is selected from any one of the structures shown in (III-1) to (III-16):

5. The N-containing miscellaneous organic compound according to claim 4, characterized in that: Each occurrence of R1 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, hydroxyl, nitro, amino, alkyl having 1-10 carbon atoms, alkoxy having 3-10 carbon atoms, alkylthio having 1-10 carbon atoms, aryl having 6-10 carbon atoms, or heteroaromatic group having 5-10 ring atoms, or a group formed by a combination of the above groups.

6. The N-containing miscellaneous organic compound according to claim 1, characterized in that: Each occurrence of L is independently selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkylthio group having 1 to 10 carbon atoms, a Substituted or unsubstituted phenyl, or R a Substituted or unsubstituted biphenyl; R a Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, hydroxy, nitro, amino, alkyl having 1-6 carbon atoms, alkoxy having 1-6 carbon atoms, alkylthio having 1-6 carbon atoms, aryl having 6-10 carbon atoms, or a heteroaromatic group having 5-10 ring atoms, or a group formed by a combination of the above groups.

7. The N-containing miscellaneous organic compound according to claim 1, characterized in that: Said * -LA is selected from any of the following groups: Wherein: n is selected from 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

8. The N-containing miscellaneous organic compound according to claim 1, characterized in that: The N-containing organic compound is selected from any of the following structures:

9. A hole transport material, characterized in that: The hole transport material is selected from the N-containing miscellaneous organic compounds as described in any one of claims 1 to 8.

10. An organic electronic device, characterized in that: The organic electronic device comprises an anode, a cathode, a photoactive layer between the anode and the cathode, and a hole transport layer between the photoactive layer and the anode, wherein the hole transport layer material is selected from the N-containing miscellaneous organic compound according to any one of claims 1 to 8.

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