TW201431853A - Electron transmission material and organic light-emitting element - Google Patents

Abstract

This invention relates to an electron transmission material comprising the compound represented by formula (I) wherein each A1 is the same or different and represents an aromatic ring, and each X is the same or different and represents an electron-withdrawing group. Using the coordination of the electron transmission material and a hole transmission material, this invention may use the exciplex formed by the electron transmission material and the hole transmission material to emit light.

Description

Electron transport material and organic light emitting element

The present invention relates to an electroactive material suitable for use in a light-emitting element, and more particularly to an electron-transporting material suitable for use in an organic light-emitting element, and an organic light-emitting element having the electron-transporting material.

Among various types of light-emitting elements, organic light-emitting diodes have been widely used in many electronic devices (such as mobile phones, flat panel displays, etc.) due to their wide viewing angle, low power consumption, high reaction rate, high contrast, and simple process. .

In general, the illuminating mechanism of the organic light-emitting diode belongs to electroluminescence, which is performed by externally applying a bias voltage to inject electrons and holes from the cathode and the anode into the organic material layer to form high-energy excitons, and It releases energy in the form of light (or heat).

A variety of organic molecules, such as small molecule organic light-emitting compounds, luminescent metal complexes, conjugated polymers, and mixtures thereof, are known to have electroluminescence, and in many ways, these organic molecular materials are used. A dopant in the host material.

However, there is still a need for continuous improvement in existing materials and component structures to achieve satisfactory luminous efficiency.

One of the main objects of the present invention is to provide a novel material which is different from the electroactive materials known in the prior art and which can be used in the electron transport layer of an organic light-emitting element.

Another primary object of the present invention is to utilize the novel materials described above to achieve a particular illumination mechanism. In such a light-emitting mechanism, an exciplex can be formed between the electron transport material and the hole transport material to emit light.

To achieve the foregoing primary and other objects, the present invention provides an electron transporting material comprising a compound of the following formula (I): Wherein each A ₁ is the same or different and represents an aromatic ring, each X being the same or different and representing an electron withdrawing group (EWG).

In addition, the present invention also provides an organic light emitting device comprising: an anode; at least one hole transport layer on the anode, the hole transport layer comprising a hole transport material; at least one electron transport layer located at the Above the hole transport layer, the electron transport layer comprises an electron transport material; and a cathode is disposed on the electron transport layer, wherein the electron transport material is as shown in the formula (I), causing the organic light emitting element to be externally biased Pressing, an excimer complex luminescence can be formed between the hole transport layer and the electron transport layer.

The invention further provides an organic light-emitting element, which is substantially composed of the following layers: an anode layer; at least one hole transport layer on the anode layer, the hole transport layer comprising a hole transport material; at least one An electron transport layer over the hole transport layer, the electron transport layer comprising an electron transport material as shown in formula (I); and a cathode layer on the electron transport layer, wherein the electron transport layer Both the HOMO of the material and the LUMO of the electron transporting material have a specific energy level difference, so that the organic light emitting element can form an exciplex luminescence between the hole transport layer and the electron transport layer under an applied bias voltage.

In an embodiment of the invention, the interface between the hole transporting material and the electron transporting material is designed to satisfy a specific energy level difference, and each of the two has a relatively high triplet excited state energy level to effectively limit the carrier. The exciplex complex single and triplet excited states are generated at the interlayer interface. Therefore, proper control of the HOMO energy level of the hole transport material and the LUMO energy level of the electron transport material enables the organic light emitting element to form an exciplex of various colors between the hole transport layer and the electron transport layer under an applied bias voltage. Luminescence, the component illumination wavelength range includes, but is not limited to, blue to red, as shown in the following examples and figures.

The invention also provides a composite organic light-emitting device, comprising: an anode; a hole transport layer on the anode, the hole transport layer comprises a first hole transport material; a buffer layer located in the hole Above the transport layer, the buffer layer comprises a second hole transport material different from the first hole transport material; an electron transport layer located above the buffer layer, the electron transport layer comprising the formula (I) An electron transporting material is shown; and a cathode is located over the electron transport layer. By adjusting the thickness of the second hole transport material in the buffer layer, the composite organic light-emitting element can generate two-region light emission by using an exciplex light-emitting mechanism and electron tunneling.

The present invention further provides a tandem organic light-emitting element comprising: an anode; a cathode; at least two organic light-emitting units (each of which can independently adopt a two-layer type, a hybrid type, and a composite type of light-emitting mechanism), Between the anode and the cathode, wherein the organic light-emitting units each independently comprise an electron transport layer and a hole transport layer, and optionally include a buffer layer, the hole transport layer includes a hole transport material, The electron transporting layer includes an electron transporting material as shown in the formula (I); and an intermediate connecting layer disposed between the organic light emitting units, wherein the HOMO of the hole transporting material is in each of the organic light emitting units The LUMOs of the electron transporting materials correspond to each other, so that the organic light emitting unit forms an exciplex light emission between the hole transport layer and the electron transport layer under an applied bias voltage, so that the tandem organic light emitting device can be widely realized. The effect of gamut illuminating.

Hereinafter, the definitions of the terms of the present invention, the electron transporting materials, and the characteristics of the respective layers of the organic light-emitting elements will be described in order, and specific embodiments and examples of the present invention will be hereinafter described.

Term definition

The components and components of the present invention are described in terms of "a", "an" or "an" Therefore, unless otherwise indicated, the description is to be understood to include one or at least one

In this article, the terms "including", "including" and "having" are non-exclusive and open tortuous. That is, a process, apparatus, or component that comprises a plurality of components is not necessarily limited to the listed components, but may include other components not specifically listed but inherent to the process, apparatus, or component. In addition, "substantially composed of" means consisting mainly of certain features or components, and there are no features or elements that would substantially alter the operating principle or distinctive features (eg, change the excimer complex luminescence) A feature or component of a phenomenon, but encompasses other features or elements that do not materially alter the principles of operation or distinctive features.

As used herein, unless otherwise specified, "or" means an inclusive "or" rather than an exclusive "or". For example, the following three cases satisfy the description of "A or B": A is true (or exists) and B is pseudo (or non-existent), A is pseudo and B is true, and both A and B are true.

As used herein, the term "charge transfer" (eg, "electron transport" or "hole transport"), when referring to a layer, material or structure, means that the layer, material or structure may contribute to the charge (eg, electron or The hole) migrates through the layer, material or structure with higher efficiency and less charge loss. As used herein, a hole transport material transports a positive charge while an electron transport material carries a negative charge.

As used herein, the term "aromatic ring" refers to an aromatic carbocyclic or heterocyclic ring structure which may be a single ring or a polycyclic ring formed by condensing or covalently bonding to each other, and may be substituted or not Replaced by. The "aromatic ring" may be an aromatic hydrocarbon ring, and examples thereof include, but are not limited to, benzene, naphthalene, anthracene, biphenyl, phenanthrene, anthracene, and the like; and the "aromatic ring" may also be a heteroaromatic ring, that is, at least in the molecule. An aromatic ring containing a hetero atom (e.g., a non-carbon atom such as oxygen, nitrogen, sulfur, etc.), examples of which include, but are not limited to, pyridine, pyrazine, pyrimidine, pyridazine, anthracene, oxazole, oxazole, thiazole, thiophene, Furan and its analogues. Further, the number of atoms of the "aromatic ring" is not particularly limited and may be 5 to 30 atoms, for example, 5 to 25, 5 to 20, 5 to 15 or 5 to 10 atoms.

The phrase "electron-drawing group" refers to a group which reduces the electron density of an aromatic ring, and examples thereof include, but are not limited to, a halogen group, a nitro group, a carbonyl group, a cyano group, a pyridyl group, a benzimidazolyl group, an oxadiazolyl group, and an anthracene group. Base with phosphino group. For example, "electron-drawing group" can also be the following groups: Wherein each A ₂ is the same or different and represents an aromatic ring, and the definition of the aromatic ring is as described above.

As used herein, all groups may be substituted as needed unless otherwise indicated.

As used herein, "HOMO" refers to the highest occupied molecular orbital domain, while "LUMO" refers to the lowest unoccupied molecular orbital domain.

The term "excited complex luminescence" refers to the luminescence phenomenon caused by the formation of an exciplex in different adjacent molecules.

Electronic transmission material

The present invention relates generally to an electron transporting material comprising a compound of the following formula (I): Wherein each A ₁ is the same or different and represents an aromatic ring, each X is the same or different and represents an electron withdrawing group, and the aromatic ring and the electron withdrawing group are as defined above.

In one embodiment, the three A ₁ systems are identical to each other; in one embodiment, two A ₁ systems are identical to each other; in one embodiment, the three A ₁ systems are different from each other. In one embodiment, the three X systems are identical to one another; in one embodiment, two X systems are identical to each other; in one embodiment, the three X systems are different from one another.

The aromatic ring represented by A ₁ may be an aromatic hydrocarbon ring or a heteroaromatic ring, and the number of atoms thereof may be, for example, in the range of 6-30, 6-25, 6-20, 6-15 or 6-10.

In the present invention, the substitution position of X on A ₁ is not particularly limited as long as the compound formed has a specific electron transporting ability. For example, if A ₁ is a benzene ring, the position of X relative to the three "triazine ring" may be ortho, meta or para. If A ₁ is another aromatic ring, the position of X relative to the three "mouth + well" ring can be any position that facilitates electron pull.

Organic light-emitting element

In the present invention, an organic light-emitting element mainly comprises: an anode; at least one hole transport layer on the anode, the hole transport layer comprises a hole transport material; at least one electron transport layer is located in the electricity Above the hole transport layer, the electron transport layer comprises the above electron transport material; and a cathode is located above the electron transport layer.

An anode refers to an electrode that is particularly effective for injecting positive charge carriers, which may be a material containing a metal, a mixed metal, an alloy, a metal oxide, or a mixed oxide. The anode may be, for example, an oxide of a Group 2 metal, an element of Groups 4-6 or 8-11. If the anode is to be translucent, a mixed oxide of Group 13 and Group 14 elements, such as indium tin oxide (ITO), can be used to facilitate observation of the generated light. In addition, the anode may also include organic materials such as polyaniline, polythiophene or polypyrrole.

In general, the anode can be fabricated by chemical or physical vapor deposition, such as metal organic chemical vapor deposition (MOCVD), plasma enhanced chemical vapor deposition (PECVD), ion beam sputtering, electron beam evaporation, and electrical resistance. Evaporation, etc., but not limited to this.

The hole transport layer may include a small molecule hole transport material, examples of which include, but are not limited to, N, N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)benzidine (NPB), 4 , 4',4"-tris(N-carbazolyl)-triphenylamine (TCTA), 1,3-bis(carbazol-9-yl)benzene (mCP), 1,1-bis[(di-4) -toluidine)phenyl]cyclohexane (TAPC), 5-(4,6-dichlorotrisole "well +-2-yl)amino fluorescein (DTAF), 4,4',4 "-Tris(N-3-methylphenyl-N-anilino)-triphenylamine (mt-DATA), N,N'-diphenyl-N,N'-di-[4-(N,N- Diphenylamino)phenyl]benzidine (NPNPB), 4,4',4"-tris(N,N-diphenylamino)-triphenylamine (t-DATA), α-phenyl-4-N , N-diphenylamine styrene (TPS), triphenylamine (TPA) and the like.

The hole transport layer may also include polymeric hole transport materials, examples of which include, but are not limited to, polyvinylcarbazole, (phenylmethyl) polydecane, poly(dioxythiophene), polyaniline, and polypyrrole. Further, the above small molecule hole transporting material may be doped into a polymer such as polystyrene to obtain a hole transporting polymer.

Examples of various types of hole transport materials can be found in Kirk Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 18, p. 837 860, 1996, by Y. Wang, the entire disclosure of which is incorporated herein by reference.

The hole transport layer can be coated by any deposition technique. In some embodiments, the hole transport layer can be coated by solution deposition. In some embodiments, the hole transport layer can be coated by a continuous solution deposition process.

Cathode refers to an electrode that is particularly effective for injecting negative charge carriers, which can be any metal or non-metal that has a lower work function than the anode. Materials for the cathode include, but are not limited to, Group 1 metals, Group 2 metals, Group 12 metals, and lanthanides, and materials such as aluminum, indium, calcium, lanthanum, cerium, magnesium, and combinations thereof can be used as the cathode. . In general, the cathode can be formed by chemical or physical vapor deposition.

In one embodiment, the organic light emitting device is provided with a hole injection layer between the hole transport layer and the anode to promote positive charge injection and migration through the layer in a relative efficiency and a small amount of charge loss.

The hole injection layer may contain a polymer or a small molecule, and may be in the form of a solution, an emulsion, a dispersion, a suspension, a colloidal mixture or the like. In one embodiment, the hole injection layer is formed of a polymeric material such as poly(ethylene dioxythiophene) (PEDOT), and the polymeric material may be mixed with a protic acid such as polystyrenesulfonic acid (PSS). In general, the hole injection layer can be formed by any deposition technique. In some embodiments, the hole injection layer can be formed using a solution deposition process. In some embodiments, the hole injection layer can be formed using a continuous solution deposition process.

In an embodiment, the organic light emitting device is provided with an electron injection layer between the electron transport layer and the cathode.

For example, an organometallic compound containing Li such as Liq, LiF, Li ₂ O, or an organometallic compound containing Cs, CsF, Cs ₂ O or Cs ₂ CO _{3 may be} deposited between the electron transport layer and the cathode layer as An electron injection layer is used to reduce the operating voltage, enhance the flatness of the layer, facilitate electron transport or injection, and enhance the performance of components or devices.

In addition, in an embodiment, the foregoing layers or materials may be deuterated as needed to reduce the probability of decomposition of each layer or material by holes, electrons, excitons, exciplexes, etc., thereby improving the stability of the component and Service life.

In the present invention, the organic light-emitting element can be mainly illuminated in two ways, and neither of them is obtained by doping the electron transport layer with a fluorescent or phosphorescent dopant.

The first illuminating mechanism is to perform interface illuminating through a bi-layer structure of a hole transport layer and an electron transport layer. At this time, the hole transport layer and the electron transport layer are adjacent to each other, and under an external bias. An exciplex luminescence phenomenon is formed at the interface between the two.

The second illuminating mechanism is to provide a luminescent layer between the hole transport layer and the electron transport layer, and the luminescent layer contains a mixture of electroactive materials in which HOMO and LUMO are matched with each other, for example, a mixture of the aforementioned hole transporting material and electron transporting material. , the mixing ratio may be about 99:1, 95:5, 90:10, 85:15, 80:20, 75:25, 70:30, 65:35, 60:40, 55:45 or 50:50 . In such a mixed form of the organic light-emitting element, an exciplex illuminating phenomenon can be formed between the mixture of the light-emitting layers when a bias voltage is applied.

In one embodiment, the HOMO of the hole transport layer for performing the exciplex light emission is preferably between -5.0 eV and -6.5 eV, and more preferably between -5.1 eV and -6.1 eV; In one embodiment, the LUMO of the electron transport layer for the excimer complex luminescence is preferably between -2.5 eV and -3.5 eV, and more preferably between -2.8 eV and -3.0 eV.

In general, various processes can be used to fabricate such organic light-emitting elements. For example, the desired layer is deposited sequentially on a particular substrate (eg, glass, plastic, or metal), and means that may be used include, but are not limited to, thermal evaporation, vapor deposition, spin coating, screen printing, ink jet printing, and the like. If it is desired to form the layer structure by, for example, liquid phase deposition, any liquid medium capable of forming a thin film can be used for deposition, such as a medium composed of water and one or more organic solvents.

In one embodiment, a commercially available ITO substrate is used, and a non-essential hole injection layer, one or more hole transport layers, and unnecessary light are formed on the substrate by spin coating or thermal evaporation. a layer (containing a mixture of an electron transporting material and a hole transporting material), one or more electron transporting layers, an optional electron injecting layer, and a cathode, and then encapsulating with a glass cover, a desiccant, and a UV curable epoxy to form An organic light emitting element.

In the present invention, the thickness of each layer is not particularly limited and may be, for example, in the range of 10 to 5000 angstroms, such as 50 to 2000 angstroms, 50 to 1000 angstroms, 100 to 3,000 angstroms, 100 to 1,500 angstroms or 100 to 1000 angstroms. The scope. In one embodiment, the thickness of the anode is between 100 and 5000 angstroms, and the thickness of the hole injection layer (if any) is between 50 and 3000 angstroms, and the thickness of the hole transport layer is between Between 50 and 1000 angstroms, the thickness of the luminescent layer (if any) is between 50 and 1000 angstroms, the thickness of the electron transport layer is between 50 and 1000 angstroms, and the electron injection layer (if any) The thickness of the cathode is between 50 and 3000 angstroms and the thickness of the cathode is between 100 and 2000 angstroms.

In the present invention, the color of the illuminating light can be changed by adjusting various parameters of the organic light emitting element. For example, the type of the hole transport material can be changed, thereby changing the energy level difference between the hole transport material and the electron transport material to adjust the desired light color, and the light wavelength has a maximum in the range of about 400 to about 750 nm. Luminous radiation value. In one embodiment, the organic light emitting device emits blue light (about 450 to about 495 nm); in one embodiment, the organic light emitting device emits green light (about 520 to about 570 nm); in one embodiment, organic The light emitting element can emit yellow light (about 570 to about 590 nm); in an embodiment, the organic light emitting element can emit orange light (about 590 to about 620 nm); in an embodiment, the organic light emitting element can emit red light. (about 620 - about 740 nm).

In addition, an embodiment of the present invention further discloses a composite organic light-emitting element that utilizes the foregoing two-layer structure or a mixed layer structure, which can simultaneously emit light of two or more different wavelengths to achieve the effect of mixing light colors. For example, by emitting light of two or more different wavelengths, the composite organic light-emitting element can exhibit a white light-emitting effect as a whole. As used herein, "white light" refers to visible light that causes the visual perception to be white, and it should be broadly interpreted to include a variety of generally collectively referred to as white light, including but not limited to white light, warm white light, cool white light, and the like.

In the embodiment of the composite organic light-emitting device, if the two-layer structure is taken as an example, it mainly contains an anode; a hole transport layer is located above the anode, and the hole transport layer includes a first hole transport material. a buffer layer, located above the hole transport layer, the buffer layer includes a second hole transport material different from the first hole transport material; an electron transport layer located on the buffer layer, The electron transport layer includes a first electron transport material; and a cathode is disposed over the electron transport layer.

The HOMO of the first hole transporting material and the LUMO of the first electron transporting material form an exciplex light emitting due to electron tunneling under an applied bias voltage, and the HOMO of the second hole transporting material and the first The LUMO of an electron transporting material forms another exciplex luminescence at the interface between the two.

If the mixed layer structure is taken as an example, the composite organic light emitting device further comprises a light emitting layer interposed between the buffer layer and the electron transport layer, and the light emitting layer comprises a third hole transporting material and a second electron transporting material. The mixture may have a mixing ratio of 99:1 to 1:99 as described above, and wherein the third hole transporting material may be the same as the second hole transporting material, and the second electron transporting material may be combined with the first electron transporting material The same, thereby simplifying the process.

Under external bias, the electron transporting material and the hole transporting material in the mixed layer can form an exciplex illuminating light (for example, blue light), and the hole transporting material and the electron transporting material respectively located on both sides of the buffer layer can be electronically Tunneling to form another exciplex glow (eg orange light).

In general, the thinner the thickness of the buffer layer, the more the hole transport material and the electron transport material located on both sides of the buffer layer are more likely to form an exciplex glow due to electron tunneling. Therefore, the thickness of the buffer layer can be adjusted, and the different exciplex luminescence phenomenon in the composite organic light-emitting element is proportionally regulated. For example, in one embodiment, the buffer layer has a thickness for electron tunneling, which is preferably less than 15 nm, such as between 14 and 1 nm, 13 to 2 nm, and 12 to 3 nm. , 11 to 4 nm, 10 to 5 nm, 9 to 6 nm, 8 to 7 nm, and so on.

In addition, in the above-mentioned composite type organic light-emitting element, the color shift phenomenon generated by such a structure (the case where the spectrum is shifted under different voltage driving, such as the experimental data and the pattern presented in the text) can be utilized. A particular voltage is selected to produce a particular color of light.

In addition, an embodiment of the present invention further discloses a tandem organic light-emitting element using the foregoing two-layer structure or a mixed layer structure, which comprises a plurality of organic light-emitting units capable of forming an exciplex light-emitting phenomenon, and between different organic light-emitting units. An electrical connection is made through an intervening connection layer.

In a preferred embodiment, different organic light-emitting units can generate different exciplex luminescence phenomena to achieve the effect of mixing light colors. For example, by emitting two or more different wavelengths of visible light, the tandem organic light-emitting element can exhibit a white light-emitting effect as a whole, wherein the definition of "white light" is as described above.

In the tandem organic light-emitting element, the manner in which the different organic light-emitting units form the excited complex light-emitting layer may be the same or different. For example, all the organic light-emitting units may use the foregoing double-layer structure or mixed layer structure, or some units may use a two-layer structure. Other units use a mixed layer structure, or some units use a composite structure, while other units use a two-layer structure or a mixed layer structure.

Each unit may be connected in series by an intermediate connection layer (or a charge generation layer), and carrier injection and charge balance may be performed between the units through the intermediate connection layer. In an embodiment, the interposer layer may comprise an organic material, an inorganic material, a metal, a metal oxide, or a combination thereof. For example, the organic material may be LiF, Cs ₂ CO ₃ , CsF, etc.; the metal may be Al, Ag, Au, Mg, Ca, Li, etc.; the metal oxide may be ITO, IZO, AZO, MoO ₃ , WO ₃ , V ₂ O ₅ and the like. If the tandem organic light-emitting element includes a plurality of interposer layers, the composition of each of the interposer layers may be the same or different, and the thickness may be, for example, from 1 nm to 100 nm.

EXAMPLES: Synthesis of Compounds

Synthesis of Compound A

Step A-1: Take a 100 ml single-necked flask, place 3-bromobenzonitrile (2 g, 11 mmol) and a stirrer into the bottle, add dichloromethane (20 ml), and add at room temperature. Trifluoromethanesulfonic acid (2 ml, 14.5 mmol) was stirred for 24 hours. The reaction was quenched with saturated aqueous sodium hydrogencarbonate, and extracted with dichloromethane. EtOAcjjjjjjjjjjjjjjjjjjjjjjjj Solid product (1.32 g, 2.42 mmol, 67%).

Step A-2: Take a 100 ml single-necked flask, add p-bromobenzoic acid (5 g, 25 mmol) and a stirrer, add SOCl ₂ (27 ml, 375 mmol) at room temperature, heat to reflux for 3 hours, then distill. Drop SOCl ₂ . N-phenyl-o-phenylenediamine (3.05 g, 16.5 mmol) and triethylamine (2.76 ml, 20 mmol) were added to dichloromethane (55 ml) to give the intermediate of decylamine. Further purification, filtered, directly with acetic acid as a solvent, heated to dissolve, and refluxed for 14 hours for acid-catalyzed ring-closing reaction, after which acetic acid was removed, and the remaining acetic acid was neutralized with aqueous sodium hydroxide solution, and extracted with dichloromethane. The organic layer was dried with EtOAc EtOAc EtOAcjjjjjjj

Step A-3: Take a 50 ml two-necked flask and add the product of step A-2 (1 g, 2.9 mmol), diboron reagent (0.87 g, 3.5 mmol), potassium acetate (0.88 g, 10 mmol), PdCl ₂ (dppf) (0.07 g, 0.1 mmol) and stirrer, rack the condenser, vacuum and then argon, deionized water tetrahydrofuran (18 ml), heated to 85 ^o C, reacted for 12 hours, cooled to extraction at room temperature, water and dichloromethane, the organic layer was dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure, and then solid was purified (SiO _2, EA / hexane = 1/5) purified by column chromatography The product was obtained as a white solid (0.75 g, 1.9 mmol, 65%).

Step A-4: Take a 100 ml flask, add the product from step A-1 (1.5 g, 2.7 mmol), the product from step A-3 (3.48 g, 8.78 mmol), Pd ₂ (dba) ₃ (0.07 g) , 0.082 mmol), 2-(dicyclohexylphosphine)biphenyl (0.19 g, 0.54 mmol), K ₃ PO ₄ (5.82 g, 27.5 mmol), stirrer, rack condensate, vacuum and argon Then, 1,4-two "mouth + oxime" (28 ml) and water (6 ml) were driven through a syringe, heated to reflux, and stirred for two days. After returning to room temperature, 1,4-dioxanol was removed by a reduced pressure concentrator and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then evaporated, evaporated , 2.15 mmol, 78%). Mp 324 ^o C (DSC); IR (KBr) ν 3055, 1596, 1492, 1451, 1368, 1262, 842, 791, 746, 697, 666, 615, 503; ¹ H NMR (CD ₂ Cl ₂ , 400 MHz ) δ 9.04 (s, 3H), 8.80 (d, J = 8.0 Hz, 3H), 7.89 (d, J = 8.0 Hz, 3H), 7.84 (d, J = 7.6 Hz, 3H), 7.74-7.67 (m , 15H), 7.57-7.51 (m, 9H), 7.40-7.24 (m, 15H); ¹³ C NMR (CD ₂ Cl ₂ , 400 MHz) δ 172.3, 152.5, 143.8, 141.9, 141.2, 138.2, 137.7, 137.4 , 131.8, 130.6, 129.9, 129.3, 129.0, 128.1, 128.0, 127.6, 123.9, 123.4, 120.2, 111.1; HRMS (m/z, FAB+) Cacld. for C ₇₈ H ₅₁ N ₉ 1113.4267, found 1113.4272.

Synthesis of Compound B

Step B-1: Take a 100 ml single-necked flask, add m-bromobenzoic acid (5 g, 25 mmol) and a stirrer, add SOCl ₂ (27 ml, 375 mmol) at room temperature, heat to reflux for 3 hours, then distillate. Drop SOCl ₂ . Then, using dichloromethane (55 ml) as a solvent, N-phenyl-o-phenylenediamine (3.05 g, 16.5 mmol) and triethylamine (2.76 ml, 20 mmol) were added to give the intermediate of the decylamine. After further purification, the mixture was directly filtered with acetic acid as a solvent, heated to dissolve, and refluxed for 14 hours for acid-catalyzed ring-closing reaction, after which acetic acid was withdrawn, and the remaining acetic acid was neutralized with an aqueous solution of sodium hydroxide, and extracted with dichloromethane. the organic layer was dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure, and then the solid was purified by column chromatography (SiO _2, EA / hexane = 1/9), to give the product as a white solid (4.7 g, 13.46 M, 81%).

Step B-2: Take a 50 ml two-necked flask and add the product of step B-1 (1.05 g, 3.0 mmol), diboron reagent (0.84 g, 3.3 mmol), potassium acetate (0.88 g, 10 mmol), PdCl. ₂ (dppf) (0.07 g, 0.1 mmol) and stirrer, rack the condenser, vacuum and argon, DMSO (18 ml), heat to 80 ^o C, react for 6 hours, cool to room temperature The mixture was extracted with water and methylene chloride. EtOAcjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj Solid product (0.75 g, 1.9 mmol, 63%).

Step B-3: Take a 100 ml flask, add the product from step A-1 (1.5 g, 2.75 mmol), the product from step B-2 (3.48 g, 8.78 mmol), Pd ₂ (dba) ₃ (0.07 g) , 0.082 mmol), 2-(dicyclohexylphosphine)biphenyl (0.19 g, 0.54 mmol), K ₃ PO ₄ (5.82 g, 27.5 mmol), stirrer, rack condensate, vacuum and argon Then, 1,4-two "mouth + oxime" (28 ml) and water (6 ml) were driven through a syringe, heated to reflux, and stirred for two days. After returning to room temperature, 1,4-dioxanol was removed by a reduced pressure concentrator and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure and purified solid was purified by column chromatography _{(SiO 2, CH 2 Cl 2} / EA = 5/1), to give a white solid of compound B (1.9 g, 1.71 mmol, 69%). Mp 200~201 ^o C;IR (KBr) ν 3060, 1596, 1525, 1451, 1374, 1324, 1266, 1170, 1087, 899, 843, 789, 744, 696, 647, 499; ¹ H NMR (CD ₂ Cl ₂ , 400 MHz) δ 8.92 (s, 3H), 8.77 (d, J = 7.2 Hz, 3H), 7.94 (s, 3H), 7.82 (d, J = 7.6 Hz, 3H), 7.78 (d, J = 8.0 Hz, 3H), 7.67-7.57 (m, 9H), 7.53-7.49 (m, 6H), 7.46-7.42 (m, 3H), 7.40-7.26 (m, 18H); ¹³ C NMR (CD ₂ Cl ₂ , 400 MHz) δ 171.4, 151.8, 143.0, 140.8, 140.5, 137.4, 137.1, 136.7, 131.3, 130.7, 130.0, 129.2, 128.9, 128.7, 128.3, 128.2, 127.6, 127.4, 123.3, 122.9, 119.7, 110.6, 109.6; HRMS (m/z, FAB+) Cacld. for C ₇₈ H ₅₁ N ₉ 1113.4267, found 1113.4275.

Synthesis of Compound C

Step C-1: Take 100 ml of a single-necked flask, add 3-bromobenzonitrile (5 g, 27.5 mmol), ammonium chloride (1.62 g, 30.3 mmol), sodium azide (3.57 g, 54.9 mmol) and stirrer, condenser shelf, heated to 90 ^o C and reacted for 3 hours, cooled to ambient temperature, salt was filtered off, the filtrate was added 10% aqueous HCl, a white solid precipitated solid was filtered and washed with water. The filtered solid, benzamidine chloride (4.1 ml, 35.3 mmol) and stirrer were placed in a 250 ml round bottom flask, toluene (50 ml) was added, a condenser was placed, heated to reflux and reacted for 12 hours, cooled. To the room temperature, the toluene was removed by a rotary concentrator, and the solid was precipitated from n-hexane. The solid was washed with n-hexane and filtered to give a white solid product (5.58 g, 21.7 mmol, 79%).

Step C-2: Take a 100 ml flask, add the product from step C-1 (4 g, 13.3 mmol), diboron reagent (3.71 g, 14.6 mmol), potassium acetate (3.13 g, 31.9 mmol), PdCl ₂ (dppf) (0.2 g, 0.27 mmol) and stirrer, rack the condenser, vacuum, argon, deionized water tetrahydrofuran (50 ml), heated to 85 ^o C, reacted for 12 hours, cooled to extraction at room temperature, water and dichloromethane, the organic layer was dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure, and then solid was purified (SiO _2, EA / hexane = 1/3) purified by column chromatography , a white solid product (3.72 g, 10.7 mmol, 80%).

Step C-3: Take a 100 ml flask, add the product from step A-1 (1.47 g, 2.69 mmol), the product from step C-2 (3 g, 8.62 mmol), Pd ₂ (dba) ₃ (0.074 g) , 0.081 mmol), 2-(dicyclohexylphosphine)biphenyl (0.19 g, 0.54 mmol), K ₃ PO ₄ (5.7 g, 26.9 mmol), stirrer, rack condensate, vacuum and argon Then, 1,4-two "mouth + oxime" (42 ml) and water (9 ml) were driven through a syringe, heated to reflux, and stirred for two days. After returning to room temperature, it was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure and purified solid was purified by column chromatography _{(SiO 2, CHCl 3 / MeOH} = 20/1), to give the compound C as a white solid (2.4 g , 2.47 mmol, 92%). Mp 272 ^o C (DSC); IR (KBr) ν 3061, 1525, 1490, 1264, 1170, 964, 897, 788, 728, 691, 472; ¹ H NMR (CDCl ₃ , 400 MHz) δ 9.09 ( s, 3H), 8.83 (d, J = 7.6 Hz, 3H), 8.44 (s, 3H), 8.11 (t, J = 8.0 Hz, 9H), 7.88 (d, J = 7.6 Hz, 6H), 7.69 ( t, J = 8.0 Hz, 3H), 7.60 (t, J = 8.0 Hz, 3H), 7.53-7.49 (m, 9H); ¹³ C NMR (CDCl ₃ , 400 MHz) δ 171.2, 164.4, 164.1, 141.5, 140.1, 136.5, 131.6, 131.2, 130.3, 129.5, 129.2, 128.9, 128.4, 127.5, 126.8, 125.8, 125.4, 124.3, 123.7; HRMS (m/z, FAB+) Cacld. for C ₆₃ H ₃₉ N ₉ O ₃ 969.3176 , found 969.3178.

Synthesis of Compound D

Step D-1: 1-(4-Iodophenyl)-2-phenyl-1H-benzo[d]imidazole (5 g, 12.6 mmol) and stirrer were placed in a 250 ml double-necked flask. 25 ml of addition funnel, and the reaction apparatus was fired under vacuum to remove water, and after returning to temperature, argon gas was introduced. Water removal with a syringe into tetrahydrofuran (50 ml), the temperature of the reaction vessel decreased to -78 ^o C, and at this low temperature was slowly added dropwise n-butyl lithium reagent (1.6M, 12ml, 19.2mmol), the reaction After 1 hour, trimethyl borate (2.9 ml, 25.2 mmol) was poured into a bottle, slowly returned to room temperature, and reacted for 4 hours, added with 10% aqueous HCl, stirred for 16 hours, extracted with dichloromethane, organic layer The extract was washed with EtOAc EtOAc (EtOAc m.

Step D-2: Take a 100 ml two-necked flask, add the product of step A-1 (0.65 g, 1.19 mmol), the product from step D-1 (1.24 g, 3.9 mmol), Pd ₂ (dba) ₃ (0.033 g , 0.036 mmol), 2-(dicyclohexylphosphine)biphenyl (0.084 g, 0.24 mmol), K ₃ PO ₄ (2.54 g, 12 mmol), stirrer, rack condensate, vacuum and argon Then, 1,4-two "mouth + oxime" (13 ml) and water (3 ml) were driven through a syringe, heated to reflux, and stirred for two days. After returning to room temperature, 1,4-dioxanol was removed by a reduced pressure concentrator and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure and purified solid was purified by column chromatography _{(SiO 2, CH 2 Cl 2} / EA = 4/1), to give compound D as a white solid of (0.86 g, 0.77 mmol, 64%). Mp 323 ^o C (DSC); IR (KBr) ν 3059, 1606, 1513, 1441, 1380, 1260, 1181, 913, 850, 792, 742, 695, 649, 626, 428; ¹ H NMR (CD ₂ Cl ₂ , 400 MHz) δ 9.18 (s, 3H), 8.87 (d, J = 7.6 Hz, 3H), 7.99 (d, J = 7.6 Hz, 3H), 7.84 (d, J = 7.6 Hz, 6H), 7.92 (d, J = 8.4 Hz, 3H), 7.87 (d, J = 8.0 Hz, 3H), 7.76 (t, J = 8.0 Hz, 3H), 7.84 (d, J = 7.6 Hz, 6H), 7.38-7.19 (m, 24H); ¹³ C NMR (CD ₂ Cl ₂ , 400 MHz) δ 172.3, 152.8, 143.8, 141.2, 140.8, 138.1, 137.4, 137.3, 131.9, 130.7, 130.0, 129.1, 128.8, 128.5, 128.2, 123.9 , 123.5, 120.3, 111.0; HRMS (m/z, FAB+) Cacld. for C ₇₈ H ₅₁ N ₉ 1113.4267, found 1113.4274.

Synthesis of Compound E

Step E-1: Take a 250 ml two-necked flask, add 3-bromoaniline (25 g, 145.3 mmol) and K ₂ CO ₃ (20.1 g, 145.3 mmol), mount the addition funnel and condenser, and attach the nitrogen system. The o-fluoronitrobenzene (15.36 ml, 145.3 mmol) was slowly added dropwise from the addition funnel, heated to 160 ^o C, and reacted for two days, and then purified by column chromatography (SiO ₂ , EA / hexane = 1 /5), an orange solid (18.6 g, 63.45 mmol, 43.7%). Following the reduction of the nitro group, the above orange solid and SnCl ₂ (72.2 g, 381 mmol) were placed in a 500 ml single-necked flask, and 233 ml of ethanol was added thereto, and the mixture was heated under reflux for 12 hours, and then an aqueous sodium hydrogencarbonate solution was added. The solution was taken to aq. EtOAc (EtOAc)EtOAc. Another 500 ml single-necked flask was used to place the obtained brown body, benzamidine chloride (9.8 ml, 84.3 mmol), triethylamine (9.41 ml, 67.5 mmol), dichloromethane (185 ml) and a stir bar. The mixture was stirred for 12 hours, extracted with dichloromethane, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give the phthalamide intermediate. After refluxing for 12 hours, the acetic acid was removed, and the remaining acetic acid was neutralized with aqueous sodium hydroxide solution, extracted with dichloromethane, and then the organic layer was evaporated, then re-precipitated with dichloromethane and n-hexane, and filtered to give a white solid product. (15.1 g, 43.24 mmol, 77%).

Step E-2: Take a 250 ml flask, add the product from step E-1 (7 g, 20 mmol), diboron reagent (6.1 g, 24 mmol), potassium acetate (4.72 g, 48 mmol), PdCl ₂ (dppf) (0.3 g, 0.4 mmol) and stirrer, rack the condenser, vacuum, argon, deionized tetrahydrofuran (126 ml), heated to reflux, reacted for 12 hours, cooled to room temperature and extracted with water and dichloromethane, the organic layer was dried over anhydrous magnesium sulfate, and filtered and the filtrate was concentrated under reduced pressure, and then solid was purified (SiO _2, EA / hexane = 1/4) by using column chromatography to obtain White solid product (5.56 g, 14 mmol, 70%).

Step E-3: Take a 100 ml flask, add the product from step A-1 (1.72 g, 3.15 mmol), the product from step E-2 (4 g, 10.1 mmol), Pd ₂ (dba) ₃ (0.09 g) , 0.1 mmol), 2-(dicyclohexylphosphine)biphenyl (0.22 g, 0.63 mmol), K ₃ PO ₄ (6.67 g, 31.5 mmol), stirrer, rack condensate, vacuum and argon Then, 1,4-two "mouth + oxime" (47.5 ml) and water (9.5 ml) were driven through a syringe, heated to reflux, and stirred for two days. After returning to room temperature, 1,4-dioxanol was removed by a reduced pressure concentrator and extracted with dichloromethane. The organic layer was taken, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure, and then purified by column chromatography (SiO ₂ , EA/CH ₂ Cl ₂ = 1/7) with dichloromethane and The alkane was reprecipitated to give compound E (2.63 g, 2.36 mmol, 75%) as a white solid. Mp 270~271 ^o C;IR (KBr) ν 3058, 1601, 1527, 1494, 1475, 1378, 1326, 1273, 1181, 1087, 1003, 921, 890, 834, 787, 744, 699, 646, 505, 433; ¹ H NMR (CDCl ₃ , 400 MHz) δ 8.95 (s, 3H), 8.76 (d, J = 7.6 Hz, 3H), 7.93 (d, J = 8.0 Hz, 3H), 7.83 (d, J = 7.6 Hz, 3H), 7.73-7.71 (m, 6H), 7.68-7.64 (m, 9H), 7.56 (t, J = 7.6 Hz, 3H), 7.39-7.26 (m, 21H); ¹³ C NMR (CDCl ₃ , 400 MHz) δ 170.9, 151.8, 142.0, 139.7, 137.1, 136.6, 136.3, 131.0, 130.1, 129.1, 128.3, 128.0, 127.1, 126.9, 126.1, 125.5, 123.2, 122.9, 119.6, 110.2; HRMS (m/ z, FAB+) Cacld. for C ₇₈ H ₅₁ N ₉ 1113.4267, found 1113.4283.

Synthesis of Compound F

Step F-1: Take a 100 ml flask, add the product from step A-1 (1 g, 1.83 mmol), diboron reagent (1.67 g, 6.57 mmol), potassium acetate (1.3 g, 13.2 mmol), PdCl ₂ (dppf) (0.08 g, 0.11 mmol) and stirrer, rack the condenser, evacuate, argon gas, dehydrated tetrahydrofuran (35 ml), heat to 85 ^o C, react for 12 hours, cool to extraction at room temperature, water and dichloromethane, the organic layer was dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure, and then solid was purified (SiO _2, EA / hexane = 1/2) purified by column chromatography , a white solid product (1.04 g, 1.51 mmol, 83%).

Step F-2: Take the 250 ml two-necked flask, the product of step F-1 (3 g, 4.37 mmol), 3-bromobenzonitrile (2.64 g, 14.5 mmol), Pd(PPh ₃ ) ₄ (0.78 g , 0.67 mmol) and the flask placed stirrer, condenser shelves, purged with argon after the evacuation, with a syringe into _{Na 2 CO 3 (aq) (} 19.8 mL, 39 mmol, 2.0 M), P t Bu ₃ (26.2 mL, 1.34 mmol, 0.05 M dissolved in toluene) and toluene (100 mL) were heated to reflux, stirred and reacted for 72 hours. After returning to room temperature, water was added to quench the reaction, and the aqueous solution was extracted with dichloromethane. The organic layer was dried with EtOAc EtOAcjHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHH ^{mp 290 o C (DSC);} IR (KBr) ν 3062, 2230, 1587, 1527, 1488, 1452, 1392, 1347, 1262, 1166, 1136, 1088, 900, 784, 689, 648, 492, 438; 1 H NMR (CDCl ₃ , 400 MHz) δ 8.97 (s, 3H), 8.85 (d, J = 7.6 Hz, 3H), 8.03 (s, 3H), 7.99 (d, J = 7.8 Hz, 3H), 7.85 ( d, J = 7.6 Hz, 3H), 7.77-7.72 (m, 6H), 7.67 (t, J = 7.6 Hz, 3H); ¹³ C NMR (CDCl ₃ , 400 MHz) δ 171.6, 142.0, 139.5, 136.9, 131.6, 131.4, 131.2, 130.8, 129.9, 129.7, 129.0, 127.5, 118.9, 113.2; HRMS (m/z, FAB+) Cacld. for C ₄₂ H ₂₄ N ₆ 612.2026, found 612.2060; Anal. Calcd. C, 82.33; H, 3.95; N, 13.72, found C, 82.37; H, 4.14; N, 13.56.

Synthesis of Compound G

Step G-1: Take a 500 ml flask and add the product of step A-1 (6 g, 11 mmol), Pd ₂ (dba) ₃ (0.76 g, 11 mmol), Xantphos ligand (0.95 g, 1.64). Ment) and stirrer, rack the condenser, vacuum and then argon, use a syringe to drive 4-tert-butylthiophenol (6.25 ml, 36.3 mmol), i Pr ₂ NEt (10.9 ml, 66 mmol) And 1,4-two "mouth + oxime" (210 ml), heated to reflux, stirred and reacted for 48 hours, returned to room temperature, added water to quench the reaction, the aqueous solution was extracted with dichloromethane, and the organic layer was taken. , dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure and purified solid was purified by column chromatography _{(SiO 2, CH 2 Cl 2} / hexane = 7/1), to give the product as a white solid (8.5 g, 10.6 M, 96%).

Step G-2: Take 25 ml single-neck flask, was added 30% H ₂ O ₂ aqueous solution (1.5 ml, 15 mmol), at -20 ^o C was slowly added dropwise trifluoroacetic anhydride (3.96 ml, 28 mmol), After stirring for 5 minutes at 5 ^o C, the product of step G-1 (0.5 g, 0.62 mmol) was added, and the mixture was stirred at room temperature for 3 hours. Under ice bath, saturated aqueous sodium carbonate solution was added until pH = 5, and aqueous solution was used. The organic layer was extracted with EtOAc EtOAc (EtOAc)EtOAc. Mp 298 ^o C (DSC); IR (KBr) ν 3070, 2963, 2869, 1594, 1524, 1476, 1432, 1398, 1365, 1324, 1150, 1092, 1013, 891, 839, 796, 759, 710, 685 , 627, 583, 513; ¹ H NMR (CDCl ₃ , 400 MHz) δ 9.30 (s, 3H), 8.92 (d, J = 7.8 Hz, 3H), 8.20 (d, J = 6.6 Hz, 3H), 8.01 (d, J = 7.4 Hz, 6H), 7.76 (t, J = 7.6 Hz, 3H), 7.59 (d, J = 7.4 Hz, 6H); ¹³ C NMR (CDCl ₃ , 400 MHz) δ 170.2, 157.1, 142.9, 137.8, 136.5, 133.1, 131.4, 129.8, 128.0, 127.6, 126.5, 35.8, 31.6; HRMS (m/z, FAB+) Cacld. for C ₅₁ H ₅₁ N ₃ O ₆ S ₃ 897.2940, found 897.2940; Anal. Calcd. C, 68.20; H, 5.73; N, 4.68; S, 10.71, found C, 67.71; H, 5.72; N, 4.59; S, 10.49.

Synthesis of Compound H

Step H-1: Take 100 ml of a single-necked flask, put 3-iodobenzonitrile (2 g, 8.73 mmol) and a stirrer into the bottle, add dehydrated dichloromethane (20 ml), and add three at room temperature. Fluoromethanesulfonic acid (2 ml, 14.5 mmol) was stirred for 24 hours. The reaction was quenched with saturated aqueous sodium hydrogen sulfate, and extracted with dichloromethane. EtOAcjjjjjjjjjjjjjjjjj Product (1.45 g, 2.1 mmol, 73%).

Step H-2: Take a 250 ml two-necked flask, add the product of step H-1 (10 g, 14.6 mmol), Pd(PPh ₃ ) ₄ (0.5 g, 0.43 mmol) and stirrer, and condense the tube and pump after vacuum purged with argon, into a syringe with diphenylphosphine (8.4 ml, 48.3 mmol), triethylamine (6.6 ml, 48.2 mmol), and toluene (120 ml), heated to 80 ^o C, for 24 hours, After returning to room temperature, a water quenching reaction was carried out, and the aqueous solution was extracted with dichloromethane. The organic layer was taken and dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure, and purified by column chromatography (SiO ₂ , EA / Hexane = 9/1), re-precipitated with methylene chloride and methanol and filtered to give a white solid product (6.3 g, 7.3 mmol, 50%).

Step H-3: Take a 25 ml single-necked flask, add the product of step H-2 (1.5 g, 1.74 mmol) and dichloromethane (10 ml), dissolve it with an ultrasonic oscillator, and add 30% H. _An aqueous solution of ₂ O ₂ (1.3 ml, 13 mmol), EtOAc. Re-precipitation with methylene chloride and n-hexane afforded compound H (1.55 g, 1.7 mmol, 98%). ^{mp 287 o C (DSC);} IR (KBr) ν 3052, 1635, 1593, 1523, 1436, 1356, 1274, 1198, 1115, 996, 922, 891, 796, 751, 723, 694, 641, 543; 1 H NMR (CDCl ₃ , 400 MHz) δ 8.99 (d, J = 12.4 Hz, 3H), 8.73 (d, J = 7.6 Hz, 3H), 7.89-7.85 (m, 3H), 7.73-7.68 (m, 12H ), 7.66-7.62 (m, 3H), 7.57-7.47 (m, 18H); ¹³ C NMR (CDCl ₃ , 400 MHz) δ 170.9, 136.1, 136.0, 135.9, 133.9, 132.8, 132.7, 132.5, 132.4, 132.2 , 132.1, 131.7, 129.0, 128.9, 128.7, 128.6; HRMS (m/z, FAB+) Cacld. for C ₅₇ H ₄₂ N ₃ O ₃ P ₃ 909.2439, found 909.2440; Anal. Calcd. C, 75.24; H, 4.65 ;N, 4.62, found C, 75.48; H, 4.36; N, 4.60.

Synthesis of Compound I

2,4,6-tris(3-bromophenyl)-1,3,5-three "mouth + well" (1.69 g, 3.09 mmol), 1 H -pyrazole (1.26 g, 18.51 mmol), copper (II) Oxide (74 mg, 0.93 mmol), tris(acetonitrile)iron (III) (984 mg, 2.79 mmol), cesium carbonate (6.19 g, 19 mmol) and anhydrous DMF (60 mL) in argon Under reflux for 72 hours. The DMF was evaporated and the crude product was dissolved in CHCl ₃ and filtered to remove non-soluble solid. The organic solution was extracted with brine and dried MgSO _4. To _{Al 2 O 3 (CH 2 Cl} 2 / Hex / MeOH = 5/2 / 0.1) was purified by column chromatography to afford the compound I as a white solid (1.27 g, 81% yield). ¹ H NMR (CDCl ₃ , 400 MHz) δ 9.04 (d, J = 1.6 Hz, 3H), 8.72 (dd, J = 8.0, 1.6 Hz, 3H), 8.13 (d, J = 2.8 Hz, 3H), 8.02 (dd, J = 8.0, 1.6 Hz, 3H), 7.82 (d, J = 1.6, 3H), 7.69 (t, J = 8.0 Hz, 3H), 6.57 (separation of asymmetric triplet, 3H); ¹³ C NMR (CDCl ₃ , 100 MHz) δ 170.5, 140.9, 140.2, 136.8, 129.5, 126.7, 123.2, 119.0, 109.2, 107.7; HRMS (m/z, ESI+) Calcd for C ₃₀ H ₂₁ N ₉ 507.1920, found (M + H+): 508.1996; Anal. Calcd. For C ₃₀ H ₂₁ N ₉ : C, 70.99; H, 4.17; N, 24.84. Found: C, 70.68; H, 4.08; N, 25.03; Compound I is soluble in CH ₂ Cl ₂ and CHCl ₃ .

Embodiment: Characteristic measurement of organic light-emitting elements

An organic light-emitting device was fabricated by vacuum evaporation, and relevant parameters were measured to prepare (1) I-V-L curve, (2) external quantum efficiency and luminous power efficiency versus brightness, and (3) luminescence spectrum.

Organic light-emitting element using compound G

Element Structure 1: ITO/PEDOT/NPB(200)/TCTA(150)/Compound G(650)/Liq/Al, where the value in parentheses is the thickness of the layer in angstroms.

In the present embodiment, two layers of hole transport layers NPB and TCTA and a layer of compound G are used as electron transport layers to confirm the formation of exciplex luminescence between TCTA and compound G.

The relevant measurement curves of this component 1 can be seen in Figures 1A, 1B and 1C, and the relevant efficiency data of this component 1 is shown in Table 1, where V _on represents the driving voltage of the component; L 100 represents the operating voltage of the luminance at 100 nits. L _max represents maximum brightness; I _max represents maximum current; h _ext represents maximum external quantum efficiency; h _c represents maximum current efficiency; h _p represents maximum luminous power efficiency.

Organic light-emitting element using compound H

Element structure 2: ITO / PEDOT / TAPC (200) / mCP (150) / compound H (650) / Liq / Al;

Element structure 3: ITO/PEDOT/TAPC (200)/mCP (150) / 1:1 mixture of compound H and mCP (200) / compound H (450) / Liq / Al;

Element structure 4-8: ITO/PEDOT/hole transport material (250) / compound H (750) / Liq / Al;

In the present embodiment, the element structure 2 confirms the phenomenon of formation of exciplex luminescence between the mCP and the compound H; the element structure 3 confirms the use of the 1:1 mixture of the electron transport material compound H and the hole transport material mCP. The phenomenon of excimer complex luminescence; and the structure of components 4-8 confirms the phenomenon of formation of exciplex luminescence between various hole transport materials and compound H, wherein the tested hole transport materials include: Element structure 4: NPB (150)/TCTA(50)/mCP(50) Component structure 5: NPB(200)/TCTA(50) Component structure 6: TAPC (250) Component structure 7: DTAF (250) Component structure 8: mt-DATA ( 250)

The relevant measurement curves of the component structures 2 and 3 can be seen in Figures 2A to 2D, and the relevant efficiency data are shown in Table 2; the correlation measurement curves of the component structures 4-8 can be seen in Figures 2E to 2G, and the relevant efficiency data are as shown in Table 3. Show.

Organic light-emitting element using Compound I

Element Structure 9-12: ITO/PEDOT/NPB(200)/TCTA(50)/1:1 mixture of Compound I and TCTA (x)/Compound I (750-x)/LiF/Al

In the present embodiment, the phenomenon that the mixture of the electron transporting material compound I and the hole transporting material TCTA is excited at different thicknesses is confirmed, wherein the thickness of the mixture (weight ratio 1:1) is represented by x. When x is 0, it means that there is no mixture layer. The thickness tested includes: Component structure 9: x is 0 Component structure 10: x is 50 angstroms Component structure 11: x is 150 angstroms Component structure 12: x is 250 angstroms

The associated measurement curves for element structures 9-12 can be seen in Figures 3A through 3C, and the associated efficiency data is shown in Table 4, where L 1000 represents the operating voltage at 1000 nits.

It can be seen from the foregoing examples and embodiments that the electron transporting material of the present invention can be combined with a hole transporting material to achieve an exciplex luminescence phenomenon in two bi-layer types or a mixed type. Not only can various luminescent colors be formed, but also satisfactory luminous efficiency can be achieved.

Composite organic light-emitting element

Element structure 13-15: 1:1 mixture of ITO/PEDOT:PSS/TAPC(35-x)/mCP(x)/compound H and mCP (20)/compound H (45)/LiF/Al

This example confirms the exciplex luminescence phenomenon in the case where mCP is contained as a buffer layer. In order to understand the influence of the thickness of the buffer layer, the following three structures are tested in this embodiment: Element structure 13: x is 0 (ie, there is no buffer layer) Element structure 14: x is 6 nm Element structure 15: x is 15 nm

The relevant measurement curves of the element structures 13-15 can be seen in Figures 4A and 4B. Figure 4C shows the spectral changes of the element structure 14 at different brightnesses, and the relevant efficiency data for each element is shown in Table 5.

The white light phenomenon produced by the physical characteristics of the element structures 13-15 and the element structure 14 can be presumed to occur in the luminescent layer composed of a 1:1 mixture of the compound H and the mCP when the buffer layer is present and has a specific thickness. The first type of exciplex luminescence (emitting a relatively short-wavelength blue light), and between the compound H and the TAPC located on both sides of the buffer layer, the accumulated electrons have a chance to tunnel to the TAPC because the buffer layer is thin enough. The second excimer luminescence (emission of orange light of a relatively long wavelength) is generated, so that the composite organic light-emitting element as a whole exhibits white light.

On the other hand, if the thickness of the buffer layer is too large (as in the case of the element structure 15), it is presumed that between the compound H and the TAPC, the electrons have a large barrier to form an excited state due to the observed blue light emission phenomenon. Complex glow. In addition, it can be observed from FIG. 4C that in the composite organic light-emitting element of the element structure 14, spectral changes occur under different voltage driving, for example, the spectrum shows a blue shift phenomenon at a high current density, and the main light-emitting area thereof is The proportion of blue exciplex complex binding regions increases.

Tandem organic light-emitting element

Element Structure 16: ITO/PEDOT: PSS/TAPC (20) / mCP (15) / mCP: Compound H (20) / Compound H (45) / Liq (1) / Al (1) / MoO ₃ (5) / DTAF(20)/DTAF: Compound H(20)/Compound H(50)/Liq/Al

This embodiment confirms the physical properties of the tandem excited composite organic light-emitting element, wherein the structure TAPC (20) / mCP (15) / mCP: compound H (20) / compound H (45) as the first organic light-emitting unit , with structure DTAF(20)/DTAF: compound H(20)/compound H(50) as the second organic light-emitting unit, and Liq(1)/Al(1)/MoO ₃ (5) as the intermediate connection layer Separate two organic light-emitting units. Although two organic light-emitting units are described herein as an example, it should be understood that three, four, five or more organic light-emitting units may be used as needed to form a tandem organic light-emitting element.

In this embodiment, under the applied bias, the mixture layer mCP in the first organic light-emitting unit: compound H (20) can emit blue light, and the mixture layer DTAF in the second organic light-emitting unit: compound H (20) can be The yellow light is emitted, so that the tandem organic light-emitting element emits white light as a whole.

The associated measurement curves for component structure 16 can be seen in Figures 5A through 5C, and the associated efficiency data is shown in Table 6. Among them, it is worth noting that unlike the severe color shift phenomenon that is commonly found in general tandem organic light-emitting elements, the element structure 16 of the present embodiment has no such problem, as shown in FIG. 5C.

Accordingly, the inventors have fully described the concept of specific embodiments and examples in the foregoing description. It is to be understood that those skilled in the art can make various changes, changes and modifications in the scope of the invention as defined by the appended claims. Therefore, the present invention is to be construed as being limited by the scope of the invention.

In addition, some of the features of the various embodiments described herein may also be provided in combination in a separate embodiment, and the various embodiments may be provided separately or in any sub-combination. In addition, the relevant numerical values described in the range should include each value in the range.

1A, 1B and 1C are respectively a luminance-voltage-current density curve, a quantum efficiency-brightness-power efficiency curve and a spectrum diagram of the component 1; FIGS. 2A, 2B, 2C and 2D are the luminances of the component 2 and the component 3, respectively. - voltage-current density curve, quantum efficiency-brightness-power efficiency curve and spectrum; Figure 2E, 2F and 2G are the brightness-voltage-current density curve of component 4-8, quantum efficiency-brightness-power efficiency Graphs and spectra; Figures 3A, 3B, and 3C are the luminance-voltage-current density plots, quantum efficiency-brightness-power efficiency plots, and spectra of components 9-12, respectively; Figures 4A and 4B are components 13-, respectively. 15 luminance-voltage-current density graph and quantum efficiency-brightness-power efficiency graph, FIG. 4C is a spectrum diagram of component 14 at different brightness; and FIGS. 5A, 5B, and 5C are luminance-voltage of component 16 respectively. Current density plot, quantum efficiency-brightness-power efficiency plot and spectrogram.

no

Claims (32)

An electron transporting material comprising a compound represented by the following formula (I): Each of the A ₁ groups is the same or different and represents an aromatic ring, and each X is the same or different and represents an electron withdrawing group. The electron transporting material of claim 1, wherein at least one of A ₁ is an aromatic hydrocarbon ring. The electron transporting material according to claim 2, wherein the aromatic hydrocarbon ring is a C ₆ - C ₂₀ aromatic hydrocarbon ring. The electron transporting material according to claim 2, wherein at least one of A ₁ is a benzene ring, and the X system bonded to the benzene ring is at a meta position. The electron transporting material according to claim 1, wherein each X system is independently selected from the group consisting of the following groups: Each of the A ₂ groups is the same or different and represents an aromatic ring. The electron transporting material of claim 5, wherein at least one of A ₂ is a substituted or unsubstituted aromatic hydrocarbon ring. The electron transporting material according to claim 6, wherein the aromatic hydrocarbon ring is a C ₆ - C ₂₀ aromatic hydrocarbon ring. The electron transporting material according to claim 1, wherein the compound represented by the formula (I) is any one of the formulae (II) to (IV): An organic light-emitting element comprising: an anode; at least one hole transport layer on the anode, the hole transport layer comprising a hole transport material; at least one electron transport layer on the hole transport layer, The electron transporting layer includes an electron transporting material; and a cathode on the electron transporting layer, wherein the electron transporting material comprises the electron transporting material according to any one of claims 1 to 8, such that the organic light emitting component Excited complex luminescence is formed between the hole transport layer and the electron transport layer under an applied bias voltage. The organic light-emitting device of claim 9, further comprising a light-emitting layer interposed between the hole transport layer and the electron transport layer, such that the organic light-emitting element is excited in the light-emitting layer under an applied bias voltage The complex glows. The organic light-emitting element of claim 10, wherein the light-emitting layer is composed of a mixture of the hole transport material and the electron transport material. The organic light-emitting device of claim 9, wherein the hole transporting material is selected from the group consisting of N,N'-bis(naphthalen-1-yl)-N,N'-di(phenyl)benzidine (NPB) ), 4,4',4"-tris(N-carbazolyl)-triphenylamine (TCTA), 1,3-bis(carbazol-9-yl)benzene (mCP), 1,1-double [( Di-4-toluamino)phenyl]cyclohexane (TAPC), 5-(4,6-dichlorotrisole "well +-2-yl)amino fluorescein (DTAF), 4,4 ',4"-tris(N-3-methylbenzene-N-anilino)-triphenylamine (mt-DATA), N,N'-diphenyl-N,N'-di-[4-(N a group consisting of N-diphenylamino)phenyl]benzidine (NPNPB) and mixtures thereof. The organic light-emitting element according to claim 9, wherein the hole transport layer and the electron transport layer are in contact with each other. The organic light-emitting element according to claim 9, which is a blue light, a green light, a yellow light, an orange light or a red light organic light emitting diode. The organic light-emitting device of claim 9, further comprising: a hole injection layer between the hole transport layer and the anode; and an electron injection layer between the electron transport layer and the cathode. An organic light-emitting element consists essentially of: an anode layer; at least one hole transport layer on the anode layer, the hole transport layer comprising a hole transport material; at least one electron transport layer, Located on the hole transport layer, the electron transport layer includes an electron transport material; and a cathode layer over the electron transport layer, wherein the HOMO of the hole transport material and the LUMO system of the electron transport material are mutually Correspondingly, the organic light-emitting element is caused to form an exciplex light-emitting between the hole transport layer and the electron transport layer under an applied bias voltage. The organic light-emitting element according to claim 16, wherein the electron-transporting material is the electron-transporting material according to any one of claims 1 to 8. The organic light-emitting device according to claim 17, wherein the hole transporting material is selected from the group consisting of N,N'-bis(naphthalen-1-yl)-N,N'-di(phenyl)benzidine ( NPB), 4,4',4"-tris(N-carbazolyl)-triphenylamine (TCTA), 1,3-bis(carbazol-9-yl)benzene (mCP), 1,1-double [ (di-4-toluamino)phenyl]cyclohexane (TAPC), 5-(4,6-dichlorotrisulphate + well-2-yl)amino fluorescein (DTAF), 4, 4',4"-tris(N-3-methylphenyl-N-anilino)-triphenylamine (mt-DATA), N,N'-diphenyl-N,N'-di-[4-( A group consisting of N,N-diphenylamino)phenyl]benzidine (NPNPB) and mixtures thereof. A composite organic light-emitting device comprising: an anode; a hole transport layer on the anode, the hole transport layer comprising a first hole transport material; a buffer layer located above the hole transport layer The buffer layer includes a second hole transport material different from the first hole transport material; an electron transport layer located above the buffer layer, the electron transport layer including a first electron transport material; A cathode, located above the electron transporting layer, wherein the first electron transporting material comprises the electron transporting material of any one of claims 1 to 8. The composite organic light-emitting device of claim 19, wherein the composite organic light-emitting device has a first excitation state of the HOMO of the first hole transporting material and the LUMO of the first electron transporting material under an applied bias voltage The bulk luminescence, the HOMO of the second hole transporting material and the LUMO of the first electron transporting material form a second excimer complex luminescence. The composite organic light-emitting device of claim 19, further comprising a light-emitting layer interposed between the buffer layer and the electron transport layer, the light-emitting layer comprising a third hole transport material and a second electron transport material The second electron-transporting material includes the electron-transporting material according to any one of claims 1 to 8, such that the composite organic light-emitting element is under an applied bias, the HOMO of the third hole transporting material and the second The LUMO of the electron transporting material forms a third exciplex illuminating light, and the HOMO of the first hole transporting material and the LUMO of the second electron transporting material form a fourth exciplex illuminating. The composite organic light-emitting element according to claim 21, wherein the second hole transporting material is the same as the third hole transporting material, and the first electron transporting material is the same as the second electron transporting material. The composite organic light-emitting device according to claim 21, wherein the third exciplex light is blue light, and the fourth excited complex light is orange light. The composite organic light-emitting device according to claim 21, wherein the first, second and third hole transporting materials are each independently selected from N, N'-bis(naphthalen-1-yl)-N, N'-bis(phenyl)benzidine (NPB), 4,4',4"-tris(N-carbazolyl)-triphenylamine (TCTA), 1,3-bis(carbazol-9-yl) Benzene (mCP), 1,1 bis[(di-4-toluamino)phenyl]cyclohexane (TAPC), 5-(4,6-dichlorotriene "mouth + well"-2-yl) Aminofluorescein (DTAF), 4,4',4"-tris(N-3-methylphenyl-N-anilino)-triphenylamine (mt-DATA), N,N'-diphenyl- A group consisting of N,N'-di-[4-(N,N-diphenylamino)phenyl]benzidine (NPNPB) and mixtures thereof. The composite type organic light-emitting element according to claim 19, wherein the buffer layer has a thickness for electron tunneling. A composite organic light-emitting device according to claim 19, which is a white organic light-emitting device. A tandem organic light-emitting device, comprising: an anode; a cathode; at least two organic light-emitting units disposed between the anode and the cathode, wherein the organic light-emitting units each independently comprise an electron transport layer and a hole transmission a layer, the hole transport layer comprising a hole transporting material, the electron transporting layer comprising the electron transporting material of any one of claims 1 to 8; and at least one intermediate connecting layer disposed on the organic light emitting unit In each of the organic light emitting units, the HOMO of the hole transporting material and the LUMO of the electron transporting material correspond to each other, so that the organic light emitting unit is applied to the hole transport layer and the electron transporting layer under an applied bias voltage. Excited complex luminescence is formed between the layers. The tandem organic light-emitting device of claim 27, wherein the at least one organic light-emitting unit further comprises a light-emitting layer interposed between the electron transport layer and the hole transport layer, such that the organic light-emitting unit is under an applied bias voltage. Excited complex luminescence is formed in the luminescent layer. The tandem organic light-emitting element according to claim 28, wherein the light-emitting layer of each of the organic light-emitting units is composed of a mixture of a hole transport material and an electron transport material. The tandem organic light-emitting device of claim 27, wherein the hole transporting materials are each independently selected from the group consisting of N,N'-bis(naphthalen-1-yl)-N,N'-di(phenyl) Benzidine (NPB), 4,4',4"-tris(N-carbazolyl)-triphenylamine (TCTA), 1,3-bis(carbazol-9-yl)benzene (mCP), 1, 1-‐bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), 5-(4,6-dichlorotris("+"-2-yl)aminofluorescein (DTAF) , 4,4',4"-tris(N-3-methylbenzene-N-anilino)-triphenylamine (mt-DATA), N,N'-diphenyl-N,N'-di- A group consisting of [4-(N,N-diphenylamino)phenyl]benzidine (NPNPB) and mixtures thereof. The tandem organic light-emitting element of claim 27, wherein the organic light-emitting units respectively emit visible light of different colors. A tandem organic light-emitting element according to claim 27, which is a white organic light-emitting element.