CN113004336B - Transition metal complexes, polymers, mixtures, compositions and organic electronic devices - Google Patents

Transition metal complexes, polymers, mixtures, compositions and organic electronic devices Download PDF

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CN113004336B
CN113004336B CN202011276234.0A CN202011276234A CN113004336B CN 113004336 B CN113004336 B CN 113004336B CN 202011276234 A CN202011276234 A CN 202011276234A CN 113004336 B CN113004336 B CN 113004336B
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CN113004336A (en
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梁志明
李炎
许洋华
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Guangzhou Chinaray Optoelectronic Materials Ltd
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    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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    • H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum

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Abstract

The invention discloses a transition metal complex, a polymer, a mixture, a composition and an organic electronic device. According to the transition metal complex, as the metal organic complex contains ketone groups and has excellent electron transmission capability, in addition, the aromatic amine groups contained in the compound also have excellent hole transmission capability, and the transition metal complex has a more stable six-membered ring structure, so that the transition metal complex can be used as a doping material of a light-emitting layer, and can improve the light-emitting efficiency and the service life of an organic electronic device, especially an OLED (organic light-emitting diode).

Description

Transition metal complexes, polymers, mixtures, compositions and organic electronic devices
The present application claims priority from chinese patent office, application number 201911323057.4, chinese patent application entitled "transition metal complexes, polymers, mixtures, compositions and uses thereof," filed on 12/20 2019, the entire contents of which are incorporated herein by reference.
Technical Field
The invention relates to the field of organic electroluminescence, in particular to a transition metal complex, a polymer, a mixture, a composition and an organic electronic device thereof.
Background
Among 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, easy assembly, and low power consumption, and thus are the most developing display technologies. 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 the use of fac-tris (2-phenylpyridine) iridium (III) [ Ir (ppy) 3 ]As a phosphorescent light-emitting material, 4'-N, N' -dicarbazole-biphenyl (CBP) is a high quantum efficiency OLED as a host material (appl. Phys. Lett.1999,75,4). Another example of a phosphorescent material is the sky blue complex bis [2- (4 ',6' -difluorophenyl) pyridine-N, C2]Iridium (III) 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, device performance, in particular lifetime, still needs to be improved.
The diketone type ligand is one of the more commonly used ancillary ligands in red iridium (III) complexes, such as acetylacetone (acac). The diketone auxiliary ligand is formed by bonding a lone pair electron on two oxygen atoms with a metal center, but because the bond energy of an oxygen-metal bond is relatively low, the coordination chemical bond is relatively fragile, the chemical bond is broken during high-temperature evaporation or under a long-time external electric field, the ligand is easily separated from the complex, and the service life of a device is shortened.
It is therefore desirable to develop such novel high performance metal complexes to further increase the lifetime of the device.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, there is a need to improve the stability of metal-organic complexes and the lifetime of organic light emitting devices, and it is an object of the present invention to provide transition metal complexes, polymers, mixtures, compositions and organic electronic devices thereof. The metal organic complex luminescent material has the advantages of simple synthesis, novel structure and good performance.
Based on existing diketone type ligands, oxygen-metal bond substitution is necessary to increase the lifetime of the device. In order to strengthen the strength of the coordination chemical bond between the ligand and the metal center, one oxygen atom in the diketone type can be changed to be coordinated by a carbon atom, because the bond energy of the carbon-metal bond is higher than that of the oxygen-metal bond, so that the bond between the auxiliary ligand and the metal center is strengthened.
In addition, in order to enhance the stability of the ligand and the metal center, the ligand and the metal center are changed into a six-membered ring structure, and the six-membered ring structure is more evenly distributed in atomic space, so that the tension in the ring is relaxed and becomes smaller, the complex becomes stable, and the service life of the device is prolonged.
The technical proposal is as follows:
a transition metal complex represented by the general formula (1):
wherein:
m is selected from iridium, platinum, gold, ruthenium, rhodium, osmium, rhenium, nickel, copper, silver, zinc, tungsten, or palladium;
m is selected from 0 or 1 or 2; n is selected from 1 or 2 or 3;
Ar 1 ，Ar 2 selected from a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring system having 5 to 30 ring atoms;
g1 is selected from a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring system having 5 to 30 ring atoms;
g2 G3 is independently selected from hydrogen, deuterium, a linear alkane having 1 to 30 carbon atoms, a branched or cyclic alkane having 3 to 30 carbon atoms, a linear alkene having 1 to 30 carbon atoms, a branched alkene having 1 to 30 carbon atoms, an alkane ether having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring system having 3 to 30 ring atoms;
T 1 ，T 2 Independently selected from the group consisting of absent, or single bond, or:
the joining site;
R 1 -R 4 independently at each occurrence selected from H, D, or a linear alkyl group having 1 to 30C atoms, a linear alkoxy group having 1 to 30C atoms, or a linear thioalkoxy group having 1 to 30C atoms, or a branched or cyclic alkyl group having 3 to 30C atoms, a branched or cyclic alkoxy group having 3 to 30C atoms, or a branched or cyclic thioalkoxy group having 3 to 30C atoms, or a branched or cyclic silyl group having 3 to 30C atoms, or a substituted keto group having 1 to 30C atoms, or an alkoxycarbonyl group having 2 to 30C atoms, or an aryloxycarbonyl group having 7 to 30C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxy group, a nitro group, a CF 3 A group, cl, br, F, a crosslinkable group or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems, R 1 -R 2 Can bond to each other to form a ring.
A polymer comprising at least one 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), a dopant material (dopans), and the like.
A composition comprising a transition metal complex as described above or a polymer or mixture as described above, and at least one organic solvent.
An organic electronic device comprising at least one functional layer comprising or prepared from a transition metal complex or polymer or mixture as described above.
The beneficial effects are that:
the metal organic 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. Because the metal organic complex contains ketone group and has excellent electron transmission capability, and the aromatic amine group contained in the compound also has excellent hole transmission capability, and has a more stable six-membered ring structure, the brightness and the current efficiency of the device can be improved, and meanwhile, the starting voltage is reduced, so that the service life of the device is prolonged.
Detailed Description
The present invention provides a transition metal complex, a polymer, a mixture, a composition and an organic electronic device thereof, and the present invention is further described in detail below for the purpose, technical scheme and effect of the present invention to be 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, 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 metal-organic complex, the organometallic complex, and the transition metal complex have the same meaning and are interchangeable.
In the present invention, "substituted" means that a hydrogen atom in a substituted group is substituted by a substituent.
In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood to be optionally substituted with groups acceptable in the art, including but not limited to: c (C) 1-30 Alkyl, heterocyclyl having 3 to 20 ring atoms, aryl having 5 to 20 ring atoms, heteroaryl having 5 to 20 ring atoms, silyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, -NRR', cyano, isocyano, thiocyanate, isothiocyanate, hydroxy, trifluoromethyl, nitro or halogen, and which may be further substituted with substituents acceptable in the art; it is understood that R and R 'in-NRR' are each independently substituted with a group acceptable in the art, including but not limited to H, C 1-6 Alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, aryl having 5 to 20 ring atoms or heteroaryl having 5 to 10 ring atoms; the C is 1-6 Alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, aryl having 5 to 20 ring atoms, or heteroaryl having 5 to 10 ring atoms is optionally further substituted with one or more of the following groups: c (C) 1-6 Alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, halogen, hydroxy, nitro or amino.
In the present invention, the "number of ring atoms" means the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below, unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.
In the present invention, aromatic groups have the same meaning and are interchangeable between them.
In the present invention, heteroaromatic groups have the same meaning, they can be interchanged.
An aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including monocyclic groups and polycyclic ring systems. Heteroaromatic groups refer to hydrocarbon groups (containing heteroatoms) containing 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 groups 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, in particular less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, groups such as 9,9' -spirobifluorene, 9-diaryl fluorene, triarylamine, diaryl ether, and the like are also considered aromatic groups for the purposes of this invention.
Specifically, examples of the aromatic group are: benzene, naphthalene, anthracene, phenanthrene, perylene, naphthacene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, and derivatives thereof.
Specifically, examples of the heteroaromatic group 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.
The non-aromatic ring system comprises from 1 to 10 carbon atoms in the ring system, further from 1 to 6 carbon atoms, including not only saturated but also partially unsaturated cyclic groups, which may be unsubstituted or mono-or polysubstituted by groups R, which may be identical or different in each occurrence, and may also comprise one or more heteroatoms, further the heteroatoms being selected from Si, N, P, O, S and/or Ge, further the heteroatoms being selected from Si, N, P, O and/or S. These may be, for example, cyclohexyl-like or piperidine-like groups, or cyclooctadiene-like cyclic groups. The term applies equally to fused non-aromatic ring systems.
The invention relates to a transition metal complex, which comprises a structure shown in a general formula (1):
wherein:
m is selected from iridium, platinum, gold, ruthenium, rhodium, osmium, rhenium, nickel, copper, silver, zinc, tungsten, or palladium;
m is selected from 0 or 1 or 2; n is selected from 1 or 2 or 3;
Ar 1 ，Ar 2 selected from a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring system having 5 to 30 ring atoms;
g1 is selected from a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring system having 5 to 30 ring atoms;
g2 G3 is independently selected from hydrogen, deuterium, a linear alkane having 1 to 30 carbon atoms, a branched or cyclic alkane having 3 to 30 carbon atoms, a linear alkene having 1 to 30 carbon atoms, a branched alkene having 1 to 30 carbon atoms, an alkane ether having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring system having 3 to 30 ring atoms;
T 1 ，T 2 Independently selected from the group consisting of absent, or single bond, or:
the joining site;
R 1 -R 4 independently at each occurrence selected from H, D, or a linear alkyl group having 1 to 30C atoms, a linear alkoxy group having 1 to 30C atoms, or a linear thioalkoxy group having 1 to 30C atoms, or a branched or cyclic alkyl group having 3 to 30C atoms, a branched or cyclic alkoxy group having 3 to 30C atoms, or a branched or cyclic thioalkoxy group having 3 to 30C atoms, or a branched or cyclic silyl group having 3 to 30C atoms, or a substituted keto group having 1 to 30C atoms, or an alkoxycarbonyl group having 2 to 30C atoms, or an aryloxycarbonyl group having 7 to 30C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxy group, a nitro group, a CF 3 A group, cl, br, F, a crosslinkable group or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems, R 1 -R 2 Can bond to each other to form a ring.
R，R 1 ～R 4 Any one of (1) C1-C10 alkyl, further selected from the group consisting of: 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, pentafluoroethyl, 2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl and octynyl; (2) C2-C10 aromatic or heteroaromatic radicals, in particular selected from the following radicals: 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 aromatic and heteroaromatic groups mentioned above, biphenylene, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, tetrahydropyrene and cis-or trans-indenofluorene.
In an embodiment, the metal element M is selected from any one of iridium (Ir), gold (Au), platinum (Pt), ruthenium (Ru), and palladium (Pd).
In one embodiment, the metal element M is selected from iridium (Ir) or platinum (Pt). In a preferred embodiment, the metallic element M is iridium (Ir).
From the heavy atom effect, ir is particularly preferably used as the central metal 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.
In a preferred embodiment, m+n=3; in another preferred embodiment, m+n=2.
In a preferred embodiment, m is selected from 1 or 2.
In one embodiment, ar 1 ，Ar 2 Selected from a substituted or unsubstituted aromatic group having 6 to 20 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms; in one embodiment, ar 1 ，Ar 2 Selected from a substituted or unsubstituted aromatic group having 6 to 15 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 15 ring atoms; in one embodiment, ar 1 ，Ar 2 One selected from aromatic groups and one selected from N-containing heteroaromatic groups.
In one embodiment, G1 is selected from a substituted or unsubstituted aromatic group having 6 to 20 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms; in one embodiment, G1 is selected from substituted or unsubstituted aromatic groups having 6 to 15 ring atoms.
In one embodiment, ar 1 ，Ar 2 G1 is selected from the following groups:
wherein,
x is selected from CR 4 Or N;
y is selected from CR 4 R 5 ，NR 4 ，O，S，PR 4 ，BR 4 Or SiR 4 R 5 ；
R 4 -R 5 Independently at each occurrence selected from H, D, or a linear alkyl group having 1 to 30C atoms, a linear alkoxy group having 1 to 30C atoms, or a linear thioalkoxy group having 1 to 30C atoms, or a branched or cyclic alkyl group having 3 to 30C atoms, having 3 to 30Branched or cyclic alkoxy of C atoms or branched or cyclic thioalkoxy groups of 3 to 30C atoms or branched or cyclic silyl groups of 3 to 30C atoms or substituted keto groups of 1 to 30C atoms or alkoxycarbonyl groups of 2 to 30C atoms or aryloxycarbonyl groups of 7 to 30C atoms, cyano groups (-CN), carbamoyl groups (-C (=O) NH) 2 ) Haloformyl group, 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 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.
When X is a binding site, X is selected from C.
Further, ar 1 ，Ar 2 G1 is selected from the following groups:
further, ar 1 ，Ar 2 G1 is selected from:
specifically, ar 1 ，Ar 2 G1 is selected from the following groups:
in one embodiment, R 1 -R 2 May be bonded to each other in a ring, specifically,the structure is as follows:
wherein: x and Y have the same meanings as described above.
In one embodiment of the present invention, in one embodiment,any one structure selected from (A-1) to (A-26):
wherein: q is selected from C or N; x and Y are as defined above; * Represents the site of attachment to M.
Preferably, the method comprises the steps of,two Q's of the structural formulae (A-1) to (A-16), (A-19) to (A-24) and (A-26), one selected from C and the other selected from N, are monovalent anionic ligands.
Further, the method comprises the steps of,any one structure selected from (B-1) to (B-50):
preferably, the method comprises the steps of,selected from (B-1), (B-50), (B-47), (B-13), (B-27), (B-4), (B-5), (B-36), (B-13), (B-39) or (B-32)。
In one embodiment, T 1 ，T 2 Independently selected from the absence or single bond.
In one embodiment, T 2 Selected from single bonds, T 1 Is selected from the absence, in particular, formula (1) is selected from formula (2):
wherein:
g2 is selected from a linear alkane having 2 to 30 carbon atoms, a branched or cyclic alkane having 3 to 30 carbon atoms, a linear alkene having 2 to 30 carbon atoms, a branched alkene having 2 to 30 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring system having 3 to 30 ring atoms.
Preferably, G2 is selected from vinyl groups or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms, substituted or unsubstituted heteroaromatic groups having 6 to 10 ring atoms; more preferably, G2 is selected from vinyl groups or benzene and derivatives thereof.
In one embodiment, T 1 Selected from single bonds, T 2 Is selected from the absence, in particular, formula (1) is selected from formula (3):
in one embodiment, T 1 ，T 2 Selected from the group consisting of absent, or single bond. Specifically, the following formula:
in one embodiment, T 2 Selected from single bonds, T 1 Selected from the group consisting of
In one embodiment, G2 and G3 are preferably selected from the following groups:
wherein: x and Y have the same meanings as described above.
In one embodiment, X is selected from CR in the groups selected from G2 and G3 4 。
In one embodiment, G2 and G3 are selected from
In one embodiment, G2 and G3 are selected from:
in one embodiment of the present invention, in one embodiment,for monovalent anionic ligands, preference is given to those of any of the structures (C-1) to (C-13):
/>
wherein,
x is selected from CR 5 Or N;
y is selected from CR 5 R 6 ，NR 5 ，O，S，PR 5 ，BR 5 Or SiR 5 R 6 ；
R 3 -R 6 Independently at each occurrence selected from H, D, or a linear alkyl group having 1 to 30C atoms, a linear alkyl group having 1 to 30C atomsAlkoxy or linear thioalkoxy group having 1 to 30C atoms, or branched or cyclic alkyl having 3 to 30C atoms, branched or cyclic alkoxy having 3 to 30C atoms, or branched or cyclic thioalkoxy group having 3 to 30C atoms, or branched or cyclic silyl group having 3 to 30C atoms, or substituted keto group having 1 to 30C atoms, or alkoxycarbonyl group having 2 to 30C atoms, or aryloxycarbonyl group having 7 to 30C atoms, cyano group (-CN), carbamoyl group (-C (=o) NH 2 ) Haloformyl group, 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 5 -R 6 A ring which may be bonded to each other and/or to the group is a monocyclic or polycyclic aliphatic or aromatic ring.
Preferably, the method comprises the steps of,selected from (C-1), (C-4) or (C-7).
R 3 Preferably selected from H, or a linear alkyl group having 1 to 30C atoms, or a branched or cyclic alkyl group having 3 to 30C atoms, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms. Preferably, R 3 Selected from H or methyl.
Further, the method comprises the steps of,any one of the structures selected from (D-1) to (D-45): />
Wherein: the H atom on the ring may be further substituted.
In one embodiment, formula (1) is selected from any one of the structures of formulas (3-1) - (3-4):
wherein: ar (Ar) 2 Selected from substituted or unsubstituted N-containing heteroaromatic groups having from 5 to 30 ring atoms. Preferably Ar 2 An N-containing heteroaromatic group selected from substituted or unsubstituted having 6 to 10 ring atoms; more preferably Ar 2 Selected from the group consisting of
Preferably, m in the general formulae (3-1) to (3-4) is selected from 1 or 2; n is selected from 1 or 2.
Specific examples of M selected from Ir in the transition metal complex of the general formula (1) according to the present invention are given below, but are not limited thereto.
In the following table, L representsL1 represents->/>
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In one embodiment, when M is selected from Pt, (Pt-1) through (Pt-590) are the same as formulas (1) through (590), except that M is selected from Ir instead of M is selected from Pt; and m=2 in the structural formulae (1) to (590) is modified to m=1 or m=1 is modified to m=0.
The transition metal complex according to the present invention can be used as a functional material in an electronic device. The organic functional material includes, but is not limited to, 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 body (Emitter), and a Host material (Host).
In certain embodiments, the transition metal complexes according to the invention are functional materials that are not luminescent materials.
In one embodiment, the transition metal complex according to the invention is a luminescent material having a luminescence wavelength between 300nm and 1000 nm; further, the luminescence wavelength is between 350nm and 900 nm; further, the emission wavelength is between 400nm and 800 nm. Luminescence here refers to photoluminescence or electroluminescence.
In certain embodiments, the transition metal complexes according to the invention have an electroluminescent efficiency of > 30%; further, the electroluminescent efficiency is more than or equal to 40%; furthermore, the electroluminescent efficiency is more than or equal to 50%; in particular, the electroluminescent efficiency is not less than 60%.
In one embodiment, the transition metal complex according to the invention is used as phosphorescent guest.
As a phosphorescent guest material, it is necessary to have an appropriate triplet energy level, i.e., T 1 . In certain embodiments, transition metal complexes according to the invention, T 1 Not less than 2.0eV; further, the T 1 Not less than 2.2eV; further, the T 1 Not less than 2.4eV; in particular, the T 1 ≥2.6eV。
Good thermal stability is desirable as a functional material. Generally, transition metal complexes according to the invention have a glass transition temperature Tg of greater than or equal to 100 ℃, in one embodiment greater than or equal to 120 ℃, in another embodiment greater than or equal to 160 ℃, and in one embodiment greater than or equal to 180 ℃.
In certain embodiments, transition metal complexes according to the invention have ((HOMO- (HOMO-1)). Gtoreq.0.2 eV; further, the ((HOMO- (HOMO-1)). Gtoreq.0.25 eV; still further, the ((HOMO- (HOMO-1)). Gtoreq.0.3 eV; still further, the ((HOMO- (HOMO-1)). Gtoreq.0.4 eV; in particular, the ((HOMO- (HOMO-1)). Gtoreq.0.45 eV).
In further embodiments, the transition metal complexes according to the invention have a (((LUMO+1) -LUMO) of 0.15eV or more, further the (((LUMO+1) -LUMO) of 0.20eV or more, further the (((LUMO+1) -LUMO) of 0.25eV or more, still further the (((LUMO+1) -LUMO) of 0.30eV or more, in particular the (((LUMO+1) -LUMO) of 0.35eV or more.
The invention further relates to a polymer comprising at least one repeating unit of a structural unit of a transition metal complex as described above.
In one embodiment, the polymer is synthesized by a method selected from SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD-and ULMAN.
In one embodiment, the polymers according to the invention have a glass transition temperature (Tg) of 100℃or more; further, tg is not less than 120 ℃; further, tg is more than or equal to 140 ℃; still further, tg is greater than or equal to 160 ℃; in particular, tg is greater than or equal to 180 ℃.
In one embodiment, the polymers according to the invention have a molecular weight distribution (PDI) in the range of 1 to 5; further, the PDI value range is 1-4; still further, the PDI value range is 1-3; still further, the PDI value ranges from 1 to 2, and in particular, the PDI value ranges from 1 to 1.5.
In one embodiment, the polymers according to the invention have a weight average molecular weight (Mw) ranging from 1 to 100 tens of thousands; further, mw ranges from 5 to 50 tens of thousands; still further, mw ranges from 10 to 40 thousand; still further, mw ranges from 15 to 30 thousand; in particular, mw ranges from 20 to 25 tens of thousands.
In certain embodiments, the polymer according to the present invention is a non-conjugated polymer. Further, it is a non-conjugated polymer in which a structural unit of one of the transition metal complexes is contained as a repeating unit in a side chain.
The invention also provides a mixture, which is characterized by comprising at least one transition metal complex or polymer and at least one other organic functional material, wherein the at least one other organic functional material can 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 luminescent material (Emitter), a Host material (Host) and an organic dye. Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of these 3 patent documents being hereby incorporated by reference.
In certain embodiments, the amount of transition metal complex in the mixture according to the invention is from 0.01wt% to 30wt%; further, the content of the transition metal complex is 0.5wt% to 20wt%; still further, the transition metal complex is present in an amount of 2wt% to 15wt%; in particular, the content of the transition metal complex is 5wt% to 15wt%.
In one embodiment, the mixture according to the invention comprises a transition metal complex or polymer according to the invention and a triplet host material.
In another embodiment, the mixture according to the invention comprises a transition metal complex or polymer according to the invention, one triplet matrix material and another triplet emitter.
In another embodiment, the mixture according to the invention comprises a transition metal complex or polymer according to the invention and a thermally activated delayed fluorescence luminescent material (TADF).
In another embodiment, the mixture according to the invention comprises a transition metal 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 the phosphorescent light emitting body.
Examples of metal complexes that can be used as triplet hosts (Host) include, but are not limited to, the general structures:
M 1 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; m 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 wherein the metal coordinates to the O and N atoms m is an integer having a value from 1 to the maximum coordination number of the metal;
in one embodiment, M 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 is selected from compounds comprising at least one of the following groups:
wherein: x is X 1 Ar has the meanings given above for X, X and Y 3 Ar has the meaning as Ar 1 ；Ar 1 And Ar is a group 2 The meaning is as described above; r is RThe following groups may be selected: hydrogen, deuterium, halogen atoms (F, cl, br, I), cyano, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl, v being selected from integers ranging from 1 to 20.
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 generally have a small singlet-triplet energy level difference (ΔE st ) Triplet excitons may be converted to singlet excitons for light emission by intersystem crossing. 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), 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, 49,2013,10385, adachi, et al, adv. Mater. 25,2013,3319, 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:
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 general 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 between 1 and 6. Preferably, the triplet emitters comprise chelating ligands, i.e. ligands, which coordinate to the metal via at least two binding sites, and particularly preferably the triplet emitters comprise two or three identical or different bidentate or polydentate ligands. Chelating ligands are beneficial for improving the stability of metal complexes. In a preferred embodiment, the metal complexes useful as triplet emitters are of the form:
the metal atom M is selected from transition metal element or lanthanoid or actinoid, preferably Ir, pt, pd, au, rh, ru, os, re, cu, ag, ni, co, W or Eu, particularly preferably Ir, au, pt, W or Os.
Ar 1 ，Ar 2 Each occurrence, which may be the same or different, is a cyclic group wherein Ar1 contains at least one donor atom, i.e., an atom having a lone pair of electrons, such as nitrogen, through which the cyclic group is coordinately bound to the metal; wherein Ar2 contains at least one carbon 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 organic ligands may be selected from phenylpyridine derivatives or 7, 8-benzoquinoline derivatives. All of these organic ligands may be substituted, for example by alkyl or fluorine or silicon containing. The auxiliary ligand may preferably be selected from the group consisting of acetone acetate and picric acid.
Examples of materials and applications of triplet emitters can be found in WO0070655 (A2), WO0141512 (A1), WO0202714A2, WO0215645 (A1), WO2005033244, WO2005019373, US20050258742, US20070087219, US20070252517, US2008027220, WO2009146770, US20090061681, WO2009118087, WO2010015307, WO2010054731, WO2011157339, WO2012007087, WO2013107487, WO2013094620, WO2013174471, WO 2014031977,WO 2014112450,WO2014007565,WO 2014024131,Baldo et al.Nature (2000), 750,Kido et al.Appl.Phys.Lett (1994), 2124,Wrighton et al.J.Am.Chem.Soc (1974), 998. 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 certain embodiments, the transition metal complexes according to the invention have a molecular weight of 1200g/mol or less; further, the molecular weight is less than or equal to 1100g/mol; further, the molecular weight is less than or equal to 1000g/mol; still further, the molecular weight is less than or equal to 950g/mol; in particular, the molecular weight is less than or equal to 900g/mol.
It is another object of the invention to provide a material solution for printed OLEDs.
In certain embodiments, the transition metal complexes according to the invention have a molecular weight of 800g/mol or more; further, the molecular weight is more than or equal to 900g/mol; further, the molecular weight is more than or equal to 1000g/mol; still further, the molecular weight is more than or equal to 1100g/mol; in particular, the molecular weight is greater than or equal to 1200g/mol.
In other embodiments, the transition metal complexes according to the invention have a solubility in toluene of > 2mg/ml at 25 ℃; further, the solubility in toluene is more than or equal to 3mg/ml; further, the solubility in toluene is more than or equal to 4mg/ml; in particular, the solubility in toluene is not less than 5mg/ml.
The invention also relates to a composition comprising at least one transition metal complex or polymer or mixture as described above, and at least one organic solvent; the at least one organic solvent is selected from aromatic, heteroaromatic, ester, aromatic ketone, aromatic ether, aliphatic ketone, aliphatic ether, alicyclic, olefin compound, boric acid ester, phosphate compound, or mixture of two or more solvents.
In one embodiment, a composition according to the invention is characterized in that said at least one organic solvent is chosen from solvents based on aromatic or heteroaromatic groups.
Examples of aromatic or heteroaromatic-based solvents suitable for the present invention are, but are not limited to: para-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluenes, 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, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 4-difluorodiphenyl methane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenyl methane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenyl methane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, 2-quinolinecarboxylic acid, ethyl ester, 2-methylfuran, etc.;
Examples of aromatic ketone-based solvents suitable for the present invention are, but are not limited to: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropionophenone, 3-methylpropionophenone, 2-methylpropionophenone, and the like;
examples of aromatic ether-based solvents suitable for the present invention are, but are not limited to: 3-phenoxytoluene, butoxybenzene, 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, 3-dipropoxybenzene, 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;
in some embodiments, the composition according to the invention, the at least one organic solvent may be chosen from: aliphatic ketones such as 2-nonene, 3-nonene, 5-nonene, 2-decanone, 2, 5-adipone, 2,6, 8-trimethyl-4-nonene, fenchyl ketone, phorone, isophorone, 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 at least one solvent in accordance with the present compositions may be selected from ester-based solvents: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. In particular selected from octyl octanoate, diethyl sebacate, diallyl phthalate, isononyl isononanoate.
The solvent may be used alone or as a mixture of two or more organic solvents.
In certain embodiments, a composition according to the present invention comprises at least one transition metal complex or polymer or mixture as described above and at least one organic solvent, and may further comprise another organic solvent. Examples of other organic solvents 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 some embodiments, a solvent particularly suitable for the present invention is a solvent having Hansen (Hansen) solubility parameters within the following ranges:
δ d (dispersion force) of 17.0-23.2 MPa 1/2 In particular in the range from 18.5 to 21.0MPa 1/2 Is defined by the range of (2);
δ p (polar force) is 0.2-12.5 MPa 1/2 In particular in the range of 2.0 to 6.0MPa 1/2 Is defined by the range of (2);
δ h the (hydrogen bond force) is between 0.9 and 14.2MPa 1/2 In particular in the range of 2.0 to 6.0MPa 1/2 Is not limited in terms of the range of (a).
The composition according to the invention, wherein the organic solvent is selected taking into account its boiling point parameters. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; further, the boiling point of the organic solvent is more than or equal to 180 ℃; further, the boiling point of the organic solvent is more than or equal to 200 ℃; still further, the boiling point of the organic solvent is more than or equal to 250 ℃; in particular, the organic solvent has a boiling point of 275 ℃ or more or 300 ℃ or more. Boiling points in these ranges are beneficial in preventing nozzle clogging of inkjet printheads. The organic solvent may be evaporated from the solvent groups to form a film comprising the functional material.
In one embodiment, the composition according to the invention is a solution.
In another embodiment, the composition according to the invention is a suspension.
The transition metal complex or polymer or mixture according to the invention may be included in the composition in embodiments of the invention in an amount of 0.01 to 10wt%, further 0.1 to 15wt%, still further 0.2 to 5wt%, in particular 0.25 to 3wt%.
The invention also relates to the use of said composition as a coating or printing ink for the production of organic electronic devices, in particular by a printing or coating process.
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, offset Printing, flexography, rotary Printing, spray coating, brush coating, pad Printing, or slot die coating, among others. Gravure printing, inkjet printing and inkjet printing are preferred. The solution or suspension may additionally include 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.
The present invention also provides the use of a transition metal complex, polymer, mixture or composition as described above in an organic electronic device selected from, but not limited to, organic Light Emitting Diodes (OLEDs), organic photovoltaic cells (OPVs), organic light emitting cells (OLEEC), organic Field Effect Transistors (OFET), organic light emitting field effect transistors, organic lasers, organic spintronic devices, organic sensors, organic plasmon emitting diodes (Organic Plasmon Emitting Diode), and the like, in particular OLEDs. In the embodiment of the invention, the organic metal complex or the polymer is further used for a light-emitting layer of an OLED device.
The invention further relates to an organic electronic device comprising at least one functional layer comprising at least one transition complex, polymer or mixture as described above or prepared from a composition as described above. 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), etc., particularly organic electroluminescent devices such as OLED, OLEEC, organic light emitting field effect transistor.
In some embodiments, the functional layer of the electroluminescent device is a light emitting layer.
In the light emitting device described above, in particular an OLED, it comprises 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 wafer or glass. In particular, the substrate has a smooth surface. Substrates free of surface defects are a particularly desirable choice. In one embodiment, the substrate is flexible, optionally in a polymer film or plastic, having a glass transition temperature Tg of 150 ℃ or higher; further, tg exceeds 200 ℃; still further, tg exceeds 250 ℃; in particular, tg exceeds 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, metal oxide, or conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL), 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; further, the absolute value is less than 0.3eV; in particular, the absolute value is 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 organic electronic 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; further, the absolute value is less than 0.3eV; in particular, the absolute value is less than 0.2eV. In principle, all materials which can be used as cathode of the OLED are possible as devices according to the invention A cathode material. Examples of cathode materials include, but are not limited to: al, au, ag, ca, ba, mg, liF/Al, mgAg alloy and BaF 2 /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 in detail above and in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of which 3 patent documents are hereby incorporated by reference.
The light emitting device according to the present invention has a light emitting wavelength of 300nm to 1000 nm; further, the light emission wavelength is between 350nm and 900 nm; further, the emission wavelength is between 400nm and 800 nm.
The invention also relates to the use of the electroluminescent 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 following examples, but it is not limited thereto, and it is to be understood that the appended claims summarize the scope of the invention and that certain changes made to the various embodiments of the invention which are contemplated by one skilled in the art are to be covered by the spirit and scope of the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
1. Synthesis of transition metal organic complexes
Synthesis example 1 Synthesis of Complex (40)
Synthetic intermediate (40-a):
2-phenylpyridine (8 g,3 eq) was put in a single-necked flask, iridium trichloride (5.2 g,1 eq) and sodium carbonate (9.23 g,5 eq) were added, a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of water was added, the mixture was heated to 110℃and reacted for 12 hours, cooled to room temperature, poured into a sodium chloride aqueous solution, and the yellow was filtered. After the solid was dried, it was dissolved in a mixed solution of 300mL of methylene chloride and 100mL of methanol, and then silver trifluoromethane sulfonate (4.95 g,3 eq) was added to react for 12 hours, and the resultant was filtered and dried to obtain a yellow solid intermediate (40-a) in 80% yield.
Synthetic intermediate (40-b):
(2-bromophenyl) aniline (10 g,1 eq) was placed in a single-necked flask, 300mL of methylene chloride was added to dissolve the solid, then benzoyl chloride (41.53 g,5 eq) was slowly added to react at room temperature for 10 hours, poured into an aqueous sodium chloride solution, the yellow material was filtered, and the solid was dried to give a yellow solid intermediate (40-b) in 84% yield.
Synthetic intermediate (40-c):
in a dry two-necked flask was placed pinacol biborate (24.15 g,1.5 eq), intermediate (40-b) (22.33 g,1 eq), pd (dppf) 2 Cl 2 (2.3 g,0.05 eq), potassium acetate (24 g,4 eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the mixture was stirred at 90 ℃ for reaction for 12 hours, cooled to room temperature, dried by spinning after completion of the reaction, dried over dichloromethane and water solution, dried over magnesium sulfate, dried by spinning again, and then separated and purified by a silica gel column. The solid intermediate (40-c) was obtained in 78% yield.
Synthetic complex (40):
the intermediate (40-a) (1 g,1 eq) and the intermediate (40-c) (3.07 g,5 eq) were placed in a single-necked flask, and 20mL of 2-isopropyl alcohol was added thereto, followed by nitrogen purging. Potassium phosphate (1.63 g,5 eq) was added and reacted at room temperature for 24 hours. Filtering with diatomite, washing with methanol, oven drying, and separating and purifying with silica gel chromatographic column. The product was collected, spin-dried and recrystallized to give yellow solid complex (40), yield 57%, mass spectrum peak m/z=773.2011 [ m ]] + 。
Synthesis example 2 Synthesis of Complex (115)
Synthetic intermediate (115-a):
in a dry two-necked flask was placed phenylboronic acid (11.72 g,1 eq), 2-bromoquinoline (20 g,1 eq), pd (PPh 3 ) 4 (5.55 g,0.05 eq), potassium carbonate (39.85 g,3 eq), then a mixed solution of 500mL of dioxane and 50mL of water was added, the mixture was circulated three times by vacuum-pumping and nitrogen-charging, the reaction was stirred at 95℃for 12 hours, cooled to room temperature, the dichloromethane layer was dried by spinning with a water solution, and then separation and purification were carried out by a silica gel column to obtain an intermediate (115-a) in 82% yield.
Synthetic intermediate (115-b):
(2-bromophenyl) aniline (10 g,1 eq) was placed in a single-necked flask, 300mL of methylene chloride was added to dissolve the solid, then cyclohexanecarbonyl chloride (43.32 g,5 eq) was slowly added and reacted at room temperature for 10 hours, poured into an aqueous sodium chloride solution, the yellow material was filtered, and the solid was dried to give intermediate (115-b) as a yellow solid in 76% yield.
Synthetic intermediate (115-c):
in a dry two-necked flask was placed pinacol biborate (24.15 g,1.5 eq), intermediate (115-b) (22.72 g,1 eq), pd (dppf) 2 Cl 2 (2.3 g,0.05 eq), potassium acetate (24 g,4 eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the mixture was stirred at 90 ℃ for reaction for 12 hours, cooled to room temperature, dried by spinning after completion of the reaction, dried over dichloromethane and water solution, dried over magnesium sulfate, dried by spinning again, and then separated and purified by a silica gel column. The solid intermediate (115-c) was obtained in 67% yield.
Synthetic intermediate (115-d):
intermediate (115-c) (21.18 g,3 eq) and potassium phosphate (18.48 g,5 eq) were placed in a single-necked flask, iridium trichloride (5.2 g,1 eq) was added, a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of water was added, the mixture was heated to 110℃and reacted for 12 hours, cooled to room temperature, poured into an aqueous sodium chloride solution, and the yellow was filtered. After the solid was dried, it was dissolved in a mixed solution of 300mL of methylene chloride and 100mL of methanol, and then silver trifluoromethane sulfonate (13.42 g,3 eq) was added to react for 12 hours, and filtration and drying gave an intermediate (115-d) as a yellow solid in 46% yield. Synthetic complex (115):
Intermediate (115-d) (1 g,1 eq) and intermediate (115-a) (0.34 g,1.5 eq) were placed in a single-necked flask, 50mL of tetrahydrofuran was added, and after blowing nitrogen, sodium carbonate (0.59 g,5 eq) was added and reacted at room temperature for 24 hours. Filtering with diatomite, washing with methanol, oven drying, separating and purifying with silica gel chromatographic column, spin drying, and recrystallizing to obtain yellow solid complex (115) with yield of 49% and mass spectrum peak m/z=953.3543 [ M ]] + 。
Synthesis example 3 Synthesis of Complex (127)
Synthetic intermediate (127-a):
2- (2-pyridine) -benzimidazole (10.2 g,3 eq) was placed in a single-necked flask, iridium trichloride (5.2 g,1 eq) and sodium carbonate (9.23 g,5 eq) were added, a mixed solution of 300mL of ethylene glycol ether and 100mL of water was added, the mixture was heated to 110℃and reacted for 12 hours, cooled to room temperature, poured into an aqueous sodium chloride solution, and the yellow was filtered. After the solid was dried, it was dissolved in a mixed solution of 300mL of methylene chloride and 100mL of methanol, and then silver trifluoromethane sulfonate (4.95 g,3 eq) was added to react for 12 hours, and filtration and drying gave an intermediate (127-a) as a yellow solid in 80% yield.
Synthetic intermediate (127-b):
(2-bromophenyl) aniline (10 g,1 eq) was placed in a single-necked flask, 300mL of methylene chloride was added to dissolve the solid, then 1-adamantanecarbonyl chloride (35.22 g,3 eq) was slowly added to react at room temperature for 10 hours, poured into an aqueous sodium chloride solution, the yellow material was filtered, and the solid was dried to give a yellow solid intermediate (127-b) in 53% yield.
Synthetic intermediate (127-c):
in a dry two-necked flask was placed pinacol biborate (24.15 g,1.5 eq), intermediate (127-b) (26.02 g,1 eq), pd (dppf) 2 Cl 2 (2.3 g,0.05 eq), potassium acetate (24 g,4 eq) and then 250mL of dioxane in a 3:1 ratio were addedThe mixed solution of the ring and the water is stirred and reacted for 12 hours at 90 ℃, cooled to room temperature, dried by spin after the reaction is completed, dried by using dichloromethane and water solution, dried by using magnesium sulfate and then dried by spin, and then separated and purified by using a silica gel chromatographic column. The solid intermediate (127-c) was obtained in 54% yield.
Synthetic complex (127):
intermediate (127-a) (1 g,1 eq) and intermediate (127-c) (3.13 g,5 eq) were placed in a single-necked flask, and 20mL of 2-isopropanol was added thereto, followed by nitrogen purging. Potassium phosphate (1.45 g,5 eq) was added and reacted at room temperature for 24 hours. Filtering with diatomite, washing with methanol, oven drying, and separating and purifying with silica gel chromatographic column. The product was collected, recrystallized after spin-drying to give the red solid complex (127) in 48% yield with mass spectrum peak m/z=911.2939 [ m ]] + 。
Synthesis example 4 Synthesis of Complex (164)
Synthetic intermediate (164-a):
2- (1H-imidazol-1-yl) pyridine (7.58 g,3 eq) was placed in a single-necked flask, iridium trichloride (5.2 g,1 eq) and sodium carbonate (9.23 g,5 eq) were added, a mixed solution of 300mL of ethylene glycol ether and 100mL of water was added, the mixture was heated to 110℃and reacted for 12 hours, cooled to room temperature, poured into an aqueous sodium chloride solution, and the yellow was filtered. After the solid was dried, it was dissolved in a mixed solution of 300mL of methylene chloride and 100mL of methanol, and then silver trifluoromethane sulfonate (4.95 g,3 eq) was added to react for 12 hours, and filtration and drying gave an intermediate (164-a) as a yellow solid in 73% yield.
Synthetic intermediate (164-b):
in a dry two-necked flask was placed aniline (25 g,1 eq), 2-bromo-3-iodonaphthalene (89.38 g,1 eq), cesium carbonate Cs 2 CO 3 (174.93 g,3 eq) and a small amount of copper powder (1.7 g,0.1 eq) were then added 250mL of dimethylformamide aidDMF), heating to 130 ℃ for 24 hours, distilling off the solvent in vacuo, drying the dichloromethane layer with magnesium sulfate and spin-drying, and separating and purifying with silica gel chromatographic column. The intermediate (164-b) was obtained as a solid in 83% yield.
Synthetic intermediate (164-c):
intermediate (164-b) (10 g,1 eq) was placed in a single-necked flask, 300mL of dichloromethane was added to dissolve the solid, then cyclohexanecarbonyl chloride (24.58 g,5 eq) was slowly added and reacted at room temperature for 10 hours, poured into aqueous sodium chloride solution, the yellow material was filtered and the solid was dried to give intermediate (164-c) as a yellow solid in 69% yield.
Synthetic intermediate (164-d):
in a dry two-necked flask was placed pinacol biborate (24.15 g,1.5 eq), intermediate (164-c) (25.89 g,1 eq), pd (dppf) 2 Cl 2 (2.3 g,0.05 eq), potassium acetate (24 g,4 eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the mixture was stirred at 90 ℃ for reaction for 12 hours, cooled to room temperature, dried by spinning after completion of the reaction, dried over dichloromethane and water solution, dried over magnesium sulfate, dried by spinning again, and then separated and purified by a silica gel column. The solid intermediate (164-d) was obtained in 66% yield.
Synthetic complex (164):
intermediate (164-a) (1 g,1 eq) and intermediate (164-d) (3.62 g,5 eq) were placed in a single-necked flask, and 20mL of 2-isopropanol was added thereto, followed by nitrogen purging. Potassium phosphate (1.69 g,5 eq) was added and reacted at room temperature for 24 hours. Filtering with diatomite, washing with methanol, oven drying, and separating and purifying with silica gel chromatographic column. The product was collected, spin-dried and recrystallized to give yellow solid complex (164) in 52% yield with mass spectrum peak m/z=809.2509 [ m] + 。
Synthesis example 5 Synthesis of Complex (188)
Synthetic intermediate (188-a):
in a dry 500mlPlacing isochroman-4-one (26.47 g,1.1 eq), anthranilic alcohol (20 g,1 eq), ruCl in a double-mouth bottle 2 (PPh 3 ) 3 (1.56 g,0.01 eq), potassium hydroxide (18.22 g,2 eq), vacuum-pumping and nitrogen-charging for three times, then adding 300mL of anhydrous toluene, stirring at 120 ℃ for 24 hours, adding dichloromethane for extraction after the reaction solution is spin-dried, concentrating, and separating and purifying by a silica gel chromatographic column to obtain an off-white intermediate (188-a) with the yield of 65%.
Synthetic intermediate (188-b):
intermediate (188-a) (12.19 g,3 eq) was placed in a single-necked flask, iridium trichloride (5.2 g,1 eq) and sodium carbonate (9.23 g,5 eq) were added, a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of water was added, the mixture was heated to 110℃and reacted for 12 hours, cooled to room temperature, poured into an aqueous sodium chloride solution, and the yellow was filtered. After the solid was dried, it was dissolved in a mixed solution of 300mL of methylene chloride and 100mL of methanol, and then silver trifluoromethane sulfonate (13.42 g,3 eq) was added to react for 12 hours, and filtration and drying gave an intermediate (188-b) as a yellow solid in 54% yield.
Synthetic intermediate (188-c):
2-ethylbutyric acid (10 g,1 eq) was placed in a single-necked flask, then 30mL of thionyl chloride was slowly added for dissolution, reacted at room temperature for 2 hours, then evaporated in vacuo until a white solid appeared, and the reaction was directly carried out without purification.
Synthetic intermediate (188-d):
(2-bromophenyl) aniline (10 g,1 eq) was placed in a single-necked flask, 300mL of methylene chloride was added to dissolve the solid, then intermediate (188-c) (23.86 g,3 eq) was slowly added, reacted at room temperature for 10 hours, poured into an aqueous sodium chloride solution, the yellow was filtered, and the solid was dried to give intermediate (188-d) as a yellow solid in 69% yield.
Synthetic intermediate (188-e):
in a dry two-necked flask was placed pinacol biborate (24.15 g,1.5 eq), intermediate (188-d) (21.95 g,1 eq), pd (dppf) 2 Cl 2 (2.3 g,0.05 eq), potassium acetate (24 g,4 eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 90℃for 12 hours, cooled to room temperature, and the reaction was completedAnd (3) carrying out post spin drying, drying with dichloromethane and water, drying with magnesium sulfate, then carrying out spin drying, and then carrying out separation and purification by using a silica gel chromatographic column. The solid intermediate (188-e) was obtained in 44% yield.
Synthetic complex (188):
Intermediate (188-b) (1 g,1 eq) and intermediate (188-e) (2.44 g,5 eq) were placed in a single-necked flask, and 20mL of 2-isopropanol was added thereto, followed by nitrogen purging. Potassium phosphate (1.32 g,5 eq) was added and reacted at room temperature for 24 hours. Filtering with diatomite, washing with methanol, oven drying, and separating and purifying with silica gel chromatographic column. The product was collected, spin-dried and recrystallized to give the red solid complex (188), yield 59%, mass spectrum peak m/z=923.2728 [ m] + 。
Synthesis example 6 Synthesis of Complex (244)
Synthetic intermediate (244-a):
in a dry two-necked flask was placed phenylboronic acid (11.72 g,1 eq), 1-bromoisoquinoline (20 g,1 eq), pd (PPh 3 ) 4 (5.55 g,0.05 eq), potassium carbonate (39.85 g,3 eq), then a mixed solution of 500mL dioxane and 50mL water was added, the mixture was circulated three times by vacuum-pumping and nitrogen-charging, the reaction was stirred at 95℃for 12 hours, cooled to room temperature, the dichloromethane layer was dried by spinning with a water solution, and then separation and purification were carried out by a silica gel column to obtain an intermediate (244-a) in 86% yield.
Synthetic intermediate (244-b):
intermediate (244-a) (10.72 g,3 eq) was placed in a single-necked flask, iridium trichloride (5.2 g,1 eq) and sodium carbonate (9.23 g,5 eq) were added, a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of water was added, the mixture was heated to 110℃and reacted for 12 hours, cooled to room temperature, poured into an aqueous sodium chloride solution, and the yellow was filtered. After the solid was dried, it was dissolved in a mixed solution of 300mL of methylene chloride and 100mL of methanol, and then silver trifluoromethane sulfonate (13.42 g,3 eq) was added to react for 12 hours, and filtration and drying gave an intermediate (244-b) as a yellow solid in 63% yield.
Synthetic intermediate (244-c):
7-bromoindole (10 g,1 eq) was placed in a single-necked flask, 300mL of methylene chloride was added to dissolve the solid, then benzoyl chloride (35.85 g,5 eq) was slowly added to react at room temperature for 10 hours, poured into aqueous sodium chloride solution, and the yellow material was filtered, and after drying the solid, a yellow solid intermediate (244-c) was obtained in 77% yield.
Synthetic intermediate (244-d):
in a dry two-necked flask was placed pinacol biborate (24.15 g,1.5 eq), intermediate (244-c) (19.03 g,1 eq), pd (dppf) 2 Cl 2 (2.3 g,0.05 eq), potassium acetate (24 g,4 eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the mixture was stirred at 90 ℃ for reaction for 12 hours, cooled to room temperature, dried by spinning after completion of the reaction, dried over dichloromethane and water solution, dried over magnesium sulfate, dried by spinning again, and then separated and purified by a silica gel column. The solid intermediate (244-d) was obtained in 58% yield.
Synthetic complex (244):
intermediate (244-b) (1 g,1 eq) and intermediate (244-d) (2.32 g,5 eq) were placed in a single-necked flask, and 20mL of 2-isopropanol was added thereto, followed by nitrogen purging. Potassium phosphate (1.42 g,5 eq) was added and reacted at room temperature for 24 hours. Filtering with diatomite, washing with methanol, oven drying, and separating and purifying with silica gel chromatographic column. The product was collected, recrystallized after spin-drying to give the red solid complex (244), yield 63%, mass spectrum peak m/z=821.2033 [ m ] + 。
Synthesis example 7 Synthesis of Complex (411)
Synthetic intermediate (411-a):
in a dry two-necked flask were placed 2-bromopyridine (5.19 g,1.2 eq), 4-dibenzofuran boronic acid (5.73 g,1 eq), pd (PPh 3 ) 4 (1.56 g,0.05 eq), potassium carbonate (14.93 g,4 eq), then 250mL dioxane was added, the mixture was stirred at 90℃for reaction for 12 hours, cooled to room temperature, dried by spinning after completion of the reaction, dried over dichloromethane and water, dried over magnesium sulfate and spun againDried, and then separated and purified by silica gel column to obtain a solid intermediate (411-a) in 89% yield.
Synthetic intermediate (411-b):
intermediate (411-a) (12.82 g,3 eq) was placed in a single-necked flask, iridium trichloride (5.2 g,1 eq) and sodium carbonate (9.23 g,5 eq) were added, a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of water was added, the mixture was heated to 110 ℃, reacted for 12 hours, cooled to room temperature, poured into a sodium chloride aqueous solution, and the yellow was filtered. After the solid was dried, it was dissolved in a mixed solution of 300mL of methylene chloride and 100mL of methanol, and then silver trifluoromethane sulfonate (13.42 g,3 eq) was added to react for 12 hours, and filtration and drying gave an intermediate (411-b) as a yellow solid in 77% yield.
Synthetic intermediate (411-c):
1-bromocarbazole (10 g,1 eq) was placed in a single-port bottle, 300mL of methylene chloride was added to dissolve the solid, then benzoyl chloride (28.56 g,5 eq) was slowly added to react at room temperature for 10 hours, poured into aqueous sodium chloride solution, and the yellow material was filtered, and after drying the solid, a yellow solid intermediate (411-c) was obtained in 77% yield.
Synthetic intermediate (411-d):
in a dry two-necked flask was placed pinacol biborate (24.15 g,1.5 eq), intermediate (411-c) (22.2 g,1 eq), pd (dppf) 2 Cl 2 (2.3 g,0.05 eq), potassium acetate (24 g,4 eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the mixture was stirred at 90 ℃ for reaction for 12 hours, cooled to room temperature, dried by spinning after completion of the reaction, dried over dichloromethane and water solution, dried over magnesium sulfate, dried by spinning again, and then separated and purified by a silica gel column. The solid intermediate (411-d) was obtained in 79% yield.
Synthetic complex (411):
intermediate (411-b) (1 g,1 eq) and intermediate (411-d) (2.39 g,5 eq) were placed in a single-necked flask, and 20mL of 2-isopropanol was added thereto, followed by nitrogen purging. Potassium phosphate (1.28 g,5 eq) was added and reacted at room temperature for 24 hours. Filtering with diatomite, washing with methanol, oven drying, and separating and purifying with silica gel chromatographic column. The product was collected, recrystallized after spin-drying to give complex (411) as a yellow solid in 39% yield with mass spectrum peak m/z=951.2122[M] + 。
Synthesis example 8 Synthesis of Complex (524)
Synthetic intermediate (524-a):
in a dry two-necked flask were placed 2-bromopyridine (23.41 g,1.2 eq), benzofuran-2-boronic acid (20 g,1 eq), pd (PPh 3 ) 4 (7.14 g,0.05 eq), potassium carbonate (52.36 g,4 eq), then 250mL dioxane was added, the reaction was stirred at 90 ℃ for 12 hours, cooled to room temperature, dried by spinning after the completion of the reaction, dried with dichloromethane and water, dried by magnesium sulfate and then spun again, and then separated and purified by silica gel chromatography to give a solid intermediate (524-a) in 85% yield.
Synthetic intermediate (524-b):
the intermediate (524-a) (10.20 g,3 eq) was placed in a single-necked flask, iridium trichloride (5.2 g,1 eq) and sodium carbonate (9.23 g,5 eq) were added, a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of water was added, the mixture was heated to 110℃and reacted for 12 hours, cooled to room temperature, poured into an aqueous sodium chloride solution, and the yellow was filtered. After the solid was dried, it was dissolved in a mixed solution of 300mL of methylene chloride and 100mL of methanol, and then silver trifluoromethane sulfonate (13.42 g,3 eq) was added to react for 12 hours, and filtration and drying gave a yellow solid intermediate (524-b) in 77% yield.
Synthetic intermediate (524-c):
7-bromo-1H-benzimidazole (10 g,1 eq) was placed in a single-necked flask, 300mL of methylene chloride was added to dissolve the solid, then 2-naphthoyl chloride (19.35 g,2 eq) was slowly added and reacted at room temperature for 10 hours, poured into an aqueous sodium chloride solution, the yellow was filtered, and the solid was dried to give a yellow solid intermediate (524-c) in 61% yield.
Synthetic intermediate (524-d):
in a dry two-necked flask was placed pinacol biborate (24.15 g,1.5 eq), intermediate (524-c) (22.27 g,1 eq), pd (dppf) 2 Cl 2 (2.3 g,0.05 eq), potassium acetate (24 g,4 eq) and then 250mL were addedThe mixed solution of dioxane and water in the ratio of 3:1 is stirred and reacted for 12 hours at 90 ℃, cooled to room temperature, dried by spin after the reaction is completed, dried by using dichloromethane and water solution, dried by using magnesium sulfate and then dried by spin, and then separated and purified by using a silica gel chromatographic column. The solid intermediate (524-d) was obtained in 79% yield.
Synthetic complex (524):
intermediate (524-b) (1 g,1 eq) and intermediate (524-d) (2.73 g,5 eq) were placed in a single-necked flask, and 20mL of 2-isopropanol was added thereto, followed by nitrogen purging. Potassium phosphate (1.45 g,5 eq) was added and reacted at room temperature for 24 hours. Filtering with diatomite, washing with methanol, oven drying, and separating and purifying with silica gel chromatographic column. The product was collected, dried by spin-drying and recrystallized to give the yellow solid complex (524), yield 46%, mass spectrum peak m/z=852.1738 [ m] + 。
Synthesis example 9 Synthesis of Complex (559)
Synthetic intermediate (559-a):
1-phenylbenzimidazole (10 g,1 eq) was placed in a single-necked flask, 250mL of diethyl ether was added as a solvent, methyl iodide (9.5 g,1.3 eq) was then added, the reaction was stirred at 40℃for 15 hours, and after cooling to room temperature, the white solid was filtered and washed with diethyl ether. The white solid was then placed in a light-shielding single-necked flask, and silver oxide (15.5 g,1.3 eq) was added, 100mL of methylene chloride was added, and the reaction was stirred in a greenhouse for 4 hours, and the solid was filtered and dried to obtain a brown solid intermediate (559-a) in 93% yield.
Synthetic intermediate (559-b):
7-bromo-1H-2-phenylbenzimidazole (10 g,1 eq) was placed in a single-necked flask, 300mL of methylene chloride was added to dissolve the solid, then 2-naphthoyl chloride (25.73 g,5 eq) was slowly added to react at room temperature for 10 hours, poured into an aqueous sodium chloride solution, the yellow material was filtered, and the solid was dried to give a yellow solid intermediate (559-b) in 61% yield.
Synthetic intermediate (559-c):
placing in a dry double-mouth bottlePinacol ester of Di-boric acid (24.15 g,1.5 eq), intermediate (559-b) (23.92 g,1 eq), pd (dppf) 2 Cl 2 (2.3 g,0.05 eq), potassium acetate (24 g,4 eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the mixture was stirred at 90 ℃ for reaction for 12 hours, cooled to room temperature, dried by spinning after completion of the reaction, dried over dichloromethane and water solution, dried over magnesium sulfate, dried by spinning again, and then separated and purified by a silica gel column. The solid intermediate (559-c) was obtained in 81% yield.
Synthetic intermediate (559-d):
intermediate (559-c) (22.17 g,3 eq) and potassium phosphate (18.48 g,5 eq) were placed in a single-necked flask, iridium trichloride (5.2 g,1 eq) was added, a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of water was added, the mixture was heated to 110℃and reacted for 12 hours, cooled to room temperature, poured into an aqueous sodium chloride solution, and the yellow was filtered. After the solid was dried, it was dissolved in a mixed solution of 300mL of methylene chloride and 100mL of methanol, and then silver trifluoromethane sulfonate (13.42 g,3 eq) was added to react for 12 hours, and filtration and drying gave a yellow solid intermediate (559-d) in 42% yield. Synthetic complex (559):
intermediate (559-d) (1 g,1 eq) and intermediate (559-a) (1.42 g,3 eq) were placed in a single-necked flask, 50mL of tetrahydrofuran was added, and after blowing nitrogen, sodium carbonate (0.57 g,5 eq) was added and reacted at room temperature for 24 hours. Filtering with diatomite, washing with methanol, oven drying, separating and purifying with silica gel chromatographic column, spin drying, and recrystallizing to obtain yellow solid complex (559) with yield of 64% and mass spectrum peak m/z=994.2617 [ M ] ] + 。
Synthesis example 10 Synthesis of Complex (577)
Synthetic intermediate (577-a):
placing 4-dibenzofuran boric acid in a dry double-mouth bottle(20.38 g,1 eq), 1-bromoisoquinoline (20 g,1 eq), pd (PPh) 3 ) 4 (5.55 g,0.05 eq), potassium carbonate (39.85 g,3 eq), then a mixed solution of 500mL dioxane and 50mL water was added, the mixture was circulated three times by vacuum-pumping and nitrogen-charging, the reaction was stirred at 95℃for 12 hours, cooled to room temperature, the dichloromethane layer was dried by spinning with dichloromethane and water, and then separation and purification were carried out by silica gel chromatography to obtain an intermediate (577-a) in 86% yield.
Synthetic intermediate (577-b):
intermediate (577-a) (10.72 g,3 eq) was placed in a single-necked flask, iridium trichloride (5.2 g,1 eq) and sodium carbonate (9.23 g,5 eq) were added, a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of water was added, the mixture was heated to 110℃and reacted for 12 hours, cooled to room temperature, poured into an aqueous sodium chloride solution, and the yellow was filtered. After the solid was dried, it was dissolved in a mixed solution of 300mL of methylene chloride and 100mL of methanol, and then silver trifluoromethane sulfonate (13.42 g,3 eq) was added to react for 12 hours, and filtration and drying gave a yellow solid intermediate (577-b) in 63% yield.
Synthetic intermediate (577-c):
7-bromo-4-oxindole (10 g,1 eq) was placed in a single-necked flask, 300mL of methylene chloride was added to dissolve the solid, then 2-bromobenzoyl chloride (10.35 g,1 eq) was slowly added and reacted at room temperature for 10 hours, poured into aqueous sodium chloride solution, the yellow was filtered and the solid was dried to give a yellow solid intermediate (577-c) in 59% yield.
Synthetic intermediate (577-d):
in a dry double-necked flask, an intermediate (577-c) (20 g,1 eq), potassium phosphate (21.49 g,2 eq) and cuprous iodide (0.48 g,0.05 eq) were placed, then 500mL of tetrahydrofuran was added as a solution, the reaction was stirred at 80℃for 8 hours, cooled to room temperature, dried by spin-drying after completion of the reaction, dried by using methylene chloride and a water-containing liquid, dried by spin-drying after drying with magnesium sulfate, and then separated and purified by using a silica gel column. The solid intermediate (577-d) was obtained in 69% yield. Synthetic intermediate (577-e):
in a dry two-necked flask was placed pinacol biborate (24.15 g,1.5 eq), intermediate (577-d) (19.92 g,1 eq), pd (dppf) 2 Cl 2 (2.3 g,0.05 eq), potassium acetate (24 g,4 eq), howeverThen 250mL of mixed solution of dioxane and water with the ratio of 3:1 is added, the mixture is stirred at 90 ℃ for reaction for 12 hours, the mixture is cooled to room temperature, the mixture is dried by spin after the reaction, dichloromethane and water solution are used, the mixture is dried by magnesium sulfate and then dried by spin, and then the mixture is separated and purified by a silica gel chromatographic column. The solid intermediate (577-e) was obtained in 75% yield.
Synthetic complex (577):
intermediate (577-b) (1 g,1 eq) and intermediate (577-e) (1.94 g,5 eq) were placed in a single-necked flask, and 20mL of 2-isopropanol was added thereto, followed by nitrogen purging. Potassium phosphate (1.14 g,5 eq) was added and reacted at room temperature for 24 hours. Filtering with diatomite, washing with methanol, oven drying, and separating and purifying with silica gel chromatographic column. The product was collected, recrystallized after spin-drying to give the red solid complex (577) in 31% yield with mass spectrum peak m/z=1015.2010 [ m ] ] + 。
Synthesis example 11 Synthesis of Complex (592)
Synthetic complex (592):
iridium trichloride (0.52 g,1 eq) and intermediate (40-c) (4.17 g,6 eq) were placed in a single-necked flask, and 20mL of diethyl ether was added thereto, followed by nitrogen blowing. Sodium carbonate (18.45 g,10 eq) was added and the reaction was heated to 120℃for 24 hours. After the reaction was completed, the solvent was evaporated in vacuo, water and dichloromethane were added to extract the separated solution, and after the dichloromethane layer was dried by spin-drying, the solid was washed with methanol, and separated and purified by silica gel chromatography. The product was collected, recrystallized after spin-drying to give the red solid complex (592), yield 27%, mass spectrum peak m/z=1009.2930 [ m] + 。
Synthesis example 12 Synthesis of Complex (Pt-40)
Synthetic intermediate (Pt-40-a):
2-phenylpyridine (6.32 g,1.7 eq) was put in a single-necked flask, potassium chloroplatinite (9.95 g,1 eq) was added, a mixed solution of 300mL of ethylene glycol ether and 100mL of water was added, the mixture was heated to 110℃and reacted for 12 hours, cooled to room temperature, poured into an aqueous sodium chloride solution, and the yellow was filtered. After the solid was dried, it was dissolved in a mixed solution of 300mL of methylene chloride and 100mL of methanol, and then silver trifluoromethane sulfonate (18.48 g,3 eq) was added to react for 12 hours, and filtration and drying gave a yellow solid intermediate (Pt-40-a) in 40% yield.
Synthetic complex (Pt-40):
the intermediate (Pt-40-a) (1 g,1 eq) and the intermediate (40-c) (4.00 g,5 eq) were placed in a single-necked flask, and 20mL of 2-isopropanol was added thereto, followed by nitrogen purging. Potassium phosphate (2.13 g,5 eq) was added and reacted at room temperature for 24 hours. Filtering with diatomite, washing with methanol, oven drying, and separating and purifying with silica gel chromatographic column. The product was collected, recrystallized after spin-drying to give the red solid complex (Pt-40), 60% yield, mass spectrum peak m/z=621.1444 [ m] + . 2. Transition 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 Gaussian03W in Hartree. The results are shown in Table one:
List one
Material HOMO[eV] LUMO[eV] T1[eV] S1[eV] ΔE S-T
Complex (40) -5.08 -2.35 2.52 2.70 0.18
Complex (115) -5.49 -2.64 2.71 2.83 0.12
Complex (127) -5.40 -2.64 2.37 2.81 0.44
Complex (164) -5.19 -2.36 2.67 2.84 0.17
Complex (188) -5.33 -2.64 2.38 2.62 0.24
Complex (244) -5.20 -2.66 2.23 2.49 0.26
Complex (411) -5.22 -2.71 2.49 2.54 0.05
Complex (524) -5.11 -2.26 2.68 2.83 0.15
Complex (559) -5.15 -2.69 2.66 2.89 0.23
Complex (577) -5.25 -2.80 2.22 2.44 0.23
Complex (592) -5.10 -2.89 1.93 2.02 0.09
Complex (Pt-40) -5.75 -2.74 2.33 2.41 0.08
Ir(ppy) 2 (acac) -5.22 -2.41 2.68 2.79 0.11
Ir(piq) 2 (acac) -5.33 -2.73 2.19 2.51 0.32
3. Preparation and characterization of OLED devices:
the structure of the OLED device is as follows:
wherein the EML is doped with 10% w/w of (40) or (115) or (127) or (164) or (188) or (244) or (411) or (524) or (559) or (577) or (592) or Ir (ppy) by CBP 2 (acac) or Ir (piq) 2 (acac) composition. ETL consisted of LiQ (8-hydroxyquinoline-lithium) doped with 40% w/w TPBi. The material structure used for the device is as follows:
the OLED device was prepared as follows:
a. cleaning the conductive glass substrate, namely cleaning the conductive glass substrate by using various solvents, such as chloroform, ketone and isopropanol, and then performing ultraviolet ozone plasma treatment;
b、in high vacuum (1X 10) -6 Mbar) by thermal evaporation;
c. cathode LiF/Al (1 nm/150 nm) under high vacuum (1X 10) -6 Millibar) by thermal evaporation;
d. encapsulation 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 maximum luminescence Wavelength, external quantum efficiency. Detected with classical phosphorescent green dopant Ir (ppy) 2 (acac) relative comparison, relative starting voltage, relative external quantum efficiency parameter, and relative lifetime T of OLED device 95 @50mA·cm –2 As shown in table two:
green light complex data (Table II)
OLED device doping Relative starting voltage (V) Relative external quantum efficiency Relative life T 95 @50mA·cm –2
Complex (40) 91％ 111％ 120％
Complex (115) 93％ 121％ 115％
Complex (164) 92％ 118％ 117％
Complex (411) 96％ 106％ 107％
Complex (524) 95％ 118％ 109％
Complex (559) 94％ 115％ 112％
Ir(ppy) 2 (acac) 100％ 100％ 100％
Detected, with classical phosphorescent red dopant Ir (piq) 2 (acac) relative comparison, relative starting voltage, relative external quantum efficiency parameter, and relative lifetime T of OLED device 95 @50mA·cm –2 As shown in table three:
red light complex data (Table III)
OLED device doping Relative starting voltage (V) Relative external quantum efficiency Relative life T 95 @50mA·cm –2
Complex (127) 95％ 118％ 112％
Complex (188) 96％ 115％ 109％
Complex (244) 95％ 110％ 111％
Complex (577) 92％ 112％ 118％
Complex (592) 90％ 104％ 123％
Ir(piq) 2 (acac) 100％ 100％ 100％
It can be seen that if aromatic amine-containing groups are used as auxiliary ligands to replace diketones, devices made of various red and green Ir (III) complexes, respectivelyLigands for OLED devices, especially as light-emitting layer doping materials, which reduce the starting voltage, increase the light-emitting external quantum efficiency and the device lifetime T 95 . It is estimated that the compounds containing the aromatic amine groups have excellent hole transport ability, and the structures can form six-membered ring structures with finer ring tension, so that the stability of the complex is further improved, and therefore, the complex containing the groups can also improve the brightness and the current efficiency of the device, and simultaneously reduce the starting voltage, so that the service life of the device is prolonged.
Further optimization, such as optimization of device structure, optimization of the 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 merely represent a few specific and detailed embodiments, but 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.

Claims (9)

1. A transition metal complex is characterized by being represented by a general formula (1):
（1）
wherein:
m is selected from iridium or platinum;
m is selected from 0 or 1 or 2; n is selected from 1 or 2 or 3;
R 1 and R is 2 Each occurrence is independently selected from H, D, straight chain alkyl groups having 1 to 10C atomsOr a linear alkoxy group having 1 to 10C atoms, R 1 And R is 2 Can bond to each other to form a ring;
Ar 1 any one of the following groups:
；
Ar 2 any one of the following groups:
；
in Ar 1 And Ar is a group 2 In each occurrence of X is independently selected from CR 4 Or N; y is independently selected from CR for each occurrence 4 R 5 、NR 4 Or O; r is R 4 And R is 5 H or D respectively;
g1 is selected from any one of the following groups:
in G1, X is independently selected from CR for each occurrence 4 ，R 4 Is H or D, when X is a connection site, X is selected from C;
T 2 absence, or single bond, orOr->，R 3 Selected from H or D;
T 1 absence or as；
G2 is selected from vinyl groups or phenyl groups;
g3 is selected from linear alkyl groups having 1 to 30 carbon atoms, havingBranched alkanes having 3 to 30 carbon atoms, or cyclic alkanes having 3 to 10 carbon atoms,Or->；
And a represents a ligation site.
2. The transition metal complex according to claim 1, characterized in that:selected from any one of the following structures:
Wherein Q is selected from C or N; * Represents the site of attachment to M.
3. The transition metal complex according to claim 2, characterized in that:selected from any one of the following structures:
。
4. the transition metal complex according to claim 1, characterized in that: the general formula (1) is selected from any one of the following general formulas:
。
5. the transition metal complex according to claim 1, characterized in that:selected from any one of the following structures:
。
6. the transition metal complex according to claim 1, characterized in that:selected from any one of the following structures:
。
7. a mixture comprising the transition metal complex according to any one of claims 1 to 6 and at least one organic functional material selected from the group consisting of a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitter, a host material, and a doping material.
8. A composition comprising a transition metal complex according to any one of claims 1 to 6 or a mixture according to claim 7, and at least one organic solvent.
9. An organic electronic device comprising at least one functional layer comprising a transition metal complex according to any one of claims 1 to 6 or a mixture according to claim 7 or prepared from a composition according to claim 8.
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CN109608504A (en) * 2017-12-28 2019-04-12 广州华睿光电材料有限公司 Organometallic complex, polymer, mixture, composition and organic electronic device
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DE102008013691A1 (en) * 2008-03-11 2009-09-17 Merck Patent Gmbh Use of compositions of neutral transition metal complexes in opto-electronic devices
CN109790194A (en) * 2016-11-23 2019-05-21 广州华睿光电材料有限公司 Metal organic complex, high polymer, composition and organic electronic device
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