Luminescent copper halide cluster as well as preparation method and application thereof

Abstract

The invention provides a luminous copper halide cluster as well as a preparation method and application thereof. The light-emitting copper halide cluster has visible light emission with high light-emitting efficiency in a film state, the molecular structure of the light-emitting copper halide cluster is high in expansibility, and the light color is easy to regulate and control. Meanwhile, the copper halide cluster is good in machinability, and a membrane can be prepared through a vacuum sublimation method or a solution method. The two problems of the majority of copper halide cluster luminescent materials in the prior art are overcome: (1) the copper halide cluster luminescent materials are poor in processability, difficult to sublimate and low in solubility; and (2) the non-radiation loss of the excited state is serious, resulting in insufficient luminous efficiency of the film.

Description

Technical Field

[0001] This invention belongs to the field of luminescent materials technology, specifically relating to a class of luminescent copper halide clusters, their preparation methods, and applications. Background Technology

[0002] Organic light-emitting diodes (OLEDs) possess advantages such as high response, wide viewing angle, low power consumption, ultra-thinness, and flexible display, and have become a leading display technology. Monovalent copper complexes, with their abundant metal resources, low cost, structural diversity, rich photophysical properties, and high exciton utilization, hold promise as a replacement for OLEDs. 6 and d 8 Noble metal phosphorescent complexes with electronic configurations are used in OLEDs. However, most monovalent copper complexes still face challenges such as low luminescence efficiency in thin film states, wide emission spectrum, and difficulty in purification and coating through sublimation.

[0003] Furthermore, existing OLEDs based on monovalent copper complexes cannot achieve high color purity blue light (color coordinate CIE-y < 0.2). Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a type of luminescent copper halide cluster, which is a compound represented by formula (I):

[0005]

[0006] in:

[0007] X is a halogen, selected from Cl, Br, or I;

[0008] R are the same or different, and are independently selected from C. 1-12 Alkyl, C 1-12 Alkoxy, C 6-20 Aryl, 5-22 heteroaryl, -N-(C 6-20 aryl)2 or -N-(5-22 heteroaryl)2;

[0009] n is 0, 1, 2, 3, 4 or 5;

[0010] Y is selected from any one of the following chemical bonds: -O-, -S-, -Se-, -Te-, -C(O)-, -S(O)2-, -C(R'R”)-, -Si(R'R”), -N(R'-, -P(R'-), -P(=O)R'-, or -B(R'-.

[0011] R' and R" may be the same or different, and are independently selected from hydrogen, deuterium, halogen, nitrile, unsubstituted, or optionally substituted by one, two, or more Ra groups, including the following groups: C 1-12 Alkyl, -COC 1-12 Alkyl, -COOC1-12 Alkyl, -CONHC 1-12 Alkyl, C 3-20 cycloalkyl, C 1-12 Alkoxy, C 6-20 aryloxy group, C 1-12 Alkyl thio, C 6-20 Arylthio, C 1-12 alkylsulfonyl, C 6-20 arylsulfonyl, C 2-12 alkenyl, -Si(C) 1-12 Alkyl)3, -Si(C 6-20 aryl)3,-Si(5-22 heteroaryl)3,-B(C 1-12 Alkyl)2, -B(C 6-20 aryl)2, -B(5-22 heteroaryl)2, NH2, -P(C 6-20 aryl)3, phosphino (P=O), C 6-20 Aryl, 5-22 membered heteroaryl, 3-20 membered heterocyclic; or R' and R" together with their attached C or Si to form unsubstituted or substituted ring systems as follows: C 3-20 Cycloalkyl, 3-20 membered heterocyclic groups, C 6-20 Aryl or 5-22 heteroaryl groups;

[0012] Ra is selected from =O, halogen, nitrile, nitro, hydroxyl, aldehyde, C 1-12 Alkyl, -COC 1-12 Alkyl, -COOC 1-12 Alkyl, C 3-20 cycloalkyl or C 1-12 Alkyl group.

[0013] According to an embodiment of the present invention, in the compound represented by formula (I), X is a halogen selected from Cl, Br or I;

[0014] R is selected from C 1-6 Alkyl, C 1-6 Alkoxy, C 6-14 Aryl, 5-14 heteroaryl, -N-(C 5-14 aryl)2 or -N-(5-14 heteroaryl)2; n is 0, 1, 2 or 3;

[0015] Y represents a chemical bond, such as -O-, -S-, -Se-, -Te-, -C(O)-, -S(O)2-, -N(R')-, -P(R')-, -, -C(C 1-6 alkyl)2-, -Si(C 1-6 alkyl)2-, -Si(C 6-14 Aryl)2-, -C(C 6-14When aryl)2- or Y is CR'R”, R' and R” together with the C connected to them constitute an unsubstituted or =O substituted C. 6-14 Aryl;

[0016] According to an embodiment of the present invention, in the compound represented by formula (I), X is a halogen selected from Cl, Br or I;

[0017] R is selected from methyl, ethyl, tert-butyl, methoxy, phenyl, carbazole, acridine; n is 1, 2, 3 or 4.

[0018] In some embodiments of the present invention, n is 1, R is selected from methyl, ethyl or methoxy, and R is substituted at the ortho or para position of the benzene ring.

[0019] In some embodiments of the present invention, n is 3, R is selected from methyl or ethyl, and R is substituted at the ortho and para positions of the benzene ring.

[0020] Preferably, Y is a chemical bond, -O-, -S-, -Se-, -C(CH3)2-, -Si(CH3)2-, -CPh2-, -SiPh2-, or fluorene group. or anthrone group The black box marks the connection point of Y.

[0021] In some specific embodiments of the present invention, formula (I) has the structure shown in formula (I'):

[0022]

[0023] Each group has the definition described above.

[0024] In some specific embodiments of the present invention, in formula (I'), X is a halogen selected from Cl, Br or I;

[0025] R is selected from C 1-6 Alkyl, C 1-6 Alkoxy, C 6-14 Aryl, 5-14 heteroaryl, such as methyl, ethyl, tert-butyl, methoxy, phenyl, carbazolyl, acridine; n is 0, 1, 2 or 3;

[0026] n is 1, R is selected from methyl, ethyl, or methoxy, and R is substituted at the ortho or para position on the benzene ring; or...

[0027] n is 3, R is selected from methyl or ethyl, and R is substituted at the ortho and para positions of the benzene ring;

[0028] Y represents chemical bonds, -O-, -S-, -Se-, -C(C 1-6 alkyl)2-, -Si(C 1-6 alkyl)2-, -C(C 6-14aryl)2-,-Si(C 6-14 Aryl)2-, Fluorene or anthrone group The black boxes mark the connection sites for Y, such as chemical bonds, -O-, -S-, -Se-, -C(CH3)2-, -Si(CH3)2-, -CPh2-, -SiPh2-, and fluorene groups. or anthrone group The black box marks the connection site of Y; when Y is a fluorene group. or anthrone group In this case, equation (I) is selected from the structure shown below:

[0029]

[0030] In some specific embodiments of the present invention, the compound shown in formula (I) has a symmetrical structure.

[0031] In some specific embodiments of the present invention, the compound represented by formula (I) is selected from one of the following structures:

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038] According to an embodiment of the present invention, the compound shown in formula (I) is a copper halide cluster luminescent material.

[0039] The present invention also provides a method for preparing the compound shown in formula (I) above, comprising the following steps:

[0040] The compound shown in formula (I-1) reacts with copper halide CuX to give the compound shown in formula (I);

[0041]

[0042] Where R, n, Y and X have the definitions described above.

[0043] The present invention also provides the use of the above-mentioned luminescent copper halide clusters as luminescent or sensitizing materials in the preparation of organic electronic devices, preferably in the preparation of organic electroluminescent devices.

[0044] According to an embodiment of the present invention, the luminescent copper halide cluster has photoluminescence or electroluminescence properties and can emit visible light.

[0045] According to an embodiment of the present invention, when the luminescent copper halide cluster is used as a sensitizing material, the luminescent material used in conjunction is any luminescent material.

[0046] The present invention also provides an organic electroluminescent device comprising two electrodes and an organic layer located between the electrodes, wherein the organic layer comprises the aforementioned luminescent copper halide cluster.

[0047] Preferably, the organic layer is one, two or more of the following: an injection layer, a transport layer, a light-emitting layer, and a blocking layer.

[0048] Preferably, the luminescent copper halide cluster is located in the luminescent layer as a luminescent material or sensitizer.

[0049] The present invention also provides a method for preparing the organic electroluminescent device, comprising the following steps: disposing an organic layer between two electrodes; wherein the organic layer comprises the aforementioned luminescent copper halide cluster.

[0050] According to an embodiment of the present invention, the organic electroluminescent device is prepared by the following method: an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode are sequentially disposed on a substrate.

[0051] Preferably, the anode, hole injection layer, hole transport layer, electron blocking layer, light-emitting layer, hole blocking layer, electron transport layer, electron injection layer and cathode are formed by vapor deposition, spin coating or inkjet printing, for example by vapor deposition.

[0052] More preferably, the vapor deposition is performed under vacuum conditions, for example, when vapor deposition of organic materials, the vacuum level is below 1×10⁻⁶. -5 The process is carried out under Pa conditions. More preferably, the evaporation rate and thickness of each functional layer are precisely controlled using a quartz crystal film thickness gauge.

[0053] Beneficial effects:

[0054] This invention provides a class of luminescent copper halide clusters, their preparation method, and applications. Compared with known luminescent copper halide cluster materials, the luminescent copper halide clusters of this invention have the following advantages:

[0055] 1. This invention designs copper halide clusters based on donor-acceptor bisphosphine ligands, which exhibit high visible light emission efficiency in thin film state, and their molecular structure is highly scalable with easily tunable light color. Furthermore, these copper halide clusters have good processability and can be film-formed via vacuum sublimation or solution methods. This overcomes two major problems present in most previous copper halide cluster luminescent materials: (1) poor processability, difficulty in sublimation, and low solubility; (2) severe non-radiative loss in the excited state, leading to insufficient film luminescence efficiency.

[0056] 2. Compared with precious metal luminescent materials, the copper halide cluster luminescent material of the present invention has a simple synthesis and preparation process, high yield, and readily available and inexpensive raw materials.

[0057] 3. This invention ingeniously utilizes the wide emission spectrum of copper halide clusters to prepare OLEDs using copper halide clusters as sensitizers in MR-TADF luminescent materials. The prepared OLED devices exhibit excellent performance (high emission color purity and high luminous efficiency).

[0058] Terminology Definitions and Explanations

[0059] Unless otherwise stated, the definitions of groups and terms recorded in this application specification and claims, including their definitions as examples, exemplary definitions, preferred definitions, definitions recorded in tables, and definitions of specific compounds in the examples, can be arbitrarily combined and combined with each other. Such combinations and combinations of group definitions and compound structures shall fall within the scope of protection of this application.

[0060] The numerical ranges described in this application specification and claims, when the range can only be "integers", should be understood to include the two endpoints of the range and every integer within the range. For example, the number of carbon atoms "1 to 5" should be understood to include every integer of 1, 2, 3, 4, and 5.

[0061] "More than three" means three or more types.

[0062] The term "halogen" as used in this invention refers to chlorine, bromine, and iodine.

[0063] Term "C" 1-12 "alkyl" should be understood to refer to a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably C12. 1-6 Alkyl group. "C" 1-6 "Alkyl" should be understood to mean a straight-chain or branched saturated monovalent hydrocarbon group having 1, 2, 3, 4, 5, or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, and in particular, the group has 1, 2, or 3 carbon atoms ("C"). 1-3 Alkyl), such as methyl, ethyl, n-propyl or isopropyl.

[0064] The term "5-22-membered heteroaryl" should be understood to include monovalent monocyclic, bicyclic, tricyclic aromatic ring systems or more aromatic ring systems having 5 to 22 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O, and S, for example, "5-14-membered heteroaryl". The term "5-14-membered heteroaryl" should also be understood to include monovalent monocyclic, bicyclic, or tricyclic aromatic ring systems having 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 ring atoms, particularly 5, 6, 9, or 10 carbon atoms, and containing 1 to 5, preferably 1 to 3 heteroatoms independently selected from N, O, and S, and in each case, may be benzofused. Specifically, the heteroaryl group is selected from thienyl, furanyl, pyrroleyl, oxazolyl, thiazolyl, imidazoleyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl, and their benzo[derivatives], such as benzofuranyl, benzothienyl, benzooxazolyl, benzoisooxazolyl, benzoimidazolyl, benzotriazolyl, indazole, indolyl, isindolyl, etc.; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and their benzo[derivatives], such as quinolinyl, quinazolinyl, isoquinolinyl, etc.; or acrylinyl, inazinyl, purinyl, and their benzo[derivatives]; or terpenolyl, phthalazinyl, quinazolinyl, quinoxolinyl, naphridinyl, pteridinyl, carbazolyl, acridineyl, phenazinyl, phenothiazinyl, phenothiazinyl, etc. The "more aromatic ring system" is, for example, a 15- to 25-membered cyclic aromatic ring system containing 1 to 5 heteroatoms independently selected from N, O, and S.

[0065] Term "C" 6-20 "Aryl" should be understood as representing a monocyclic, bicyclic, or tricyclic hydrocarbon ring with 6 to 20 carbon atoms that is monovalent and partially aromatic, preferably "C". 6-14 "Aromatic". The term "C" 6-14 "Aryl" should be understood to preferably represent a monovalent aromatic or partially aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring ("C") having 6, 7, 8, 9, 10, 11, 12, 13, or 14 carbon atoms. 6-14 Aryl), particularly a ring with 6 carbon atoms (“C6 aryl”), such as phenyl; or biphenyl, or a ring with 9 carbon atoms (“C9 aryl”), such as indenyl or indenyl, or a ring with 10 carbon atoms (“C9 aryl”). 10 Aryl groups, such as tetrahydronaphthyl, dihydronaphthyl, or naphthyl, or rings with 13 carbon atoms (“C”). 13 Aryl groups, such as fluorene groups, or rings with 14 carbon atoms (“C”). 14 Aryl), for example, anthracene. When the C 6-20When the aryl group is substituted, it can be monosubstituted or polysubstituted. Furthermore, there are no restrictions on the substitution site; for example, it can be ortho, para, or meta substituted.

[0066] Term "C" 1-12 "Alkoxy" should be understood as "-OC". 1-12 Alkyl group, where "C" is an alkyl group. 1-12 "alkyl" has the definition as described above.

[0067] Unless otherwise stated, heterocyclic, heteroaryl, or heteroaryl groups include all their possible isomers, such as their positional isomers. Thus, for some illustrative, non-limiting examples, pyridyl or pyridylene includes pyridin-2-yl, pyridin-2-yl, pyridin-3-yl, pyridin-3-yl, pyridin-4-yl, and pyridin-4-yl; thiophenyl or thiophene includes thiophene-2-yl, thiophene-2-yl, thiophene-3-yl, and thiophene-3-yl. Attached Figure Description

[0068] Figure 1 The emission spectra of copper halide clusters 1-2 and 1-5 are shown.

[0069] Figure 2 The external quantum efficiency-brightness curves are for the devices OLED-6, OLED-11, and OLED-14. Detailed Implementation

[0070] The following detailed description, in conjunction with specific embodiments, illustrates the general formula compounds of the present invention, their preparation methods, and applications in further detail. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0071] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0072] Example 1

[0073] The synthetic route for compound 1-1 is shown below:

[0074]

[0075] [Synthesis of intermediate compound Ac-2FPh]

[0076] In a 500 mL three-necked flask, 3.86 g (20 mmol) of 4-bromo-1,2-difluorobenzene, 4.19 g (20 mmol) of 9,10-dihydro-9,9-dimethylacridine, 1.92 g (20 mmol) of sodium tert-butoxide, 0.29 g (1 mmol) of tri-tert-butylphosphine tetrafluoroborate, and 0.14 g (0.6 mmol) of palladium acetate were refluxed at 120 °C for 12 h under an argon atmosphere with 100 mL of dry toluene as solvent. The organic matter was extracted by washing with ethyl acetate and saturated brine, and dried over MgSO4. The drying agent was removed by filtration, and the solvent was removed under vacuum to obtain a grayish-brown solid. The solid was purified by silica gel chromatography (petroleum ether / dichloromethane, 5:1) to give 5.52 g of a white solid. 1 ¹H NMR (500 MHz, deuterated chloroform) δ 7.53 (dd, J = 7.6, 1.7 Hz, 2H), 7.51–7.44 (m, 1H), 7.29–7.24 (m, 1H), 7.17 (ddt, J = 8.3, 3.9, 2.0 Hz, 1H), 7.07 (td, J = 7.7, 1.7 Hz, 2H), 7.02 (td, J = 7.4, 1.4 Hz, 2H), 6.33 (dd, J = 8.1, 1.4 Hz, 2H), 1.75 (s, 6H).

[0077] Synthesis of intermediate compound L-1-1 (ligand)

[0078] In a 200 mL round-bottom flask, 4.72 g (18 mmol) of triphenylphosphine and 1.86 g (81 mmol) of sodium were added to 50 mL of anhydrous tetrahydrofuran. The mixture was refluxed and stirred for 12 h under an argon atmosphere. The cooled, deep red solution was transferred to another dry 200 mL round-bottom flask containing 1.93 g (6 mmol) of Ac-2FPh. The mixture was refluxed for 3 h under an argon atmosphere, followed by stirring at room temperature for 3 h. After the reaction was complete, an appropriate amount of methanol was added to the solution. The organic matter was extracted by washing with ethyl acetate and saturated brine, and dried over MgSO4. The drying agent was removed by filtration, and the solvent was removed under vacuum to obtain a yellow-brown solid. The solid was purified by silica gel chromatography (petroleum ether / dichloromethane, 4:1) to give 1.96 g of a white solid. 1 ¹H NMR (500MHz, deuterated chloroform) δ 7.45 (dd, J = 7.8, 1.6Hz, 2H), 7.33 (q, J = 2.5Hz, 10H), 7.30–7.18 (m, 14H), 7.03 (td, J = 7.7, 1.6Hz, 2H), 6.96 (td, J = 7.4, 1.3Hz, 2H), 6.30 (dd, J = 8.2, 1.2Hz, 2H), 1.63 (s, 6H). 13C NMR (126MHz, deuterated chloroform) δ 146.70, 146.61, 146.48, 146.39, 144.23, 144.16, 144.00, 143.94, 141.93, 140.78, 137.15, 137.11, 136.79, 136.75, 136.71, 136.67, 136.59, 136.55, 136.51, 136.47, 1 36.30, 136.24, 134.23, 134.21, 134.09, 134.07, 133.72, 133.71, 133.58, 133.56, 131.61, 130.50, 128.73, 128.54, 128.50, 128.43, 128.38, 126.31, 124.94, 120.84, 114.15, 36.00, 30.43.

[0079] [Synthesis of target product 1-1]

[0080] 50 mg (0.50 mmol) cuprous chloride was added to a 5 mL solution of dichloromethane containing 0.33 g (0.50 mmol) L⁻¹⁻¹. The mixture was stirred at room temperature for 3 h. The reaction mixture was filtered, and the solvent was removed under vacuum to give a pale yellow powder. The powder was purified by recrystallization from dichloromethane / ether to give 301 mg of pale yellow crystals. 1 ¹H NMR (500MHz, deuterated chloroform) δ 7.41–7.30 (m, 22H), 7.21 (dd, J = 15.9, 7.5Hz, 8H), 7.11 (q, J = 6.4Hz, 12H), 7.04 (t, J = 6.7Hz, 8H), 6.97 (t, J = 6.8Hz, 4H), 6.92 (t, J = 7.4Hz, 4H), 6.12 (d, J = 8.1Hz, 4H), 1.59 (s, 12H). 13C NMR (151MHz, CDCl3) δ142.47, 140.49, 136.44, 136.39, 133.94, 133.92, 133.86, 133.83, 133. 80, 133.73, 133.71, 132.50, 132.42, 132.37, 132.29, 132.16, 132.08, 132.03, 131.95, 131.86 , 130.41, 129.67, 129.59, 129.51, 129.23, 128.79, 128.71, 128.32, 128.26, 128.20, 126.66, 126.38, 126.18, 125.05, 124.91, 124.62, 120.95, 114.06, 77.24, 77.03, 76.81, 35.94, 30.62. 31 P NMR (243MHz, CDCl3) δ-18.76.

[0081] Example 2

[0082] The synthetic routes for compounds 1-2 are shown below:

[0083]

[0084] [Synthesis of target products 1-2]

[0085] (72 mg, 0.50 mmol) cuprous bromide was added to a (5 mL) solution of dichloromethane containing (0.33 g, 0.50 mmol) L⁻¹⁻¹. The mixture was stirred at room temperature for 3 h, then filtered, and the solvent was removed under vacuum to obtain a yellow powder. Purification was achieved by recrystallization from dichloromethane / ether to give 295 mg of yellow crystals. 1 ¹H NMR (500 MHz, deuterated chloroform) δ 7.42–7.29 (m, 22H), 7.26–7.18 (m, 8H), 7.12 (t, J = 7.3 Hz, 12H), 7.04 (t, J = 7.5 Hz, 8H), 6.99–6.96 (m, 4H), 6.94–6.91 (m, 4H), 6.14 (d, J = 9.4 Hz, 4H), 1.59 (s, 12H). 13C NMR (126MHz, CDCl3) δ147.02, 146.78, 146.54, 142.82, 142.57, 142.55, 142.34, 140.57, 136.63 , 136.58, 136.52, 136.48, 134.03, 134.00, 133.93, 133.90, 133.83, 133.80, 132.66, 132.57, 13 2.51, 132.42, 132.33, 132.24, 132.18, 132.09, 131.95, 131.93, 130.46, 129.25, 128.32, 128.30, 128.24, 128.18, 128.16, 126.44, 125.10, 121.02, 114.13, 77.36, 77.10, 76.85, 36.00, 30.65. 31 P NMR (243MHz, CDCl3) δ-20.68.

[0086] Example 3

[0087] The synthetic routes for compounds 1-3 are shown below:

[0088]

[0089] [Synthesis of target products 1-3]

[0090] (95 mg, 0.50 mmol) cuprous iodide was added to a (5 mL) solution of dichloromethane containing (0.33 g, 0.50 mmol) L⁻¹⁻¹. The mixture was stirred at room temperature for 3 h. The reaction mixture was filtered, and the solvent was removed under vacuum to give a green powder. The powder was purified by recrystallization from dichloromethane / ether to give 253 mg of pale yellow crystals. 1 ¹H NMR (500 MHz, deuterated chloroform) δ 7.42–7.27 (m, 22H), 7.22 (dd, J = 14.4, 7.0 Hz, 8H), 7.11 (t, J = 8.0 Hz, 12H), 7.02 (t, J = 7.5 Hz, 8H), 7.00–6.96 (m, 4H), 6.92 (t, J = 6.8 Hz, 4H), 6.16 (d, J = 8.1 Hz, 4H), 1.59 (s, 12H). 13CNMR (151MHz, CDCl3) δ142.67, 140.51, 136.71, 136.67, 136.56, 134.02, 133.95, 13 3.92, 133.86, 132.61, 132.52, 132.41, 132.32, 132.21, 132.13, 131.91, 130.51, 12 9.70, 129.61, 129.52, 129.17, 129.15, 128.14, 128.10, 128.02, 127.97, 126.69, 126.36, 126.13, 125.01, 124.53, 121.00, 114.13, 77.23, 77.02, 76.80, 35.96, 30.51. 31 P NMR (243MHz, CDCl3) δ-23.20.

[0091] Example 4

[0092] The synthetic routes for compounds 1-4 are shown below:

[0093]

[0094] Synthesis of intermediate compound L-1-2 (ligand)

[0095] In a 200 mL round-bottom flask, 5.48 g (18 mmol) of tris(o-methylphenyl)phosphine, 0.14 g (0.98 mmol) of 1-methylnaphthalene, and 1.86 g (81 mmol) of sodium were added, with 50 mL of anhydrous tetrahydrofuran as the solvent. The mixture was refluxed and stirred for 12 h under an argon atmosphere. The cooled, deep red solution was transferred to another 200 mL dry round-bottom flask containing 1.93 g (6 mmol) of Ac-2FPh, and refluxed under an argon atmosphere for 3 h, followed by stirring at room temperature for 3 h. After the reaction was complete, an appropriate amount of methanol was added to the solution. The extracted organic matter was washed with ethyl acetate and saturated brine, and dried over MgSO4. The drying agent was removed by filtration, and the solvent was removed under vacuum to obtain a yellowish-brown solid. The solid was purified by silica gel chromatography (petroleum ether / dichloromethane, 4:1) to give 1.62 g of a white solid. 1 ¹H NMR (500 MHz, deuterated chloroform) δ 7.42 (dd, J = 7.7, 1.6 Hz, 2H), 7.27–7.20 (m, 7H), 7.17–7.07 (m, 8H), 7.04–6.93 (m, 9H), 6.88 (dd, J = 7.8, 2.2 Hz, 3H), 6.80 (d, J = 5.7 Hz, 2H), 6.29 (dd, J = 8.2, 1.3 Hz, 2H), 2.30 (d, J = 15.5 Hz, 12H), 1.60 (s, 6H). 13C NMR (126MHz, deuterated chloroform) δ 141.95, 140.73, 133.56, 131.67, 130.34, 130.07, 128.61, 128.58, 126.28, 125.94, 125.05, 120.69, 113.91, 35.94, 30.67, 21.22, 21.07, 1.04.

[0096] [Synthesis of target products 1-4]

[0097] 50 mg (0.50 mmol) of cuprous chloride was added to a 5 mL solution of dichloromethane containing 0.36 g (0.50 mmol) of L-1-2. The mixture was stirred at room temperature for 3 h. The reaction mixture was filtered, and the solvent was removed under vacuum to give a yellow powder. Purification was achieved by recrystallization from dichloromethane / ether to give 222 mg of crystals. MS: m / z 1615.4057 [M] + Elemental analysis: C 98 H 90 Cl2Cu2N2P4, calculated values ​​(%): C, 72.76; H, 5.61; N, 1.73; measured values: C, 73.03; H, 5.68; N, 1.65.

[0098] Example 5

[0099] The synthetic routes for compounds 1-5 are shown below:

[0100]

[0101] [Synthesis of target products 1-5]

[0102] 72 mg (0.50 mmol) of cuprous bromide was added to a 5 mL solution of dichloromethane containing 0.36 g (0.50 mmol) of L-1-2. The mixture was stirred at room temperature for 3 h. The reaction mixture was filtered, and the solvent was removed under vacuum to give a yellow powder. The powder was purified by recrystallization from dichloromethane / ether to give 213 mg of pale yellow crystals. 1 ¹H NMR (500 MHz, deuterated chloroform) δ 7.51–7.43 (m, 8H), 7.31 (t, = 5.3 Hz, H), 28–7.05 (m, 16H), 7.05–6.87 (m, 16H), 6.73 (d, J = 8.7 Hz, 6H), 6.28 (dd, J = 7.7, 1.7 Hz, 4H), 2.60 (d, J = 20.9 Hz, 24H), 1.61 (s, 2H). 13C NMR (6MHz, deuterated chloroform) 144.22, 44.20, 43.96, 43.71, 42.62, 40.36, 38.92, 137.31, 36.01, 35.98, 35.94, 32.00, 31.98, 31.29, 30.44, 26.36, 26.19, 25.27, 21.73, 14.78, 6.20, 0.31, 2.92, 2.85, 2.82, 2.78, 2.76, 2.72. 31 P NMR (2MHz, deuterated chloroform) -26.49.

[0103] Example 6

[0104] The synthetic routes for compounds 1-6 are shown below:

[0105]

[0106] [Synthesis of target products 1-6]

[0107] 95 mg (0.50 mmol) of cuprous iodide was added to a 5 mL solution of dichloromethane containing 0.36 g (0.50 mmol) of L-1-2. The mixture was stirred at room temperature for 3 h. The reaction mixture was filtered, and the solvent was removed under vacuum to give a yellow powder. Purification was achieved by recrystallization from dichloromethane / ether to give 189 mg of crystals. MS: m / z 1799.2769 [M] + Elemental analysis: C 98 H 90 I₂Cu₂N₂P₄, calculated values ​​(%): C, 65.37; H, 5.04; N, 1.56; measured values: C, 65.44; H, 5.08; N, 1.49.

[0108] Example 7

[0109] The synthetic routes for compounds 1-65 are shown below:

[0110]

[0111] [Synthesis of intermediate compound SiAc-2FPh]

[0112] In a 200 mL three-necked flask, 1.93 g (10 mmol) of 4-bromo-1,2-difluorobenzene, 3.50 g (10 mmol) of 10,10-diphenyl-5,10-dihydrodibenzo[b,e][1,4]azasilanthracene, 0.96 g (10 mmol) of sodium tert-butoxide, 0.15 g (0.5 mmol) of tri-tert-butylphosphine tetrafluoroborate, and 0.07 g (0.3 mmol) of palladium acetate were refluxed at 120 °C for 12 h under an argon atmosphere with 60 mL of dry toluene as solvent. The organic matter was extracted by washing with ethyl acetate and saturated brine, and dried over MgSO4. The drying agent was removed by filtration, and the solvent was removed under vacuum to obtain a grayish-brown solid. The residue was purified by silica gel chromatography (petroleum ether / dichloromethane, 5:1) to give 3.68 g of a white solid.

[0113] [Synthesis of intermediate compound L-1-3 (ligand)]

[0114] In a 200 mL round-bottom flask, 5.48 g (18 mmol) of tris(o-methylphenyl)phosphine, 0.14 g (0.98 mmol) of 1-methylnaphthalene, and 1.86 g (81 mmol) of sodium were added, with 50 mL of anhydrous tetrahydrofuran as solvent. The mixture was refluxed and stirred for 12 h under an argon atmosphere. The cooled, deep red solution was transferred to another 200 mL dry round-bottom flask containing 2.77 g (6 mmol) of SiAc-2FPh, and refluxed under argon atmosphere for 3 h, followed by stirring at room temperature for 3 h. After the reaction was complete, an appropriate amount of methanol was added to the solution. The extracted organic matter was washed with ethyl acetate and saturated brine, and dried over MgSO4. The drying agent was removed by filtration, and the solvent was removed under vacuum to obtain a yellowish-brown solid. Purification was achieved by silica gel chromatography (petroleum ether / dichloromethane, 4:1) to give 1.81 g of a white solid.

[0115] [Synthesis of target products 1-65]

[0116] (72 mg, 0.50 mmol) cuprous bromide was added to a (5 mL) solution of dichloromethane containing L-1-3 (0.36 g, 0.50 mmol). The mixture was stirred at room temperature for 3 h. The reaction mixture was filtered, the solvent was removed under vacuum, and the mixture was purified by recrystallization from dichloromethane / ether to give 203 mg of yellow crystals. MS: m / z 1985.3191 [M] + ]; Elemental analysis: C 116 H 98 Br2Cu2N2P4Si2, calculated values ​​(%): C, 70.12; H, 4.97; N, 1.41; measured values: C, 70.19; H, 5.01; N, 1.46.

[0117] Example 8

[0118] The synthetic routes for compounds 1-69 are shown below:

[0119]

[0120] Synthesis of intermediate compound L-1-4 (ligand)

[0121] In a 200 mL round-bottom flask, 6.98 g (18 mmol) of tris(trimethylphenyl)phosphine, 0.14 g (0.98 mmol) of 1-methylnaphthalene, and 1.86 g (81 mmol) of sodium were added, with 50 mL of anhydrous tetrahydrofuran as solvent. The mixture was refluxed and stirred for 12 h under an argon atmosphere. The cooled, deep red solution was transferred to another 200 mL dry round-bottom flask containing 2.77 g (6 mmol) of SiAc-2FPh, and refluxed under argon atmosphere for 3 h, followed by stirring at room temperature for 3 h. After the reaction was complete, an appropriate amount of methanol was added to the solution. The extracted organic matter was washed with ethyl acetate and saturated brine, and dried over MgSO4. The drying agent was removed by filtration, and the solvent was removed under vacuum to obtain a yellowish-brown solid. Purification was achieved by silica gel chromatography (petroleum ether / dichloromethane, 4:1) to give 1.73 g of a white solid.

[0122] [Synthesis of target products 1-69]

[0123] 95 mg (0.50 mmol) of cuprous iodide was added to a 5 mL solution of dichloromethane containing 0.36 g (0.50 mmol) of L-1-4. The mixture was stirred at room temperature for 3 h. The reaction mixture was filtered, the solvent was removed under vacuum, and the mixture was purified by recrystallization from dichloromethane / ether to give 230 mg of crystals. MS: m / z 2303.5438 [M] + Elemental analysis: C 132 H 130 Cu2I2N2P4Si2, calculated values ​​(%): C, 68.77; H, 5.68; N, 1.22; measured values: C, 68.59; H, 5.59; N, 1.27.

[0124] Example 9

[0125] Preparation of luminescent thin films:

[0126] Compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-65, and 1-66 prepared in Examples 1-8 were mixed with the host material mCP (97 wt%) at a mass fraction of 3 wt% to prepare doped thin films via vacuum sublimation. The photoluminescence spectra and photoluminescence efficiencies of these thin films were measured using a spectrometer equipped with an integrating sphere, and the test results are listed in Table 1.

[0127] Table 1. Photoluminescence spectra and photoluminescence efficiencies of the compounds prepared in Examples 1-8 as thin films doped in mCP at a concentration of 3 wt%.

[0128]

[0129]

[0130] As can be seen from the test data in Table 1, the compounds prepared in Examples 1-8 all have high photoluminescence efficiency (ranging from 60% to 99%) in the thin film state, and all show high potential as luminescent or sensitizing materials for preparing high-performance OLEDs.

[0131] Example 10

[0132] Fabrication of organic electroluminescent devices 1-5 (OLED-1-OLED-5):

[0133] In this embodiment, compound 1-2 prepared in Example 2 is used as the luminescent material, commercial material mCP is used as the host material, indium tin oxide (ITO) is used as the anode, HAT-CN is used as the hole injection material, TAPC is used as the hole transport material, mCP is used as the electron blocking material, PPF is used as the hole blocking material, TmPyPB is used as the electron transport material, Liq is used as the electron injection material, and aluminum (Al) is used as the cathode material to construct an electroluminescent device with the device structure of ITO (100nm) / HAT-CN (10nm) / TAPC (40nm) / mCP (5nm) / mCP:X wt% compound 1-2 (30nm) / PPF (5nm) / TmPyPB (35nm) / Liq (1nm) / Al (100nm). X wt% is the mass fraction (doping ratio) of the luminescent copper halide clusters 1-2 in the luminescent layer, where X takes values ​​of 3, 5, 15, 25, and 100, and the fabricated devices are numbered OLED-1, OLED-2, OLED-3, OLED-4, and OLED-5, respectively.

[0134] The fabrication process of the aforementioned electroluminescent device is as follows: A glass substrate with an ITO (100nm) transparent conductive layer is cleaned with alkaline solution and rinsed with deionized water. It is then ultrasonically treated in deionized water, ethanol, and acetone sequentially for ten minutes each. After baking in a clean environment until no solvent residue remains, it undergoes ultraviolet ozone treatment for 15 minutes. The substrate is then placed in a vacuum chamber and evacuated to a vacuum level below 2×10⁻⁶. -5Pa. HAT-CN was deposited sequentially at a deposition rate of 0.2 nm / s to form a 10 nm film; TAPC was deposited at a deposition rate of 0.2 nm / s to form a 40 nm layer; mCP was deposited at a deposition rate of 0.2 nm / s to form a 5 nm film; on the light-emitting layer, compounds 1-2 and mCP were simultaneously deposited at a deposition rate of 0.2 nm / s in a ratio of X:(100-X) to form a 30 nm doped film; PPF was deposited at a deposition rate of 0.2 nm / s to form a 5 nm film as a hole-blocking layer; TmPyPB was deposited at a deposition rate of 0.2 nm / s to form a 35 nm layer as an electron transport layer. Liq was deposited at a deposition rate of 0.02 nm / s to form a 1 nm layer as an electron injection layer. Finally, aluminum was deposited on the electron injection layer at a deposition rate of 0.5 nm / s to form a cathode with a film thickness of 100 nm. The light-emitting area of ​​the device is 9 mm². 2 .

[0135] Example 11

[0136] Fabrication of Organic Electroluminescent Devices 6-10 (OLED-6-10)

[0137] Except that compounds 1-5 described in Example 5 were used as doped luminescent materials instead of compounds 1-2 in Example 9, OLEDs 6-10 were prepared under the same production conditions as OLEDs 1-5.

[0138] The structures of the organic compounds involved in Examples 10 and 11 are as follows:

[0139]

[0140] The current-voltage characteristics and luminescence characteristics of the organic light-emitting diodes prepared in Examples 10 and 11 were tested using characterization equipment, and important parameters such as external quantum efficiency, brightness, emission wavelength and emission half width at half maximum were recorded (test results are shown in Table 2).

[0141] As shown in Table 2, the highest external quantum efficiencies of OLED-1 to 10 prepared using compounds 1-2 and 1-5 of the present invention as doped luminescent materials reach 14.1% and 25.1%, respectively, with emission wavelengths ranging from 510 nm to 597 nm. The highest external quantum efficiency of the devices prepared by the present invention is higher than that of most OLEDs prepared using monovalent copper complexes previously reported.

[0142] Table 2. Performance of OLED devices in Examples 10-11

[0143]

[0144] Example 12

[0145] Fabrication of organic electroluminescent devices 11-16 (OLED-11-OLED-16):

[0146] In this embodiment, compounds 1-5 prepared in Example 5 are used as sensitizers, commercial blue light material ν-DABNA is used as guest light-emitting material, commercial host material mCP is used as host material, indium tin oxide (ITO) is used as anode, HAT-CN is used as hole injection material, TAPC is used as hole transport material, mCP is used as electron blocking material, PPF is used as hole blocking material, TmPyPB is used as electron transport material, Liq is used as electron injection material, and aluminum (Al) is used as cathode material to construct an electroluminescent device with the device structure of ITO (100nm) / HAT-CN (10nm) / TAPC (40nm) / mCP (5nm) / light-emitting layer (30nm) / PPF (5nm) / TmPyPB (35nm) / Liq (1nm) / Al (100nm). The composition of the light-emitting layer and the corresponding device number are shown in Table 3.

[0147] The fabrication process of the aforementioned electroluminescent device is as follows: A glass substrate with an ITO (100nm) transparent conductive layer is cleaned with alkaline solution and rinsed with deionized water. It is then ultrasonically treated in deionized water, ethanol, and acetone sequentially for ten minutes each. After baking in a clean environment until no solvent residue remains, it undergoes ultraviolet ozone treatment for 15 minutes. The substrate is then placed in a vacuum chamber and evacuated to a vacuum level below 2×10⁻⁶. -5 Pa. HAT-CN was deposited sequentially at a deposition rate of 0.2 nm / s to form a 10 nm film; TAPC was deposited at a deposition rate of 0.2 nm / s to form a 40 nm layer; mCP was deposited at a deposition rate of 0.2 nm / s to form a 5 nm film; on the light-emitting layer, compounds 1-5, ν-DABNA, and mCBP were simultaneously deposited at a deposition rate of 0.2 nm / s in appropriate proportions to form a 30 nm doped film; PPF was deposited at a deposition rate of 0.2 nm / s to form a 5 nm film as a hole blocking layer; TmPyPB was deposited at a deposition rate of 0.2 nm / s to form a 35 nm layer as an electron transport layer. Liq was deposited at a deposition rate of 0.02 nm / s to form a 1 nm layer as an electron injection layer. Finally, aluminum was deposited on the electron injection layer at a deposition rate of 0.5 nm / s to form a cathode with a film thickness of 100 nm. The light-emitting area of ​​the device is 9 mm². 2 .

[0148] The current-voltage characteristics and luminescence characteristics of the organic light-emitting diode prepared in Example 12 were tested using characterization equipment, and important parameters such as external quantum efficiency, brightness, emission wavelength and emission half width at half maximum were recorded (test results are shown in Table 3).

[0149] As shown in Table 3, the maximum external quantum efficiency of the sensitized blue OLED-14 prepared using compounds 1-5 of the present invention as sensitizers reaches 28.7%, significantly higher than the 22% of the corresponding unsensitized device (OLED-11). This is the highest efficiency reported for pure light OLEDs (CIE-y value < 0.2) prepared with monovalent copper complexes. These results indicate that the copper halide clusters described in this invention can be used as sensitizers for preparing high-performance blue OLEDs.

[0150] The method for forming each structural layer in the organic electroluminescent device of the present invention is not limited, and may include, but is not limited to, existing vacuum evaporation method, spin coating method and inkjet printing method.

[0151] Table 3. Performance of the sensitized OLED device in Example 12

[0152]

[0153] In Table 3, "1wt%" in the OLED-11 emissive layer refers to the mass fraction of commercial blue light material ν-DABNA in the emissive layer, and so on.

[0154] The exemplary embodiments of the present invention have been described above. However, the scope of protection of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. The compound represented by formula (I): in: X is a halogen, selected from Cl, Br, or I; R are the same or different, independently of one another, selected from C 1-12 alkyl, C 1-12 alkoxy, C 6-20 aryl, 5- to 22-membered heteroaryl, -N-(C 6-20 aryl)2or -N-(5- to 22-membered heteroaryl)2; n is 0, 1, 2, 3, 4 or 5; Y is selected from any one of the following chemical bonds: -O-, -S-, -Se-, -Te-, -C(O)-, -S(O)2-, -C(R'R”)-, -Si(R'R”), -N(R'-, -P(R'-), -P(=O)R'-, or -B(R'-. R' and R" may be the same or different, and are independently selected from hydrogen, deuterium, halogen, nitrile, unsubstituted, or optionally substituted by one, two, or more Ra groups, including the following groups: C 1-12 Alkyl, -COC 1-12 Alkyl, -COOC 1-12 Alkyl, -CONHC 1-12 Alkyl, C 3-20 cycloalkyl, C 1-12 Alkoxy, C 6-20 aryloxy group, C 1-12 Alkyl thio, C 6-20 Arylthio, C 1-12 alkylsulfonyl, C 6-20 arylsulfonyl, C 2-12 alkenyl, -Si(C) 1-12 Alkyl)3, -Si(C 6-20 aryl)3,-Si(5-22 heteroaryl)3,-B(C 1-12 Alkyl)2, -B(C 6-20 aryl)2, -B(5-22 heteroaryl)2, NH2, -P(C 6-20 aryl)3, phosphino (P=O), C 6-20 Aryl, 5-22 membered heteroaryl, 3-20 membered heterocyclic; or R' and R" together with their attached C or Si to form unsubstituted or substituted ring systems as follows: C 3-20 Cycloalkyl, 3-20 membered heterocyclic groups, C 6-20 Aryl or 5-22 heteroaryl groups; Ra is selected from =O, halogen, nitrile, nitro, hydroxyl, aldehyde, C 1-12 Alkyl, -COC 1-12 Alkyl, -COOC 1-12 Alkyl, C 3-20 cycloalkyl or C 1-12 Alkyl group.

2. The compound according to claim 1, wherein, X is a halogen, selected from Cl, Br, or I; R is selected from C 1-6 Alkyl, C 1-6 Alkoxy, C 6-14 Aryl, 5-14 heteroaryl, -N-(C 5-14 aryl)2 or -N-(5-14 heteroaryl)2; n is 0, 1, 2 or 3; Y represents a chemical bond, such as -O-, -S-, -Se-, -Te-, -C(O)-, -S(O)2-, -N(R')-, -P(R')-, -, -C(C 1-6 alkyl)2-, -Si(C 1-6 alkyl)2-, -Si(C 6-14 Aryl)2-, -C(C 6-14 When aryl)2- or Y is CR'R”, R' and R” together with the C connected to them constitute an unsubstituted or =O substituted C. 6-14 Aryl.

3. The compound according to claim 1 or 2, wherein, X is a halogen, selected from Cl, Br, or I; R is selected from methyl, ethyl, tert-butyl, methoxy, phenyl, carbazole, acridine; n is 1, 2, 3 or 4.

4. The compound according to claim 1 or 2, wherein, Equation (I) has the structure shown in equation (I'): Each group has the definition described in claim 1 or 2.

5. The compound according to claim 4, wherein, X is a halogen, selected from Cl, Br, or I; R is selected from C 1-6 Alkyl, C 1-6 Alkoxy, C 6-14 Aryl, 5-14 heteroaryl; n is 0, 1, 2 or 3; Y represents chemical bonds, -O-, -S-, -Se-, -C(C 1-6 alkyl)2-, -Si(C 1-6 alkyl)2-, -C(C 6-14 aryl)2-,-Si(C 6-14 Aryl)2-,fluorene or anthrone group The black boxes mark the connection sites of Y.

6. The compound according to any one of claims 1-5, wherein, The compound represented by formula (I) is selected from one of the following structures:

7. A method for preparing the compound according to any one of claims 1-6, wherein, Includes the following steps: The compound shown in formula (I-1) reacts with copper halide CuX to give the compound shown in formula (I); Wherein, R, n, Y and X have the definitions described in any one of claims 1-6.

8. Use of the compound according to any one of claims 1-6 as a luminescent or sensitizing material in the preparation of organic electronic devices, preferably in the preparation of organic electroluminescent devices.

9. An organic electroluminescent device comprising two electrodes and an organic layer located between the electrodes, said organic layer comprising the compound of any one of claims 1-6.

10. The method for preparing the organic electroluminescent device according to claim 9, wherein, The method includes the following steps: forming an organic layer between two electrodes; the organic layer comprising the luminescent copper halide cluster as described in any one of claims 1-6.

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