CN111278836B - Metal organic complex and application thereof in organic electronic device - Google Patents

Metal organic complex and application thereof in organic electronic device Download PDF

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CN111278836B
CN111278836B CN201880069428.8A CN201880069428A CN111278836B CN 111278836 B CN111278836 B CN 111278836B CN 201880069428 A CN201880069428 A CN 201880069428A CN 111278836 B CN111278836 B CN 111278836B
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CN111278836A (en
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梁志明
黄宏
潘君友
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Guangzhou Chinaray Optoelectronic Materials Ltd
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    • 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
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
    • C07F1/12—Gold compounds
    • C—CHEMISTRY; METALLURGY
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    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The application discloses a transition metal complex, a polymer, a mixture and application thereof in organic electronic devices, in particular to application in organic phosphorescence light emitting diodes. The application also relates to organic electronic devices, in particular organic light-emitting diodes, comprising the transition metal complexes according to the application, and to the use thereof in display and lighting technology. Through device structure optimization, the concentration of the metal complex in the matrix is changed, so that the optimal device performance can be achieved, an OLED device with high efficiency, high brightness and high stability can be conveniently realized, and better material options are provided for full-color display and illumination application.

Description

Metal organic complex and application thereof in organic electronic device
The present application claims priority from chinese patent application No. 201711342792.0 entitled "a metal-organic complex and its use in organic electronic devices," filed in chinese patent office at 12 months 14 of 2017, the entire contents of which are incorporated herein by reference.
Technical Field
The present application relates to transition metal complexes, mixtures and compositions comprising the same, and their use in organic electronic devices, in particular in organic phosphorescent light emitting diodes. The application also relates to an organic electronic device, in particular a light-emitting diode, comprising such a transition metal complex, and to the use thereof in displays and lighting devices.
Background
In flat panel displays and lighting applications, organic Light Emitting Diodes (OLEDs) have the advantages of low cost, light weight, low operating voltage, high brightness, color tunability, wide viewing angle, ease of assembly onto flexible substrates, and low energy consumption, and thus become the most promising display technology. In order to increase the luminous efficiency of organic light emitting diodes, various fluorescent and phosphorescent based luminescent material systems have been developed. An organic light emitting diode using a fluorescent material has high reliability, but its internal electroluminescent quantum efficiency is limited to 25% under electric field excitation. In contrast, since the branching ratio of the singlet excited state and the triplet excited state of excitons is 1:3, the organic light emitting diode using the phosphorescent material can achieve almost 100% internal light emission quantum efficiency. For small molecule OLEDs, triplet excitation is efficiently achieved by doping heavy metal centers, which improves spin-orbit coupling and thus intersystem crossing to the triplet state.
Complexes based on iridium (III) are a class of materials widely used in high efficiency OLEDs, with higher efficiency and stability. Baldo et al report high quantum efficiency OLEDs using fac-tris (2-phenylpyridine) iridium (III) [ Ir (ppy) 3] as the phosphorescent light-emitting material, 4'-N, N' -dicarbazole-biphenyl (CBP) as the host material (appl. Phys. Lett.1999,75,4). Another example of a phosphorescent light-emitting material is the sky blue complex iridium (III) bis [2- (4 ',6' -difluorophenyl) pyridine-N, C2] -picolinate (FIrpic), which when doped into a high triplet energy matrix exhibits extremely high photoluminescence quantum efficiencies of about 60% in solution and almost 100% in solid films (appl. Phys. Lett.2001,79,2082). Although iridium (III) systems based on 2-phenylpyridine and its derivatives have been used in large amounts for the preparation of OLEDs, phosphorescent materials containing other metal centers with these ligands have not yet been fully investigated in general.
Despite the increasing interest in phosphorescent light-emitting materials, in particular metal complexes with heavy metal centers, most efforts have been focused on the use of iridium (III), platinum (II), copper (I) and fetters (II). Other metal centers are rarely of interest. Unlike the isoelectric platinum (II) coordination compounds known to exhibit highly efficient spin-rotation properties, few examples of luminescent gold (III) complexes are reported, which may result from the presence of a low energy d-d coordination field (LF) possessed by the gold (III) metal center and the electrophilicity of the gold (III) metal center. One way to increase the luminous efficiency of gold (III) complexes is to introduce strong sigma-donor ligands, such as the stable gold (III) aryl compounds found and synthesized earliest by Yam et al, which exhibit interesting photo-induced spin-optical properties even at room temperature (j. Chem. Soc., dalton trans.1993, 1001). Another interesting donor is alkynyl. Although the spin-optically active nature of gold (I) alkynyl complexes has been largely studied, the chemistry of gold (III) alkynyl has been largely ignored, with one exception: synthesis of alkynyl gold (III) compounds of 6-benzyl-2, 2' -bipyridine (J.chem. Soc. Dalton Trans.1999, 2823), but their chiral-spinning properties have not been studied. Yam et al disclose the synthesis of a series of bis-cyclometallated alkynyl (III) compounds using a variety of strong sigma-donor alkynyl ligands, wherein all compounds exhibit very strong luminescence properties in a variety of media at both room and low temperatures (J.Am. Chem. Soc.2007,129, 4350). Furthermore, OLEDs prepared with these luminescent gold (III) compounds as phosphorescent dopant materials have external quantum efficiencies of up to 5.5%. These luminescent gold (III) compounds contain a tridentate ligand and at least one strong sigma-donor group coordinated to the metal center of gold (III). Thereafter, yam et al successively reported a novel class of phosphorescent materials (J.Am.chem.Soc.2010, 132, 14273) of metallized alkynyl (III) complexes. The optimized vapor deposition type OLED reached an EQE of 11.5% and a current efficiency of 37.4cd A-1. This suggests that the alkynyl (III) complex is a promising luminescent material. However, the stability of the compounds is still required to be improved.
In order to improve the stability of the gold (III) complex, one solution is to modify the monodentate alkynyl ligand to replace it with a monoanionic bidentate chelating ligand. However, such complexes have not yet been developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, there is a need to improve the stability of metal-organic complex materials, and an object of the present invention is to provide a transition metal complex luminescent material having simple synthesis, novel structure and better stability, in particular, to replace the former monodentate ligand with a bidentate chelating ligand, so as to obtain a more stable gold (III) complex. More preferably, the molecular bonds are shortened, the rigidity of the molecules is increased, the non-radiative transitions are reduced, and the luminous efficiency is higher.
The technical scheme provided by the invention is as follows: a transition metal complex having a general structural formula shown in chemical formula (1):
wherein the symbols and labels used have the following meanings:
m is a metal atom selected from gold, platinum or palladium;
L 1 each occurrence, which may be the same or different, is a ligand comprising O≡X, X is selected from O or N; preferably a bidentate chelating ligand, preferably a monoanionic bidentate chelating ligand;
Ar 1 at each occurrence, the same or different, is an aromatic, heteroaromatic or non-aromatic ring system having 5 to 20 ring atoms, which may be interrupted by one or more radicals R 1 Substitution, said radicals R 1 And may be the same or different in multiple occurrences;
Ar 2 at each occurrence, the same or different, is an aromatic, heteroaromatic or non-aromatic ring system having 5 to 20 ring atoms, which may be interrupted by one or more radicals R 2 Substitution, said radicals R 2 And may be the same or different in multiple occurrences;
R 1 ，R 2 the same or different, at multiple occurrences, are hydrogen or deuterium or halogen atoms or straight chain alkanes, branched alkanes, straight chain alkenes, branched alkenes, alkane ethers, aromatic, heteroaromatic or non-aromatic ring systems having from 1 to 30 carbon atoms.
The transition metal complex can be used as a guest material of a light-emitting layer in a phosphorescent organic light-emitting diode device.
A polymer comprising a transition metal complex as described above as a repeat unit.
A mixture comprising a transition metal complex or polymer as described above and at least one other organic functional material. The other organic functional material may be selected from a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), a light emitting material (Emitter), a Host material (Host), or a Dopant material (Dopant).
An organic electronic device comprising a transition metal complex or polymer according to the invention.
The organic electronic device can be selected from an Organic Light Emitting Diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an Organic Field Effect Transistor (OFET), an organic light emitting field effect transistor, an organic laser, an organic spintronic device, an organic sensor and an organic plasmon emitting diode (Organic Plasmon Emitting Diode).
The beneficial effects are that: the transition metal complex can be used in OLED, especially as a doping material of a light-emitting layer, and can provide higher light-emitting efficiency and longer service life of the device. The possible reasons for this are that the transition metal complex with novel structure replaces the traditional monodentate ligand with the bidentate ligand. Because the ligand increases the rigidity of the molecule relative to the monodentate ligand, the whole complex has better chemical, optical, electrical and thermal stability. Meanwhile, as modification is carried out on the auxiliary ligand, the influence on the wavelength of the maximum luminescence peak caused by the main ligand is low, so that the saturated luminescence color can be reserved.
Detailed Description
The invention provides a novel transition metal complex, a corresponding mixture and composition, and application thereof in an organic electronic device, and the invention is further described in detail below for making the purposes, technical schemes and effects of the invention more clear and definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the present invention, the composition and the printing ink, or ink, have the same meaning and are interchangeable between them.
In the present invention, the Host material, matrix material, host or Matrix material have the same meaning, and they are interchangeable with each other.
In the present invention, the transition metal complex, the metal organic complex, the organic metal complex have the same meaning and are interchangeable.
The present invention relates to an organometallic complex comprising at least one compound represented by chemical formula (1):
wherein the symbols and labels used have the following meanings:
m is a metal atom selected from gold, platinum or palladium.
L 1 Each occurrence, which may be the same or different, is a ligand comprising O≡X, X is selected from O or N; preferably a bidentate chelating ligand, preferably a monoanionic bidentate chelating ligand;
Ar 1 at each occurrence, the same or different, is an aromatic, heteroaromatic or non-aromatic ring system having 5 to 20 ring atoms, which may be interrupted by one or more radicals R 1 Substitution, said radicals R 1 And may be the same or different in multiple occurrences;
Ar 2 at each occurrence, the same or different, are having 5 to 20 rings An aromatic, heteroaromatic or non-aromatic ring system of atoms, which may be substituted by one or more radicals R 2 Substitution, said radicals R 2 And may be the same or different in multiple occurrences;
R 1 ，R 2 the same or different, at multiple occurrences, are hydrogen or deuterium or halogen atoms or straight chain alkanes, branched alkanes, straight chain alkenes, branched alkenes, alkane ethers, aromatic, heteroaromatic or non-aromatic ring systems having from 1 to 30 carbon atoms.
In certain preferred embodiments, an organometallic complex according to formula (1), wherein Ar 1 Selected from unsubstituted or substituted aromatic or heteroaromatic rings having from 5 to 20 ring atoms, preferably from 5 to 18 ring atoms, more preferably from 5 to 12 ring atoms.
In other preferred embodiments, the organometallic complex according to the formula (1), wherein Ar 2 Selected from unsubstituted or substituted heteroaromatic rings having from 5 to 20 ring atoms, preferably from 5 to 18 ring atoms, more preferably from 5 to 14 ring atoms, most preferably from 5 to 12 ring atoms, said heteroaromatic ring comprising at least one ring heteroatom N.
Aromatic groups refer to hydrocarbon groups containing at least one aromatic ring, including monocyclic groups and polycyclic ring systems. Heteroaromatic groups refer to hydrocarbon groups (containing heteroatoms) comprising at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. Polycyclic, these ring species, at least one of which is aromatic or heteroaromatic. For the purposes of the present invention, aromatic or heteroaromatic ring systems include not only aromatic or heteroaromatic systems, but also systems in which a plurality of aryl or heteroaryl groups may also be interrupted by short non-aromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9,9' -spirobifluorene, 9-diaryl fluorene, triarylamine, diaryl ether, etc., are likewise considered aromatic ring systems for the purposes of this invention.
Specifically, examples of aromatic groups are: benzene, naphthalene, anthracene, phenanthrene, perylene, naphthacene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, and derivatives thereof.
Specifically, examples of heteroaromatic groups are: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, naphthyridine, quinoxaline, phenanthridine, primary pyridine, quinazoline, quinazolinone, and derivatives thereof.
In certain embodiments, ar 1 Or Ar 2 Selected from a non-aromatic ring system containing 5 to 20 ring atoms which is unsubstituted or substituted by R. One possible benefit of this embodiment is that the triplet energy level of the metal complex can be increased, thereby facilitating the acquisition of a green or blue light emitter.
For the purposes of the present invention, non-aromatic ring systems contain from 1 to 10, preferably from 1 to 6, carbon atoms in the ring system and include not only saturated but also partially unsaturated ring systems, which may be unsubstituted or mono-or polysubstituted by radicals R, which may be identical or different in each occurrence, and may also contain one or more heteroatoms, preferably Si, N, P, O, S and/or Ge, particularly preferably selected from Si, N, P, O and/or S. These may be, for example, cyclohexyl-like or piperidine-like systems, or cyclooctadiene-like ring systems. The term applies equally to fused non-aromatic ring systems.
R is selected from: (1) C1-C10 alkyl, particularly preferably means the following groups: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoromethyl, 2-trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octylAlkenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl and octynyl; (2) C1-C10 alkoxy, particularly preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy or 2-methylbutoxy; (3) C2 to C10 aryl or heteroaryl, which may be monovalent or divalent depending on the application, may in each case also be referred to as radicals R 10 Substituted and possibly linked to the aromatic or heteroaromatic ring by any desired position, particularly preferred are the following groups: benzene, naphthalene, anthracene, peridinaphthyl, dihydropyrene, chrysene, perylene, fluoranthene, butachlor, pentalene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzofuran, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5, 6-quinoline, benzo-6, 7-quinoline, benzo-7, 8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, napthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinoimidazole, oxazole, benzoxazole, naphthooxazole, anthracenoxazole phenanthro-oxazole, isoxazole, 1, 2-thiazole, 1, 3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, diazoanthracene, 1, 5-naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2, 3-triazole, 1,2, 4-triazole, benzotriazole, 1,2, 3-oxadiazole, 1,2, 4-oxadiazole, 1,2, 5-oxadiazole, 1,3, 4-oxadiazole, 1,2, 3-thiadiazole, 1,2, 4-thiadiazole, 1,2, 5-thiadiazole, 1,3, 4-triazine, 1,2, 3-triazine, tetrazole, 1,2,4, 5-tetrazine, 1,2,3, 4-tetrazine, 1,2,3, 5-tetrazine, purine, diazole, and benzothiadiazine. For the purposes of the present invention, aromatic and heteroaromatic ring systems are understood to mean, in particular, in addition to the aryl and heteroaryl groups mentioned above, biphenylene, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, tetrahydropyrene and cis-or trans-indenofluorene.
In a more preferred embodiment, the organometallic complex having general formula (1) wherein Ar 1 -Ar 2 At least one is provided withAnd contains an aromatic, heteroaromatic group having a number of ring atoms greater than 6.
In a preferred embodiment, the organometallic complex having general formula (1) wherein Ar 1 -Ar 2 May be selected from one of the following formulae:
wherein, the liquid crystal display device comprises a liquid crystal display device,
A 1 、A 2 、A 3 、A 4 、A 5 、A 6 、A 7 、A 8 respectively and independently represent CR 3 Or N;
Y 1 selected from CR 4 R 5 、SiR 4 R 5 、NR 3 C (=o), S or O;
R 3 、R 4 、R 5 selected from H, D, or a linear alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms, or a silyl group, or a substituted keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group (-CN), a carbamoyl group (-C (=o) NH 2 ) Haloformyl group (-C (=O) -X wherein X represents a halogen atom), formyl group (-C (=O) -H), isocyano group, isocyanate group, thiocyanate group or isothiocyanate group, hydroxy group, nitro group, CF 3 Groups, cl, br, F, crosslinkable groups or substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 40 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 40 ring atoms, or combinations of these systems, where one or more groups R 3 ，R 4 ，R 5 A ring which may be bonded to each other and/or to the group is a monocyclic or polycyclic aliphatic or aromatic ring.
In a more preferred embodiment, the chemistryAr in formula (1) 1 ，Ar 2 And may be selected from one of the following structural groups, wherein the H in the ring may be optionally substituted:
in a more preferred embodiment, the transition metal complex according to the present invention, wherein Ar in formula (1) 1 Selected from the following general formula:
wherein #2 represents Ar as shown in the chemical formula (1) 2 Is bonded at any position of the substrate. M is a metal atom selected from gold, platinum or palladium, with gold being particularly preferred.
Z 1-18 In multiple occurrences, the same or different, contain one or more carbon, or nitrogen, or oxygen, or silicon, or boron, sulfur, or phosphorus atoms.
R 3-5 The same or different, at multiple occurrences, are hydrogen or deuterium or halogen atoms or straight chain alkanes, branched alkanes, straight chain alkenes, branched alkenes, alkane ethers, aromatic, heteroaromatic or non-aromatic ring systems having from 1 to 20 carbon atoms.
In another preferred embodiment, the transition metal complex according to the invention, wherein Ar in formula (1) 2 Selected from the following general formula:
wherein #1 represents Ar as in the formula (1) 1 Is bonded at any position of the substrate. M is a metal atom selected from gold, platinum or palladium, particularly preferredIs gold.
Z 19-36 In multiple occurrences, the same or different, contain one or more carbon, or nitrogen, or oxygen, or silicon, or boron, sulfur, or phosphorus atoms.
R 6-8 The same or different, at multiple occurrences, are hydrogen or deuterium or halogen atoms or straight chain alkanes, branched alkanes, straight chain alkenes, branched alkenes, alkane ethers, aromatic, heteroaromatic or non-aromatic ring systems having from 1 to 20 carbon atoms.
Specifically, in a more preferred embodiment, ar in formula (1) 1 ，Ar 2 At least one of the atoms forming a coordination bond with the metal center M is a carbon atom, and particularly preferably both of them are carbon atoms.
In certain more preferred embodiments, the organometallic complex according to the invention is selected from one of the following general formulae:
wherein L is 2 With L as described above 1 The definition is the same;
y, in multiple occurrences, is the same or different and comprises one or more carbon, or nitrogen, or oxygen, or silicon, or boron, sulfur, or phosphorus atoms;
R 16-20 The same or different at each occurrence is a hydrogen or deuterium or halogen atom or a linear alkane, branched alkane, linear alkene, branched alkene, alkane ether, aromatic, heteroaromatic or non-aromatic ring system which may be substituted or unsubstituted, having from 1 to 20 carbon atoms.
According to the transition metal complex of the present invention, L in the chemical formula (1) 1 Is a ligand comprising O≡X, having the general formula, wherein X is preferably selected from O or N:
in a more preferred embodiment, the transition metal complex according to the invention, L in formula (1) 1 And L in the formulae (A-1) to (A-36) 2 Is a monoanionic bidentate chelating ligand, preferably selected from the following structures:
wherein R is 9-13 The same or different, at multiple occurrences, are hydrogen or deuterium or halogen atoms or straight chain alkanes, branched alkanes, straight chain alkenes, branched alkenes, alkane ethers, aromatic, heteroaromatic or non-aromatic ring systems having from 1 to 20 carbon atoms.
V in multiple occurrences may be the same or different and is selected from the group consisting of linear alkanes, branched alkanes, linear alkenes, branched alkenes, alkane ethers, or O, S, S = O, SO having 1 to 2 carbon atoms 2 、N(R)、B(R)、Si(R) 2 、Ge(R) 2 、P(R)、P(＝O)R、P(R) 3 、Sn(R) 2 、C(R) 2 、C＝O、C＝S、C＝Se、C＝N(R) 2 Or c=c (R) 2 . And R is hydrogen or deuterium or a halogen atom or a linear alkane, branched alkane, alkane ether, alkane aromatic ring system, alkane heteroaromatic or alkane non-aromatic ring system having 1 to 20 carbon atoms.
In a particularly preferred embodiment, L in formula (1) 1 Preferably selected from the following structures:
where M is a metal atom representing gold, platinum or palladium, gold being particularly preferred.
R 14-15 At multiple occurrences, the same or different are hydrogen orDeuterium or halogen atoms or linear alkanes, branched alkanes, linear alkenes, branched alkenes, alkane ethers, aromatic, heteroaromatic or non-aromatic ring systems having 1 to 20 carbon atoms.
According to the organometallic complex of the present invention, the metal element M is selected from any one of gold (Au), palladium (Pd), and platinum (Pt).
In a particularly preferred embodiment, the metal element M is Au.
From the viewpoint of heavy atom effect, au is particularly preferably used as the center metal M of the above-mentioned metal-organic complex. This is because iridium is chemically stable and has a remarkable heavy atomic effect, resulting in high luminous efficiency.
Specific examples of suitable metal-organic complexes according to the present invention are given below, but are not limited to:
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Wherein R in the metal complexes (Au-1) to (Au-216) 21 -R 30 The same or different, at multiple occurrences, are hydrogen or deuterium or halogen atoms or straight chain alkanes, branched alkanes, straight chain alkenes, branched alkenes, alkane ethers, aromatic, heteroaromatic or non-aromatic ring systems having from 1 to 30 carbon atoms.
In a particularly preferred embodiment, the metal-organic complexes according to the invention are luminescent materials having a luminescence wavelength of between 300 and 1000nm, preferably between 350 and 900nm, more preferably between 400 and 800 nm. The term luminescence as used herein refers to photoluminescence or electroluminescence. In certain preferred embodiments, the metal-organic complexes according to the invention have a photoluminescence efficiency of > 30%, preferably > 40%, more preferably > 50%, most preferably > 60%.
In certain embodiments, the metal-organic complexes according to the invention may also be non-luminescent materials.
The invention also relates to a high polymer, wherein at least one repeating unit comprises a structure shown as a chemical formula (I). In certain embodiments, the polymer is a non-conjugated polymer wherein the structural unit of formula (I) is on a side chain. In another preferred embodiment, the polymer is a conjugated polymer.
In a preferred embodiment, the polymer is synthesized by a method selected from SUZUKI-, YAMAMOTO-, STILE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD-and ULMAN.
In a preferred embodiment, the polymers according to the invention have a glass transition temperature (Tg) of not less than 100℃preferably not less than 120℃more preferably not less than 140℃more preferably not less than 160℃and most preferably not less than 180 ℃.
In a preferred embodiment, the polymers according to the invention have a molecular weight distribution (PDI) in the range from 1 to 5; more preferably 1 to 4; more preferably 1 to 3, still more preferably 1 to 2, and most preferably 1 to 1.5.
In a preferred embodiment, the polymers according to the invention have a weight average molecular weight (Mw) in the range from 1 to 100. Mu.m; more preferably 5 to 50 tens of thousands; more preferably 10 to 40 tens of thousands, still more preferably 15 to 30 tens of thousands, and most preferably 20 to 25 tens of thousands.
The invention also relates to a mixture comprising at least one metal-organic complex or polymer according to the invention and at least one further organic functional material. The organic functional materials include hole (also called hole) injecting or transporting materials (HIM/HTM), hole Blocking Materials (HBM), electron injecting or transporting materials (EIM/ETM), electron Blocking Materials (EBM), organic Host materials (Host), singlet emitters (fluorescent emitters), triplet emitters (phosphorescent emitters), especially luminescent organometallic complexes, and doping materials (Dopant). Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1 and WO 2011110277A1, the entire contents of which 3 patent documents are hereby incorporated by reference. The organic functional material may be small molecule and high polymer materials.
In certain embodiments, the metal organic complex is present in the mixture according to the invention in an amount of 0.01wt% to 30wt%, preferably 0.5wt% to 20wt%, more preferably 2wt% to 15wt%, most preferably 5wt% to 15wt%.
In a preferred embodiment, the mixture according to the invention comprises a metal-organic complex or polymer according to the invention and a triplet matrix material.
In a further preferred embodiment, the mixtures according to the invention comprise a metal-organic complex or a polymer according to the invention, a triplet matrix material and a triplet emitter.
In a further preferred embodiment, the mixture according to the invention comprises a metal-organic complex or polymer according to the invention and a thermally activated delayed fluorescence luminescent material (TADF).
In a further preferred embodiment, the mixture according to the invention comprises a metal-organic complex or polymer according to the invention, a triplet matrix material and a thermally activated delayed fluorescence light emitting material (TADF).
Some more detailed descriptions of triplet host materials, triplet emitters and TADF materials are provided below (but are not limited thereto).
1. Triplet Host material (Triplet Host):
examples of the triplet Host material are not particularly limited, and any metal complex or organic compound may be used as the Host, as long as the triplet energy level thereof is higher than that of the light emitting body, particularly the triplet light emitting body or phosphorescent light emitting body, and examples of the metal complex that can be used as the triplet Host (Host) include, but are not limited to, the following general structures:
m3 is a metal; (Y) 3 -Y 4 ) Is a bidentate ligand, Y 3 And Y 4 Independently selected from C, N, O, P, and S; l is a secondary ligand; m3 is an integer having a value from 1 to the maximum coordination number of the metal; in a preferred embodiment, the metal complex useful as a triplet entity has the form:
(O-N) is a bidentate ligand in which the metal coordinates to the O and N atoms and m3 is an integer ranging from 1 to the maximum coordination number for the metal.
In one embodiment, M3 is selected from Ir and Pt.
Examples of the organic compound which can be a triplet body are selected from compounds containing a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenylbenzene, benzofluorene; compounds containing an aromatic heterocyclic group such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, dibenzocarbazole, indolocarbazole, pyridine indole, pyrrole bipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, oxazole, dibenzooxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, phthalazine, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, oxaanthracene, acridine, phenazine, phenothiazine, phenoxazine, benzofuran pyridine, furopyridine, benzothiophenpyridine, thiophenpyridine, benzoselenophenpyridine and selenophenedipyridine; groups containing 2 to 10 ring structures, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, are bonded to each other directly or through at least one group such as an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an alicyclic group. Wherein each Ar may be further substituted with a substituent selected from the group consisting of hydrogen, deuterium, cyano, halogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl, and heteroaryl.
In a preferred embodiment, the triplet host material may be selected from compounds comprising at least one of the following groups:
R 2 -R 7 is as defined for R 1 ，X 9 Selected from CR1R2 or NR1, Y is selected from CR 1 R 2 Or NR (NR) 1 Or O or S. R is R 1 ，n 2 ，X 1 -X 8 ，Ar 1 ～Ar 3 Is as defined above.
Examples of suitable triplet host materials are listed below, but are not limited to:
2. thermally activated delayed fluorescence luminescent material (TADF):
the traditional organic fluorescent material can only emit light by using 25% singlet excitons formed by electric excitation, and the internal quantum efficiency of the device is low (25% at maximum). Although the phosphorescent material enhances intersystem crossing due to strong spin-orbit coupling of heavy atom center, singlet excitons and triplet excitons formed by electric excitation can be effectively utilized to emit light, so that the internal quantum efficiency of the device reaches 100%. However, the problems of expensive phosphorescent materials, poor material stability, serious roll-off of device efficiency and the like limit the application of the phosphorescent materials in OLED. The thermally activated delayed fluorescence luminescent material is a third generation organic luminescent material that develops subsequent to the organic fluorescent material and the organic phosphorescent material. Such materials typically have a small singlet-triplet energy level difference (deltaest), and triplet excitons may be converted to singlet excitons by intersystem crossing to emit light. This makes it possible to fully utilize singlet excitons and triplet excitons formed under electric excitation. The quantum efficiency in the device can reach 100%. Meanwhile, the material has controllable structure, stable property and low price, does not need noble metal, and has wide application prospect in the field of OLED.
The TADF material needs to have a small singlet-triplet energy level difference, preferably deltaest <0.3eV, next preferably deltaest <0.25eV, more preferably deltaest <0.20eV, and most preferably deltaest <0.1eV. In one preferred embodiment, the TADF material has a relatively small Δest, and in another preferred embodiment, the TADF material has a relatively good fluorescence quantum efficiency. Some TADF luminescent materials can be found in the following patent documents: CN103483332 (a), TW201309696 (a), TW201309778 (a), TW201343874 (a), TW201350558 (a), US20120217869 (A1), WO2013133359 (A1), WO2013154064 (A1), adachi, et.al.Adv.Mater.,21,2009,4802,Adachi,et.al.Appl.Phys.Lett, 98,2011,083302, adachi, et al.appl. Phys. Lett, 101,2012,093306, adachi, et al.chem. Commun, 48,2012,11392,Adachi,et.al.Nature Photonics,6,2012,253,Adachi,et.al.Nature,492,2012,234,Adachi,et.al.J.Am.Chem.Soc,134,2012,14706,Adachi,et.al.Angew.Chem.Int.Ed,51,2012,11311,Adachi,et.al.Chem.Commun, 48,2012,9580, adachi, et al.chem. Commun, 48,2013,10385, adachi, et al.adv. Mater, 25,2013,3319, adachi, et al adv. Mate, 25,2013,3707, adachi, et al chem. Mate, 25,2013,3038, adachi, et al chem. Mate, 25,2013,3766, adachi, et al j. Mate. Chem. C.,1,2013,4599, adachi, et al j. Phys. Chem. A.,117,2013,5607, the entire contents of the above listed patent or article documents are hereby incorporated by reference.
Examples of some suitable TADF luminescent materials are listed below, but are not limited to:
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3. triplet Emitter (Triplet Emitter)
Triplet emitters are also known as phosphorescent emitters. In a preferred embodiment, the triplet emitter is a metal complex of the formula M (L) n, where M is a metal atom, L, which may be identical or different at each occurrence, is an organic ligand which is bonded or coordinately bound to the metal atom M via one or more positions, n being an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6. Optionally, the metal complexes are attached to a polymer via one or more positions, preferably via organic ligands.
In a preferred embodiment, the metal atom M is selected from the transition metal elements or the lanthanoids or actinoids, preferably Ir, pt, pd, au, rh, ru, os, sm, eu, gd, tb, dy, re, cu or Ag, particularly preferably Os, ir, ru, rh, re, pd, au or Pt.
Preferably, the triplet emitter comprises a chelating ligand, i.e. a ligand, coordinated to the metal via at least two binding sites, it being particularly preferred that the triplet emitter comprises two or three identical or different bidentate or polydentate ligands. Chelating ligands are beneficial for improving the stability of metal complexes.
Examples of organic ligands may be selected from phenylpyridine derivatives, 7, 8-benzoquinoline derivatives, 2 (2-thienyl) pyridine derivatives, 2 (1-naphthyl) pyridine derivatives or 2-phenylquinoline derivatives. All of these organic ligands may be substituted, for example by fluorine or trifluoromethyl. The auxiliary ligand may preferably be selected from the group consisting of acetone acetate and picric acid.
In a preferred embodiment, the metal complexes useful as triplet emitters are of the form:
wherein M is a metal selected from the transition metal elements or the lanthanides or actinides, with particular preference Ir, pt, au;
Ar 1 each occurrence, which may be the same or different, is a cyclic group containing at least one donor atom, i.e., an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which the cyclic group is coordinately bound to the metal; ar (Ar) 2 Each occurrence, which may be the same or different, is a cyclic group containing at least one C atom through which the cyclic group is attached to the metal; ar (Ar) 1 And Ar is a group 2 Are linked together by covalent bonds, may each carry one or more substituent groups, and may be linked together again by substituent groups; l' may be the same or different at each occurrence and is a bidentate chelating ancillary ligand, preferably a monoanionic bidentate chelating ligand; q1 may be 0, 1, 2 or 3, preferably 2 or 3; q2 may be 0, 1, 2 or 3, preferably 1 or 0.
Examples of materials and applications of some triplet emitters can be found in the following patent documents and literature: WO 200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP 1191614, WO 2005033244, WO 2005019373, US 2005/0258742, WO 2009146770, WO 2010015307, WO 2010031485, WO 2010054731, WO 2010054728, WO 2010086089, WO 20070087219 A1, US 20090061681 A1, US 2010086089 A1, baldo, thompson et al Nature 403, (2000), 750-753, US 200961681 A1, adachi et al appl. Phys. Lett.78 (2001), 1622-1624, J.Kido et al applied. Phys. Lett.65 (1994), 2124, kido et al chem. Lett.657,1990, US 2007/0252517 A1, johnson et al, JACS 2010086089, wright ton, JACS 2010086089, ma et al, synthh.metals 2010086089, US 2010086089 A1, WO 2010086089 A1, US 2010086089 A1, WO 2010086089 A1, CN 2010086089 A1, WO 2010086089 A1. The entire contents of the above listed patent documents and literature are hereby incorporated by reference.
Examples of some suitable triplet emitters are listed below:
it is an object of the present invention to provide a material solution for an evaporated OLED.
In a preferred embodiment, the metal-organic complexes according to the invention are used in vapor-depositing OLED devices. For this purpose, the metal-organic complexes according to the invention have a molecular weight of 1100g/mol or less, preferably 1000g/mol or less, very preferably 950g/mol or less, most preferably 900g/mol or less.
It is another object of the invention to provide a material solution for printed OLEDs.
In certain embodiments, the metal-organic complexes according to the invention have a molecular weight of 800g/mol or more, preferably 900g/mol or more, very preferably 1000g/mol or more, most preferably 1100g/mol or more.
In other embodiments, the metal organic complexes according to the invention have a solubility in toluene of 3mg/ml or more, preferably 4mg/ml or more, more preferably 6mg/ml or more, most preferably 8mg/ml or more at 25 ℃.
The invention further relates to a composition or printing ink comprising a metal organic complex or a polymer as described above or a mixture comprising the same, and at least one organic solvent.
The invention further provides a process for preparing a film comprising the metal-organic complex or the polymer according to the invention from a solution.
When used in the printing process, the viscosity and surface tension of the ink are important parameters. The surface tension parameters of a suitable ink are suitable for a particular substrate and a particular printing method.
In a preferred embodiment, the ink according to the invention has a surface tension in the range of about 19dyne/cm to 50dyne/cm at an operating temperature or at 25 ℃; more preferably in the range of 22dyne/cm to 35 dyne/cm; preferably in the range of 25dyne/cm to 33 dyne/cm.
In another preferred embodiment, the ink according to the present invention has a viscosity in the range of about 1cps to 100cps at the operating temperature or 25 ℃; preferably in the range of 1cps to 50 cps; more preferably in the range of 1.5cps to 20 cps; and preferably in the range of 4.0cps to 20 cps. The composition so formulated will be suitable for inkjet printing.
The viscosity can be adjusted by different methods, such as by appropriate solvent selection and concentration of functional material in the ink. The inks according to the invention comprising the metal-organic complexes or polymers described can be used conveniently for adjusting printing inks in the appropriate range according to the printing process used. Generally, the composition according to the invention comprises functional materials in a weight ratio ranging from 0.3% to 30% by weight, preferably ranging from 0.5% to 20% by weight, more preferably ranging from 0.5% to 15% by weight, even more preferably ranging from 0.5% to 10% by weight, most preferably ranging from 1% to 5% by weight.
In some embodiments, the at least one organic solvent is selected from aromatic or heteroaromatic based solvents, particularly aliphatic chain/ring substituted aromatic solvents, or aromatic ketone solvents, or aromatic ether solvents, in accordance with the inks of the present invention.
Examples of solvents suitable for the present invention are, but are not limited to: solvents based on aromatic or heteroaromatic: para-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, para-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluenes, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3, 4-tetramethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 1, 3-dipropoxybenzene, 4-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, dichloromethane, 4- (3-phenylpropyl) pyridine, 1, 3-dibenzene, 1, 2-dibenz-dimethylnaphthalene, 2-dibenz ether, and the like; ketone-based solvents: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylbenzophenone, 3-methylbenzophenone, 2-methylbenzophenone, isophorone, 2,6, 8-trimethyl-4-nonone, fenchyl ketone, 2-nonone, 3-nonone, 5-nonone, 2-decanone, 2, 5-adipone, isophorone, di-n-amyl ketone; aromatic ether solvent: 3-phenoxytoluene, butoxybenzene, benzylbutylbenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxane, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylben-ther, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-t-butyl anisole, trans-p-propenyl anisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, amyl ether c-hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether; ester solvent: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like.
Further, the at least one solvent according to the ink of the present invention may be selected from: aliphatic ketones such as 2-nonene, 3-nonene, 5-nonene, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonene, phorone, di-n-amyl ketone and the like; or aliphatic ethers such as amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.
In other embodiments, the printing ink further comprises another organic solvent. Examples of another organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1-trichloroethane, 1, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydronaphthalene, decalin, indene and/or mixtures thereof.
In a preferred embodiment, the composition according to the invention is a solution.
In another preferred embodiment, the composition according to the invention is a suspension.
The invention also relates to the use of said composition as a coating or printing ink for the production of organic electronic devices, particularly preferably by printing or coating.
Suitable Printing or coating techniques include, but are not limited to, ink jet Printing, jet Printing (nozle Printing), letterpress Printing, screen Printing, dip coating, spin coating, doctor blade coating, roller Printing, twist roller Printing, lithographic Printing, flexography, rotary Printing, spray coating, brush or pad Printing, jet Printing (nozle Printing), slot die coating, and the like. Preferred are inkjet printing, slot die coating, inkjet printing and gravure printing. The solution or suspension may additionally contain one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, etc. for adjusting viscosity, film forming properties, improving adhesion, etc. For details on printing techniques and their related requirements for solutions, such as solvents and concentrations, viscosities, etc., see the handbook of printing media, by Helmut Kipphan: techniques and methods of production (Handbook of Print Media: technologies and Production Methods), ISBN 3-540-67326-1.
Based on the organometallic complex, the invention also provides an application of the organometallic complex or the high polymer in an organic electronic device. The organic electronic device may be selected from, but not limited to, organic Light Emitting Diodes (OLED), organic photovoltaic cells (OPV), organic light emitting cells (OLEEC), organic Field Effect Transistors (OFET), organic light emitting field effect transistors, organic lasers, organic spintronic devices, organic sensors, and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), and the like, particularly OLED. In the embodiment of the invention, the organometallic complex is preferably used in a light-emitting layer of an OLED device.
The invention further relates to an organic electronic device comprising at least one organometallic complex or polymer as described above. Generally, such organic electronic devices comprise at least one cathode, one anode and one functional layer between the cathode and the anode, wherein the functional layer comprises at least one organometallic complex or polymer as described above. The organic electronic device may be selected from, but not limited to, organic Light Emitting Diodes (OLEDs), organic photovoltaic cells (OPVs), organic light emitting cells (olecs), organic Field Effect Transistors (OFETs), organic light emitting field effect transistors, organic lasers, organic spintronics devices, organic sensors, and organic plasmon emitting diodes (Organic Plasmon Emitting Diode).
In a particularly preferred embodiment, the organic electronic device is an electroluminescent device, particularly preferably an OLED, comprising a substrate, an anode, at least one light-emitting layer, and a cathode.
The substrate may be opaque or transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, bulovic et al Nature 1996,380, p29, and Gu et al, appl. Phys. Lett.1996,68, p2606. The substrate may be rigid or elastic. The substrate may be plastic, metal, semiconductor chip or glass. Preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice. In a preferred embodiment, the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150℃or higher, preferably over 200℃and more preferably over 250℃and most preferably over 300 ℃. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).
The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or a light emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or of the p-type semiconductor material as HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. Examples of anode materials include, but are not limited to: al, cu, au, ag, mg, fe, co, ni, mn, pd, pt, ITO aluminum doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.
The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO or conduction band level of the emitter in the light emitting layer or of the n-type semiconductor material as an Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, and most preferably less than 0.2eV. In principle, all materials which can be used as cathode of an OLED are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, au, ag, ca, ba, mg, liF/Al, mgAg alloy, baF2/Al, cu, fe, co, ni, mn, pd, pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
The OLED may further include other functional layers such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL). Materials suitable for use in these functional layers are described above.
In a preferred embodiment, the light-emitting layer of the light-emitting device according to the invention comprises an organometallic complex or a polymer according to the invention, which can be produced by means of vacuum evaporation or solution processing.
The light emitting device according to the invention has a light emission wavelength between 300nm and 1000nm, preferably between 350nm and 900nm, most preferably between 400nm and 800 nm.
The invention also relates to the use of the organic electronic device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.
The invention will be described in connection with the preferred embodiments, but the invention is not limited thereto, and it will be appreciated that the appended claims summarize the scope of the invention and those skilled in the art who have the benefit of this disclosure will recognize certain changes that may be made to the embodiments of the invention and that are intended to be covered by the spirit and scope of the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
1. Metal organic complex and energy structure thereof
The energy level of the metal-organic complex can be obtained by quantum computation, for example by means of a Gaussian03W (Gaussian inc.) using TD-DFT (time-dependent density functional theory), and specific simulation methods can be found in WO2011141110. The molecular geometry is first optimized by the semi-empirical method "group State/Hartree-Fock/Default Spin/LanL2MB" (Charge 0/Spin single), and then the energy structure of the organic molecule is calculated by the TD-DFT (time-Density functional theory) method as "TD-SCF/DFT/Default Spin/B3PW91/gen geom= connectivity pseudo =lan2" (Charge 0/Spin single). The HOMO and LUMO energy levels are calculated according to the following calibration formula, and S1 and T1 are used directly.
HOMO(eV)＝((HOMO(Gaussian)×27.212)-0.9899)/1.1206
LUMO(eV)＝((LUMO(Gaussian)×27.212)-2.0041)/1.385
Wherein HOMO (G) and LUMO (G) are direct calculations of Gaussian 03W in Hartree. The results are shown in Table one:
list one
Material HOMO[eV] LUMO[eV] T1[eV] S1[eV]
Au-1 -6.18 -2.48 2.98 3.55
Au-3 -6.03 -2.50 2.70 3.50
Au-6 -5.94 -2.51 2.51 3.45
c-Au-1 -6.18 -2.49 2.98 3.53
2. Synthesis of metal organic complexes
Synthetic example 1 synthetic complex Au-1:
synthesis of intermediate A:
2,2' -dibromobisbenzene (20 g,1 eq) was placed in a dry 1000ml double-necked flask, and the flask was evacuated and circulated three times with nitrogen, then dehydrated ether (600 ml) was added for dissolution, and after the temperature was lowered to 77K, n-butyllithium (54 ml,2 eq) was added, followed by stirring at room temperature for 2 hours. Dibutyl tin dichloride (19.6 g,1.01 eq) was then dissolved in 60ml of diethyl ether and added to the reaction using a syringe. Stirring at room temperature for one day, adding water and then separating. The diethyl ether layer was dried by spin-drying and purified by column to give intermediate a as off-white (50% yield).
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Synthetic intermediate B:
in a dry 500ml double vial was placed tetrachloroauric acid (10 g,1 eq), 200ml acetonitrile was added to dissolve, then intermediate a (10 g,1.02 eq) was added and the reaction was allowed to react at 80 ℃ for one day. The white precipitate was filtered and washed with acetonitrile and dichloromethane to afford intermediate B as off-white (31% yield).
Synthesis of Au-1:
in a dry 250ml bottle was placed 2, 8-dimethyl-4, 6-nonyldione (0.5 g,2 eq) and sodium carbonate (0.18 g,5 eq) and dissolved with a minimum amount of ethanol. Then, after 50ml of chloroform was added, intermediate B (1 g,1 eq) was added, and the reaction temperature was raised to 50℃and stirred for one day. Then, the reaction mixture was dried by spinning, dissolved in chloroform, and then solids which could not be completely dissolved were filtered off. Methanol is added into the filtrate to precipitate out, and white solid Au-1 is obtained after filtration (yield 40%).
Synthetic example 2 synthetic complex Au-3:
synthesis of intermediate C:
in a dry 1000ml double-necked flask were placed 1, 2-dibromobenzene (20 g,1 eq), 2, 3-dibromonaphthalene (24.2 g,1 eq), pinacol bisborate (21.5 g,1 eq), pd (ddpf) Cl 2 (6.2 g,0.1 eq) and potassium phosphate (90 g,5 eq) were added followed by dioxane (500 ml), the reaction was heated to 80℃and stirred for one day. The reaction mixture was then dried by spinning, and the organic phase was dried by spinning with water and dichloromethane and purified by column to give intermediate C (yield 13%) as tan.
Synthetic intermediate D:
in a dry 1000ml double flask, intermediate C (23.2 g,1 eq) was placed, circulated three times with vacuum and nitrogen, then dissolved in dry diethyl ether (600 ml), cooled to 77K and then n-butyllithium (54 ml,2 eq) was added, followed by stirring at room temperature for 2 hours. Dibutyl tin dichloride (19.6 g,1.01 eq) was then dissolved in 60ml of diethyl ether and added to the reaction using a syringe. Stirring at room temperature for one day, adding water and then separating. The diethyl ether layer was dried by spin-drying and purified by column to give intermediate D as off-white (59% yield).
Synthetic intermediate E:
in a dry 500ml double vial was placed tetrachloroauric acid (10 g,1 eq), 200ml acetonitrile was added to dissolve, then intermediate D (11.3 g,1.02 eq) was added and the reaction was allowed to react at 80 ℃ for one day. The white precipitate was filtered and washed with acetonitrile and dichloromethane to afford intermediate E (28% yield) as off-white.
Synthesis of Au-3:
in a dry 250ml bottle were placed acetylacetone (0.27 g,2 eq) and sodium carbonate (0.18 g,5 eq) and dissolved with minimal amount of ethanol. Then, after 50ml of chloroform was added, intermediate E (1.13 g,1 eq) was added, and the reaction temperature was raised to 50℃and stirred for one day. Then, the reaction mixture was dried by spinning, dissolved in chloroform, and then solids which could not be completely dissolved were filtered off. Methanol is added into the filtrate to precipitate out, and white solid Au-3 is obtained after filtration (yield 24%).
Synthetic example 3 synthetic complex Au-6:
synthetic intermediate F:
in a dry 1000ml double vial were placed 2, 3-dibromonaphthalene (48.4 g,2 eq), pinacol biborate (21.5 g,1 eq), pd (ddpf) Cl 2 (6.2 g,0.1 eq) and potassium phosphate (90 g,5 eq) were added followed by dioxane (500 ml), the reaction was heated to 80℃and stirred for one day. The reaction mixture was then dried by spinning, and the organic phase was dried by spinning with water and dichloromethane and purified by column to give intermediate F (yield 19%) as tan.
Synthetic intermediate G:
in a dry 1000ml double flask, intermediate F (26.4 g,1 eq) was placed, circulated three times with vacuum and nitrogen, then dissolved in dry diethyl ether (600 ml), cooled to 77K and then added n-butyllithium (54 ml,2 eq) and stirred at room temperature for 2 hours. Dibutyl tin dichloride (19.6 g,1.01 eq) was then dissolved in 60ml of diethyl ether and added to the reaction using a syringe. Stirring at room temperature for one day, adding water and then separating. The diethyl ether layer was dried by spin-drying and purified by column to give intermediate G as off-white (70% yield).
Synthetic intermediate H:
in a dry 500ml double vial was placed tetrachloroauric acid (10G, 1 eq), 200ml acetonitrile was added to dissolve, then intermediate G (12.6G, 1.02 eq) was added and the reaction was allowed to react at 80 ℃ for one day. The white precipitate was filtered and washed with acetonitrile and dichloromethane to afford intermediate H as off-white (28% yield).
Synthesis of Au-6:
in a dry 250ml bottle were placed acetylacetone (0.27 g,2 eq) and sodium carbonate (0.18 g,5 eq) and dissolved with minimal amount of ethanol. Then, after 50ml of chloroform was added, intermediate H (1.26 g,1 eq) was added, and the reaction temperature was raised to 50℃and stirred for one day. Then, the reaction mixture was dried by spinning, dissolved in chloroform, and then solids which could not be completely dissolved were filtered off. Methanol is added into the filtrate to precipitate out, and white solid Au-6 is obtained after filtration (yield 15%).
Synthesis example 4 Synthesis of Complex c-Au-1
Synthesis of c-Au-1:
in a dry 250ml bottle was placed 2, 8-dimethyl-4, 6-nonyldione (0.27 g,2 eq) and sodium carbonate (0.18 g,5 eq) and dissolved with a minimum amount of ethanol. Then, after 50ml of chloroform was added, intermediate B (1 g,1 eq) was added, and the reaction temperature was raised to 50℃and stirred for one day. Then, the reaction mixture was dried by spinning, dissolved in chloroform, and then solids which could not be completely dissolved were filtered off. Methanol was added to the filtrate to precipitate out, and after filtration, c-Au-1 was obtained as a white solid (yield 53%).
Preparation and characterization of oled devices:
OLED devices with ITO/NPD (60 nm)/10% (Au-1 or Au-3 or Au-6 or c-Au-1): mCP (45 nm)/TPBi (35 nm)/LiF (1 nm)/Al (150 nm)/cathode were prepared as follows:
a. cleaning the conductive glass substrate: when the cleaning agent is used for the first time, various solvents such as chloroform, ketone and isopropanol can be used for cleaning, and then ultraviolet ozone plasma treatment is carried out;
b. HTL (60 nm), EML (45 nm), ETL (35 nm): in high vacuum (1X 10) -6 Mbar) by thermal evaporation;
c. and (3) cathode: liF/Al (1 nm/150 nm) in high vacuum (1X 10) -6 Millibar) by thermal evaporation;
d. and (3) packaging: the device was encapsulated with an ultraviolet curable resin in a nitrogen glove box.
The current-voltage-luminance (JVL) characteristics of OLED devices are characterized by a characterization device while recording important parameters such as efficiency and external quantum efficiency. The maximum external quantum efficiencies of the OLED devices Au-1, au-3, au-6 and c-Au-1 were detected to be 6.5%, 5.8%, 5.7% and 3.1%, respectively.
Further optimization, such as optimization of device structure, optimization of combination of HTM, ETM and host materials, will further improve device performance, especially efficiency, drive voltage and lifetime.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that the application of the invention is not limited to the examples described above, but that several variations and modifications can be made by a person skilled in the art without departing from the inventive concept, which fall within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (5)

1. A transition metal complex, characterized in that the transition metal complex is selected from the group consisting of:
2. a mixture comprising the transition metal complex as claimed in claim 1 and at least one organic functional material selected from the group consisting of hole injection materials, hole transport materials, electron injection materials, electron blocking materials, hole blocking materials, luminophores, host materials, doping materials.
3. Use of a transition metal complex as claimed in claim 1 in an organic electronic device.
4. An organic electronic device comprising the transition metal complex as claimed in claim 1 or the mixture as claimed in claim 2.
5. The organic electronic device of claim 4, wherein the organic electronic device is selected from the group consisting of an organic light emitting diode, an organic photovoltaic cell, an organic light emitting cell, an organic field effect transistor, an organic light emitting field effect transistor, an organic laser, an organic spintronic device, an organic sensor, and an organic plasmon emitting diode.
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"Strongly Luminescent Cyclometalated Gold(III) Complexes Supported by Bidentate Ligands Displaying Intermolecular Interactions and Tunable Emission Energy";Kaai Tung Chan等;《Chem. Asian J.》;20170606;第12卷(第16期);图3 *

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Inventor after: Liang Zhiming

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