CN110105388B - Ag (I) complex-based thermal activation delayed fluorescent material and preparation method and application thereof - Google Patents

Ag (I) complex-based thermal activation delayed fluorescent material and preparation method and application thereof Download PDF

Info

Publication number
CN110105388B
CN110105388B CN201910399429.5A CN201910399429A CN110105388B CN 110105388 B CN110105388 B CN 110105388B CN 201910399429 A CN201910399429 A CN 201910399429A CN 110105388 B CN110105388 B CN 110105388B
Authority
CN
China
Prior art keywords
complex
formula
compound
group
independently
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910399429.5A
Other languages
Chinese (zh)
Other versions
CN110105388A (en
Inventor
卢灿忠
贾吉慧
梁栋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiamen Institute of Rare Earth Materials
Original Assignee
Xiamen Institute of Rare Earth Materials
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiamen Institute of Rare Earth Materials filed Critical Xiamen Institute of Rare Earth Materials
Priority to CN201910399429.5A priority Critical patent/CN110105388B/en
Publication of CN110105388A publication Critical patent/CN110105388A/en
Application granted granted Critical
Publication of CN110105388B publication Critical patent/CN110105388B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/6552—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring
    • C07F9/65522—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring condensed with carbocyclic rings or carbocyclic ring systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

A thermal activation delayed fluorescence material based on Ag (I) complex has a structure shown in a formula A. Compared with the existing complex, the complex can remarkably improve the luminous efficiency of a solution state and a thin film state, the service life of the complex is only a few microseconds (about 6 microseconds), the thin film state efficiency is close to 100 percent, and the radiation transition rate is as high as 105S‑1And the material is comparable to a noble metal phosphorescent material. In addition, the complex has low raw material price and simple and efficient synthesis, can be used for a light-emitting layer of an organic electroluminescent device, and has economic advantages when being applied to industrial practice.
Figure DDA0002059258280000011

Description

Ag (I) complex-based thermal activation delayed fluorescent material and preparation method and application thereof
Technical Field
The invention belongs to the field of fluorescent materials, and particularly relates to a thermal activation delay fluorescent material of an ionic Ag (I) complex, and a preparation method and application thereof.
Background
Organic electroluminescent diodes (OLEDs) have great potential in the display and lighting areas. The development of efficient and stable light-emitting materials is still the competitive core of OLEDs. Three classes of organic electroluminescent materials, namely fluorescent materials, phosphorescent materials and thermally activated delayed fluorescent materials, have been developed. According to the spin statistical rule, when a pair of electronsAnd the generation probability of singlet excitons and triplet excitons upon recombination with holes is 25% and 75%, respectively. Due to spin forbidden resistance, the fluorescent material can only emit light by using singlet excitons, and the exciton utilization rate is lower than 25%. For the platinum heavy metal phosphorescent materials such as Ir, Pt and the like, the spin-orbit coupling effect is enhanced due to the introduction of heavy atoms, so that T is formed1-S0The transition is partially released, thereby achieving 100% utilization of the excitons. Although platinum group heavy metal phosphorescent materials have been widely used in commercial illumination and display devices with great success, such materials are expensive and difficult to mass-produce. In addition, when a blue light material is developed, because the d-orbit of metal is not filled, and an MC state exists, the potential energy of MLCT and MC is poor, so that excitons are easy to jump to the MC state with the property of reverse bonds, the non-radiative transition is increased, and the phosphorescence efficiency of the material is reduced. The newly developed third generation Thermally Activated Delayed Fluorescence (TADF) materials have attracted extensive interest to researchers. The material has low price and easy wavelength adjustment, and is a luminescent material with larger application prospect. Lowest singlet excited state-lowest triplet state energy gap (E) of this class of materialsST) Very small (<0.3 eV). At normal temperature, triplet excitons can be thermally activated and converted into singlet excitons to emit light by intersystem crossing. Thus, the theoretical internal quantum efficiency of the device can reach 100%. In order to obtain a high-efficiency thermally activated delayed fluorescence material, a small Delta E needs to be obtained in consideration of molecular designSTAnd large nonradiative transition rates. In purely organic TADF material design, small Δ ESTContradictory to the large radiative transition rate, since a small Δ E is favored by increasing the angle between the electron donor and the electron acceptorSTHowever, as the angle increases, the transition dipole moment of the molecule decreases, and the weaker rigidity of the molecule tends to result in a larger nonradiative transition rate, resulting in lower luminous efficiency. That is, it is difficult to design these materials while taking into account the above-mentioned several factors. The thermal activation delayed fluorescence property of the metal Ag (I) which has wide reserves and low price has been reported. But Jahn-Teller distortions exist in the excited state due to the presence of metal-to-ligand charge transfer (MLCT) properties. Thus, at presentThe Ag (I) complex has high photoluminescence quantum efficiency in a solid state, and has extremely low photoluminescence quantum efficiency in a thin film state and a solution state. The design of an efficient electroluminescent device is important that the thin-film state has higher photoluminescence efficiency and lower luminescent life, and at present, a thermally activated delayed fluorescent material with both high photoluminescence efficiency and lower life is rarely seen.
Disclosure of Invention
In order to solve the above problems, the present invention provides a complex represented by the following formula a:
Figure BDA0002059258260000021
wherein R is1Is an electron donating group selected from the following structures:
Figure BDA0002059258260000022
Figure BDA0002059258260000031
dotted-represents a connection site to another unit;
in the structure, R is the same or different and is independently selected from hydrogen and C1-15Alkyl, halo C1-15Alkyl radical, C1-15Alkoxy, halo C1-15Alkoxy radical, C3-20Cycloalkyl radical, C6-20Aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclyl;
R2、R3、R4identical or different, independently of one another, from hydrogen, halogen, cyano, C1-15Alkyl, halo C1-15Alkyl radical, C1-15Alkoxy, halo C1-15Alkoxy radical, C3-20Cycloalkyl radical, C6-20Aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclyl;
n is an integer from 0 to 3;
Figure BDA0002059258260000041
represents two unconnected aryl phosphorus ligands P' or a bridged aryl phosphorus bidentate ligand
Figure BDA0002059258260000042
Said P' or
Figure BDA0002059258260000043
Connecting with Ag;
the aryl phosphorus ligand P' is selected from the structures represented by the following formulas P1-P4:
Figure BDA0002059258260000044
wherein, in the structure shown by P1-P4, the central P atom is a connecting site which is connected with Ag;
R8、R9and R10Identical or different, independently of one another, from C1-15Alkyl, halo C1-15Alkyl radical, C1-15Alkoxy, halo C1-15An alkoxy group;
bridged aryl phosphorus bidentate ligands
Figure BDA0002059258260000045
Selected from the structures represented by the following formulae P5-P9:
Figure BDA0002059258260000046
wherein, in the structures shown by P6-P9, two P atoms in each structure are connecting sites which are simultaneously connected with Ag; m is any integer from 1 to 5;
l is selected from anions.
According to an embodiment of the invention, formula a is selected from the structures shown in formula I or formula II below:
Figure BDA0002059258260000051
wherein R is1、R2、R3、R4、L、
Figure BDA0002059258260000052
Having the definitions as described above.
According to a preferred embodiment of the invention, in formula A, R1Selected from the following structures:
Figure BDA0002059258260000053
R2、R3、R4same or different, independently from each other selected from H, C1-6Alkyl, halo C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkoxy or C6-14Aryl, such as H, phenyl, trifluoromethyl, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, or alkoxy;
l is selected from inorganic anions, e.g. ClO4 -、BF4 -Or PF6 -And the like.
By way of example, the complex of formula A is selected from the following:
Figure BDA0002059258260000054
Figure BDA0002059258260000061
the invention also provides a preparation method of the complex shown as the formula A, which comprises the following steps:
Figure BDA0002059258260000062
compound A-1, [ Ag (CH)3CN)4]L and
Figure BDA0002059258260000063
reacting to obtain a complex shown as a formula A;
wherein R is1、R2、R3、R4、n、L、
Figure BDA0002059258260000064
Having the definitions as described above.
According to an embodiment of the present invention, the compound A-1, [ Ag (CH)3CN)4]L and
Figure BDA0002059258260000065
the molar ratio of (A) to (B) is 1:1-2: 1-2.
According to an embodiment of the invention, the reaction is carried out at room temperature.
According to the invention, the reaction also comprises the preparation of compound a-1, comprising:
Figure BDA0002059258260000071
1) compound A-4 and compound R1H reacts to obtain a compound A-3;
2) reacting the compound A-3 with the compound A-2 to obtain a compound A-1;
wherein R is1、R2、R3、R4N has the definitions as described above; x1、X2Identical or different, independently of one another, from the group of leaving groups.
The invention also provides application of the complex shown in the formula A in preparing organic electroluminescent devices, such as organic electroluminescent diodes.
Preferably, the complex shown in the formula A is used as a light-emitting layer in an organic electroluminescent device.
According to an embodiment of the present invention, the organic electroluminescent device further comprises a first electrode layer and a second electrode layer.
According to an embodiment of the present invention, a first functional layer is further disposed between the first electrode layer and the light emitting layer, and a second functional layer is further disposed between the light emitting layer and the second electrode layer.
According to an embodiment of the present invention, the first functional layer is a hole injection layer and/or a hole transport layer, and the second functional layer is an electron injection layer and/or an electron transport layer.
Compared with the existing luminescent material, the invention has the following advantages:
(1) compared with the noble metal complex, the complex prepared by the invention has the advantages that the metal d orbit of Ag (I) ions is filled, the MC state does not exist, and the moderate spin-orbit coupling effect is realized, so that the complex is suitable for being used as a blue light electroluminescent material.
(2) Compared with the complex reported at present, the complex prepared by the invention can obviously improve the luminous efficiency in a solution state and a thin film state.
(3) The Ag (I) complex prepared by the invention consists of bipolar N ^ N ligands and bulky P ^ P ligands. Due to the existence of larger steric hindrance effect, the nonradiative transition of the complex is also inhibited, and the complex has smaller delta ESTWhile achieving a large radiation transition rate. In addition, the service life of the complex of the invention is only a few microseconds (about 6 mu s), the film state efficiency is close to 100 percent, and the radiation transition rate is as high as 105S-1And the material is comparable to a noble metal phosphorescent material.
(4) The thermal activation delayed fluorescence material of the Ag (I) complex prepared by the invention has the advantages of low raw material price, simple and efficient synthesis and economic advantage when applied to industrial practice.
(5) The Ag (I) complex prepared by the invention can be used for a light-emitting layer of an organic electroluminescent device, and has good solubility in a polar solvent due to the anion, so that the Ag (I) complex is suitable for preparing the device by a solution processing process, thereby simplifying the preparation process of the device and reducing the preparation cost.
Terms and definitions
Unless defined otherwise, all technical and scientific terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which the claimed subject matter belongs.
The term "halogen" includes F, Cl, Br or I.
The term "halo" means substituted with at least one of halogen F, Cl, Br or I.
The term "C1-15Alkyl is understood to mean a straight-chain or branched saturated monovalent hydrocarbon radical having from 1 to 15 carbon atoms. For example, "C1-6Alkyl "denotes straight and branched chain alkyl groups having 1,2, 3,4, 5, or 6 carbon atoms. The alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a 2-methylbutyl group, a 1-ethylpropyl group, a 1, 2-dimethylpropyl group, a neopentyl group, a 1, 1-dimethylpropyl group, a 4-methylpentyl group, a 3-methylpentyl group, a 2-ethylbutyl group, a 1-ethylbutyl group, a 3, 3-dimethylbutyl group, a 2, 2-dimethylbutyl group, a 1, 1-dimethylbutyl group, a 2, 3-dimethylbutyl group, a 1, 3-dimethylbutyl group or a 1, 2-dimethylbutyl group, or the like, or isomers thereof.
The term "C1-15Alkoxy "is to be understood as meaning-O-C1-15Alkyl radical, wherein C1-15Alkyl groups have the above definitions.
The term "C3-20Cycloalkyl "is understood to mean a saturated monovalent monocyclic, bicyclic or polycyclic hydrocarbon ring (also called fused ring hydrocarbon ring) having 3 to 20 carbon atoms. Bicyclic or polycyclic cycloalkyl groups include fused cycloalkyl, bridged cycloalkyl, spirocycloalkyl; the fused ring refers to a fused ring structure formed by two or more ring structures sharing two adjacent ring atoms with each other (i.e., sharing one bond). The bridged ring refers to a condensed ring structure formed by two or more ring-assembled structures sharing two non-adjacent ring atoms with each other. The spiro ring refers to a fused ring structure formed by two or more cyclic structures sharing one ring atom with each other. Such as the C3-20Cycloalkyl may be C3-8Monocyclic cycloalkyl, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or is C7-12And cyclic cycloalkyl groups such as decalin ring; or may be C7-12Bridged cycloalkyl radicals, e.g. norbornaneAlkane, adamantane, bicyclo [2,2 ]]Octane.
The term "3-20 membered heterocyclyl" means a saturated or unsaturated monovalent monocyclic or bicyclic hydrocarbon ring comprising 1-5 heteroatoms independently selected from N, O and S, preferably "3-10 membered heterocyclyl". The term "3-10 membered heterocyclyl" means a saturated monovalent monocyclic or bicyclic hydrocarbon ring comprising 1-5, preferably 1-3 heteroatoms selected from N, O and S. The heterocyclic group may be attached to the rest of the molecule through any of the carbon atoms or nitrogen atom (if present). In particular, the heterocyclic group may include, but is not limited to: 4-membered rings such as azetidinyl, oxetanyl; 5-membered rings such as tetrahydrofuranyl, dioxolyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or a 6-membered ring such as tetrahydropyranyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl, or trithianyl; or a 7-membered ring such as diazepanyl. Optionally, the heterocyclic group may be benzo-fused. The heterocyclyl group may be bicyclic, for example but not limited to a 5,5 membered ring, such as a hexahydrocyclopenta [ c ] pyrrol-2 (1H) -yl ring, or a 5,6 membered bicyclic ring, such as a hexahydropyrrolo [1,2-a ] pyrazin-2 (1H) -yl ring. The nitrogen atom containing ring may be partially unsaturated, i.e. it may contain one, two or more double bonds, such as but not limited to 2, 5-dihydro-1H-pyrrolyl, 4H- [1,3,4] thiadiazinyl, 4, 5-dihydrooxazolyl or 4H- [1,4] thiazinyl, or it may be benzo-fused, such as but not limited to dihydroisoquinolyl, 1, 3-benzoxazolyl, 1, 3-benzodioxolyl. According to the invention, the heterocyclic radical is non-aromatic.
The term "C6-20Aryl "is understood to preferably mean a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6 to 20 carbon atoms, preferably" C6-14Aryl ". The term "C6-14Aryl "is to be understood as preferably meaning a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms (" C6-14Aryl group "), in particular a ring having 6 carbon atoms (" C6Aryl "), such as phenyl; or a biphenyl group, or a mixture of two or more,or a ring having 9 carbon atoms ("C)9Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C10Aryl radicals), such as tetralinyl, dihydronaphthyl or naphthyl, or rings having 13 carbon atoms ("C13Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C)14Aryl), such as anthracenyl. When said C is6-20When the aryl group is substituted, it may be mono-or polysubstituted. And, the substitution site thereof is not limited, and may be, for example, ortho-, para-or meta-substitution.
The term "5-20 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: having 5 to 20 ring atoms and comprising 1 to 5 heteroatoms independently selected from N, O and S, such as "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: which has 5,6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and which comprises 1 to 5, preferably 1 to 3, heteroatoms each independently selected from N, O and S and, in addition, can be benzo-fused in each case. In particular, heteroaryl is selected from thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and their benzo derivatives, such as benzofuryl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like, and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl, and the like; or azocinyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and the like.
Drawings
FIG. 1 shows the crystal structure diagrams of complexes I-1, I-2, I-3 and I-4 prepared in the examples.
FIG. 2 shows the absorption spectra and emission spectra at 77K and 300K of Ag (I) complexes of formula I-2 provided in example 5.
FIG. 3 shows the absorption spectra and emission spectra at 77K and 300K of Ag (I) complexes of formula I-4 provided in example 6.
FIG. 4 is a graph of the transient spectral lifetime of the Ag (I) complex of formula I-2 provided in example 5 at 300K.
FIG. 5 is a graph of the transient spectral lifetime of the Ag (I) complex of formula I-4 provided in example 6 at 300K.
FIG. 6 is a thermogravimetric analysis (TGA) plot of the Ag (I) complexes of formulas I-2 and I-4 provided in examples 5 and 6.
FIG. 7 is a schematic structural view of an electroluminescent device prepared in examples 7 and 8 of the present invention;
wherein: 1-a first electrode layer, 2-a hole injection layer, 3-a hole transport layer, 4-a light-emitting layer, 5-an electron transport layer, 6-an electron injection layer, 7-a second electrode layer.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
It will be understood that when an element such as a layer, region or substrate is referred to as being "on" another element, it can be in contact with the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present.
Example 1
Preparation of ligand madypz:
Figure BDA0002059258260000121
3-bromo-6-fluoro-2-methylpyridine (10mmol,1.9g) was dissolved in 40ml of dry toluene solvent, and sodium tert-butoxide (12mmol,1.1g), palladium acetate (0.25mmol,0.056g) and tri-tert-butylphosphine tetrafluoroborate (1mmol,0.29g) were added, which was stirred at room temperature for 30 min. Then, 9-dimethylacridine (10mmol,2.1g) was added, which was then refluxed at 120 ℃ for 12 hours. After the temperature of the system is reduced to room temperature, the toluene solvent is dried in vacuum by spinning, extracted by dichloromethane and washed by saturated saline three times, and after column separation, white solid 2-methyl-3- (9, 9-dimethylacridine) -6-fluoropyridine (2.0g, 50%) is obtained.1H NMR(400MHz,CDCl3)δ7.68(t,J＝7.9Hz,1H),7.49(dd,J＝7.4,1.7Hz,2H),7.08–6.92(m,5H),6.13–6.03(m,2H),2.28(s,3H),1.70(d,J＝28.4Hz,6H).
The starting material 2-methyl-3- (9, 9-dimethylacridine) -6-fluoropyridine (4.7mmol,0.518g), 3-phenyl-1-hydropyrazole (4.7mmol,0.68g) and potassium carbonate (9.4mmol,1.3g) obtained in the above step were dissolved in 20ml of dry N, N-dimethylacetamide and refluxed at 180 ℃ for 8 hours. After the temperature of the system cooled to room temperature, the mixture was extracted with dichloromethane and washed with saturated brine three times, and the crude product was separated by column chromatography to give the ligand madypz as a white solid (1.7g, 81%).1H NMR(400MHz,CD2Cl2)δ8.70(d,J＝2.6Hz,1H),8.18(d,J＝8.5Hz,1H),7.98(d,J＝7.6Hz,2H),7.75(d,J＝8.5Hz,1H),7.58–7.44(m,4H),7.39(t,J＝7.3Hz,1H),6.98(dq,J＝14.0,6.5Hz,4H),6.88(d,J＝2.6Hz,1H),6.21(d,J＝7.9Hz,2H),2.32(s,3H),1.71(d,J＝23.5Hz,6H).
Example 2
Preparation of ligand maddmpyz
Figure BDA0002059258260000131
The ligand maddmpyz was prepared in 61% overall yield by substituting the reactant 3-phenyl-1-hydropyrazole for 3, 5-dimethylpyrazole according to the method of reference example 1.
Mass spectrometry analysis gave molecular weights: 394.50.
the relative molecular mass percentage of each element (C/H/N) obtained by element analysis is as follows: c, 79.16; h, 6.64; n, 14.20.
Example 3
Preparation of the ligand moaddmppyz
Figure BDA0002059258260000132
Referring to the same procedure as in example 1, the reactant 3-bromo-6-fluoro-2-methylpyridine was replaced with 2-bromo-6-fluoropyridine, and 3-phenyl-1-hydropyrazole was replaced with 3, 5-dimethylpyrazole to give the ligand moaddmppz in a total yield of 57%.
Mass spectrometry analysis gave molecular weights: 380.49.
the relative molecular mass percentage of each element (C/H/N) obtained by element analysis is as follows: c, 78.92; h, 6.36; n, 14.73.
Example 4
Preparation of ligand moadppyz:
Figure BDA0002059258260000141
referring to the procedure of example 1, the reactant 3-bromo-6-fluoro-2-methylpyridine was replaced with 2-bromo-6-fluoropyridine to give the ligand moadppypz in 48% overall yield.
Mass spectrometry analysis gave molecular weights: 428.53.
the relative molecular mass percentage of each element (C/H/N) obtained by element analysis is as follows: c, 81.28; h, 5.65; and N, 13.07.
Example 5
Synthesis of Ag (I) complex of the structure shown in formula I-2:
Figure BDA0002059258260000142
weighing [ Ag (CH)3CN)4]BF4(0.1mmol,0.0358g) and bis (2-diphenylphosphinophenyl) ether(POP) (0.1mmol,0.054g) was dissolved in 5mL of dichloromethane and stirred at room temperature for 30 min. The ligand madypz prepared in example 1 (0.1mmol, 0.0445g) was then added and after stirring at room temperature for 1h, in CH2Cl2Recrystallization from ether solution. The total yield is 70%.1H NMR(400MHz,CD2Cl2)δ8.55(d,J＝2.7Hz,1H),7.98–7.88(m,2H),7.71(d,J＝7.6Hz,2H),7.51–7.45(m,2H),7.42–7.31(m,5H),7.29–7.05(m,20H),7.01–6.91(m,7H),6.80(dd,J＝7.2,3.4Hz,2H),6.66(d,J＝7.8Hz,2H),5.91(d,J＝8.7Hz,2H),1.77(s,3H),1.62(d,J＝40.0Hz,6H).31P NMR(162MHz,CD2Cl2) δ -7.78(dd, J (P-Ag) ═ 409.86 Hz.) the crystal structure of the Ag (I) complex of formula I-2 is shown in fig. 1. The absorption spectrum and emission spectrum are shown in FIG. 2. The transient spectral lifetime at 300K is shown in fig. 4. The thermogravimetric analysis (TGA) pattern is shown in FIG. 6.
Example 6
Synthesis of Ag (I) complex of formula I-4:
Figure BDA0002059258260000151
the reaction POP was replaced with Xantphos, and the same synthesis as in reference example 5 gave an Ag (I) complex of the structure shown as I-4 in an overall yield of 72%.1H NMR(400MHz,CD2Cl2)δ8.56(d,J＝2.7Hz,1H),7.98(q,J＝8.7Hz,2H),7.63(d,J＝7.5Hz,2H),7.56(d,J＝7.7Hz,2H),7.49(d,J＝7.6Hz,2H),7.43–7.30(m,5H),7.20(t,J＝7.5Hz,8H),7.15–6.89(m,15H),6.79(t,J＝7.7Hz,2H),6.65(dt,J＝7.3,3.7Hz,2H),5.89(d,J＝8.2Hz,2H),1.72(s,6H),1.61(d,J＝8.6Hz,9H).31P NMR(162MHz,CD2Cl2)δ-6.39(dd,J(31P-107Ag)＝416.34Hz,J(31P-109Ag) ═ 417.96Hz the crystal structure of Ag (I) complexes of formula I-4 is shown in figure 1. The absorption spectrum and emission spectrum are shown in FIG. 3. The transient spectral lifetime at 300K is shown in fig. 5. The thermogravimetric analysis (TGA) pattern is shown in FIG. 6.
The following compounds were also prepared by the methods described in reference to the above examples:
Figure BDA0002059258260000161
example 7
The Ag (I) complex with the structure shown in the formula I-2 and synthesized in the example 5 is used as a luminescent dye to prepare an electroluminescent device.
A device preparation step: and cleaning the ITO glass by using a glass cleaning agent, sequentially and respectively ultrasonically cleaning the ITO glass for 10 minutes by using distilled water, acetone and isopropanol, and treating the ITO glass for 15 minutes by using ultraviolet ozone. A layer of 40nm polyethylene dioxythiophene-poly (styrene sulfonic acid) (PEDOT: PSS) film is coated on the surface of the cleaned ITO glass in a spin mode, and the ITO glass is quenched for 20 minutes at the temperature of 140 ℃. The structural compound shown as the formula I-2 is doped in bis-4 (N-carbazolyl phenyl) phenyl phosphorus oxide (BCPO) according to the mass fraction of 15%, then dissolved in dichloromethane to prepare a solution with a certain concentration (10mg/1.8ml), and the solution is spin-coated on a PEDOT (PSS) layer to form a light-emitting layer with the thickness of 30 nm. At 4X 10-4Pa vacuum degree, 2, 8-bis (diphenylphosphoryl) dibenzo [ b, d ] of 10nm is sequentially evaporated]Furan (PPF), 30nm 1,3, 5-tris [ (3-pyridyl) -3-phenyl ] -n]Benzene (TPBI) and LiF at 1nm, and finally evaporating an aluminum electrode at 100nm through a mask. The rectangular metallic aluminum cathode and the rectangular ITO anode are mutually and vertically intersected to form a 3 multiplied by 4mm2Square cross-section of (a).
The structure of the resulting device is: ITO/PEDOT PSS (40 nm)/15% wt I-2: 85% wt BCPO (30nm)/PPF (10nm)/TPBI (30nm)/LiF (1nm)/Al (100 nm). The device emits bright sky blue light with CIE color coordinates (0.16,0.26), a turn-on voltage of 6.1V, and a maximum external quantum efficiency of 6.6%.
Example 8
The compound with the structure shown in the formula I-4 synthesized in the example 6 is used as a luminescent dye to prepare a non-doped electroluminescent device. The device preparation and the device structure of example 8 were identical to the device structure described in example 7, except that the structural compound represented by formula I-2 was replaced with the structural compound represented by formula I-4. The device described in example 8 emits bright sky blue with CIE color coordinates (0.16,0.26), a starting voltage of 6.6V, and a maximum external quantum efficiency of 6.6%.
The results of the performance tests of the devices prepared in examples 7 and 8 are shown in table 1.
TABLE 1
Figure BDA0002059258260000171
Example 9
After Ag (I) complexes shown in formulas I-2 and I-4 are doped into PMMA at a concentration of 15% to prepare a film, the photophysical property data, the emission spectrum in a film state, the service life and the quantum efficiency of the film are measured on an ultraviolet-near infrared stable transient fluorescence spectrometer with the model of FLS980, wherein the quantum efficiency is measured in an integrating sphere equipped with the film, and the low-temperature spectrum and the service life are measured in a temperature-changing table equipped with the model of LINKAM THMS 600. The results are shown in Table 2.
TABLE 2
Figure BDA0002059258260000172
As can be seen from Table 2, the complexes prepared in this application have a relatively high radiative transition rate (10)5S-1) And effectively reduces the non-radiative transition rate (10)3S-1) The photoluminescence quantum efficiency is close to 100%, and the material is a thermally activated delayed fluorescent material with high efficiency and short luminescence life, and is beneficial to preparing efficient and stable OLED devices, so that the material can be applied to the industry.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A complex represented by formula a:
Figure FDA0003224779430000011
wherein R is1Is an electron donating group selected from the following structures:
Figure FDA0003224779430000012
dotted-represents a connection site to another unit;
in the structure, R is the same or different and is independently selected from hydrogen and C1-15An alkyl group;
R2、R3、R4identical or different, independently of one another, from hydrogen, C1-15Alkyl radical, C6-20An aryl group;
n is an integer from 0 to 3;
Figure FDA0003224779430000021
represents two unconnected aryl phosphorus ligands P' or a bridged aryl phosphorus bidentate ligand
Figure FDA0003224779430000022
Said P' or
Figure FDA0003224779430000023
Connecting with Ag;
the aryl phosphorus ligand P' is selected from the structures represented by the following formulas P1-P4:
Figure FDA0003224779430000024
wherein, in the structure shown by P1-P4, the central P atom is a connecting site which is connected with Ag;
R8、R9and R10Identical or different, independently of one another, from C1-15An alkyl group;
bridged aryl phosphorus bidentate ligands
Figure FDA0003224779430000025
Selected from the structures represented by the following formulae P5-P9:
Figure FDA0003224779430000026
wherein, in the structures shown by P6-P9, two P atoms in each structure are connecting sites which are simultaneously connected with Ag; m is any integer from 1 to 5;
l is selected from anions.
2. The complex of claim 1, wherein formula a is selected from the structures of formula I or formula II:
Figure FDA0003224779430000031
wherein R is1、R2、R3、R4、L、
Figure FDA0003224779430000032
Having the definition set forth in claim 1.
3. The complex of claim 1 or 2, wherein R in formula A1Selected from the following structures:
Figure FDA0003224779430000033
R2、R3、R4same or different, independently from each other selected from H, C1-6Alkyl or C6-14An aryl group;
l is selected from inorganic anions.
4. The arrangement according to claim 1 or 2A compound represented by the formula A, wherein R is2、R3、R4Identical or different, independently of one another, from H, phenyl, methyl, ethyl, propyl, isopropyl, butyl or tert-butyl;
l is selected from ClO4 -、BF4 -Or PF6 -。
5. The complex of claim 1 or 2, wherein the complex of formula a is selected from the group consisting of:
Figure FDA0003224779430000041
6. a process for preparing a complex as claimed in any one of claims 1 to 5, comprising the steps of:
Figure FDA0003224779430000042
compound A-1, [ Ag (CH)3CN)4]L and
Figure FDA0003224779430000051
reacting to obtain a complex shown as a formula A;
wherein R is1、R2、R3、R4、n、L、
Figure FDA0003224779430000052
Having the definition as set forth in any one of claims 1 to 5.
7. The method of claim 6, wherein the reaction further comprises the preparation of compound a-1, comprising:
Figure FDA0003224779430000053
1) compound A-4 and compound R1H reacts to obtain a compound A-3;
2) reacting the compound A-3 with the compound A-2 to obtain a compound A-1;
wherein R is1、R2、R3、R4N has the definition as defined in any one of claims 1 to 5; x1、X2Identical or different, independently of one another, from the group of leaving groups.
8. Use of a complex as claimed in any one of claims 1 to 5 in the preparation of an organic electroluminescent device.
9. Use according to claim 8, characterized in that the organic electroluminescent device is selected from organic electroluminescent diodes.
10. Use according to claim 8 or 9, characterized in that the complex of formula a is used as a light-emitting layer in an organic electroluminescent device.
CN201910399429.5A 2019-05-14 2019-05-14 Ag (I) complex-based thermal activation delayed fluorescent material and preparation method and application thereof Active CN110105388B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910399429.5A CN110105388B (en) 2019-05-14 2019-05-14 Ag (I) complex-based thermal activation delayed fluorescent material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910399429.5A CN110105388B (en) 2019-05-14 2019-05-14 Ag (I) complex-based thermal activation delayed fluorescent material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN110105388A CN110105388A (en) 2019-08-09
CN110105388B true CN110105388B (en) 2021-11-26

Family

ID=67489932

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910399429.5A Active CN110105388B (en) 2019-05-14 2019-05-14 Ag (I) complex-based thermal activation delayed fluorescent material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN110105388B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112794863B (en) * 2019-11-13 2022-12-20 中国科学院理化技术研究所 Metal organic complex and preparation method and application thereof
CN110746611B (en) * 2019-11-15 2021-06-29 中国科学院理化技术研究所 Chiral Au (I) carbene complex and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104610353A (en) * 2015-02-06 2015-05-13 中国科学院福建物质结构研究所 Ionic phosphorescent Au4Ag2 complex and preparation method and use thereof
CN106833010A (en) * 2017-02-14 2017-06-13 黑龙江大学 The multiple tooth double transmitting dyestuffs of phosphine coordination silver complex, synthetic method and its application
CN106866732A (en) * 2017-02-14 2017-06-20 黑龙江大学 The multiple tooth double transmitting dyestuffs of phosphine coordination silver complex, synthetic method and its application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104610353A (en) * 2015-02-06 2015-05-13 中国科学院福建物质结构研究所 Ionic phosphorescent Au4Ag2 complex and preparation method and use thereof
CN106833010A (en) * 2017-02-14 2017-06-13 黑龙江大学 The multiple tooth double transmitting dyestuffs of phosphine coordination silver complex, synthetic method and its application
CN106866732A (en) * 2017-02-14 2017-06-20 黑龙江大学 The multiple tooth double transmitting dyestuffs of phosphine coordination silver complex, synthetic method and its application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Synthesis and structural systematics of mixed triphenylphosphine/ imidazole base adducts of silver(I) oxyanion salts";Augusto Cingolani et al.,;《J. Chem. Soc., Dalton Trans.》;19991231;第22卷;第4047-4055页 *
"Synthesis, Crystal Structure and Photoluminescence of a Three-coordinate Ag(I) Complex";TENG Teng et al.,;《Chinese J. Struct. Chem.》;20141231;第33卷(第11期);第1661-1665页 *

Also Published As

Publication number Publication date
CN110105388A (en) 2019-08-09

Similar Documents

Publication Publication Date Title
CN109251176B (en) Organic electroluminescent device
EP2539913B1 (en) Phosphorescent emitters
CN105753629B (en) Compound and the Organnic electroluminescent device for using it
KR20140043043A (en) Organic light emitting device and materials for use in same
CN108948056B (en) Thermal activation delayed fluorescent material based on aryl boron derivative and organic electroluminescent device
CN105602553B (en) Thermally activated delayed fluorescence material and its preparation and application based on 4 fluorophenyl acetonitriles
KR20220058419A (en) Heterocyclic compound, organic light emitting device comprising the same, composition for organic layer of organic light emitting device, manufacturing method of the organic light emitting device
CN114702432A (en) Compound containing acenaphthene and application thereof in organic electroluminescent device
CN110105388B (en) Ag (I) complex-based thermal activation delayed fluorescent material and preparation method and application thereof
KR102143580B1 (en) Organic light emitting device, manufacturing method of the same and composition for organic layer of organic light emitting device
CN110577488A (en) Compound with carbazole as core and application thereof in organic electroluminescent device
CN113929708A (en) Boron-containing compound and application thereof in organic electroluminescent device
CN113444072A (en) Compound and application thereof
CN107142103A (en) A kind of conjugated polymer electroluminescent organic material and its application and device comprising TADF monomers by skeleton of acridine
KR20230022872A (en) Compounds, light-emitting materials and light-emitting devices
CN116199723B (en) Phosphorescent doped material with pyridyl aza-dibenzofuran ligand and application thereof
CN109535130B (en) Dihydrobenzandazole compound, organic electroluminescent device and display device
CN112079867A (en) P-containing multi-heterocyclic structure compound and application thereof
KR20230074407A (en) Heterocyclic compound having cyano-substitution
KR102652004B1 (en) Heterocyclic compound, organic light emitting device comprising the same, manufacturing method of the same and composition for organic layer of organic light emitting device
CN113105491B (en) Pyridine diphenoxy boron fluoride compound, application thereof and organic electroluminescent device containing compound
KR102603350B1 (en) A plurality of dopant materials and organic electroluminescent device comprising the same
KR20180068863A (en) Organic Electroluminescent Compound and Organic Electroluminescent Device Comprising the Same
CN110724105B (en) Triphenylene nitrogen-containing seven-membered ring compound and preparation method and application thereof
KR20180117446A (en) Organic Electroluminescent Compound and Organic Electroluminescent Device Comprising the Same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant