WO2014021997A1

WO2014021997A1 - Monodentate gold ethynyl complexes

Info

Publication number: WO2014021997A1
Application number: PCT/US2013/045618
Authority: WO
Inventors: Srinivas Prasad SISTA; Arunkumar Natarajan; Jie Jerry LIU; Patrick Joseph Mccloskey; Joseph John Shiang
Original assignee: General Electric Co
Current assignee: General Electric Co
Priority date: 2012-07-30
Filing date: 2013-06-13
Publication date: 2014-02-06
Anticipated expiration: 2015-01-30
Also published as: US8530685B1

Description

MONODENTATE GOLD ETHYNYL COMPLEXES

BACKGROUND

[0001 ] Ongoing challenges for organic light emitting diodes (OLEDs) for lighting applications include improving efficiency and stability of the devices. Phosphorescent dyes based on iridium have been used to achieve high efficiency OLEDs. Other classes of phosphorescent dyes that have been explored in the past include platinum- and europium-based materials, and there have been few successful efforts to design phosphorescent dyes based on other heavy metals. Therefore, there is a need for a new class of materials that can enable devices having improved efficiency and stability.

BRIEF DESCRIPTION

[0002] In one aspect, the present invention relates to monodentate gold ethynyl complexes that display phosphorescence at room temperature. Complexes having a gold-carbon bond and a gold-phosphorous bond, and more specifically, complexes of formula I, may be useful for optoelectronic devices

Ar¹— =— Ar² = Au-PR₃

I wherein Ar¹ and Ar² are independently monocyclic or polycyclic aryl, unsubstituted or substituted with one or more alkyl, alkenyl, alkoxy, aryl, aryloxy, fluoro, fluoroalkyi, or perfluoroalkyl, and R is substituted or unsubstituted aryl. Accordingly, in another aspect, the present invention relates to optoelectronic devices that include a monodentate gold ethynyl complex of formula I.

DRAWINGS

[0003] These and other features, aspects, and advantages of the present invention will become better understood when the following detailed description is read with reference to the accompanying drawings in which like characters represent like parts throughout the drawings, wherein: [0004] FIG. 1 shows steady state photoluminescence (PL) spectra of thin films of gold ethynyl complexes diluted in a polystyrene matrix.

[0005] FIG. 2 shows a room temperature steady-state PL spectrum and a low temperature delayed fluorescence spectrum for the gold ethynyl complex of

Example 1.

DETAILED DESCRIPTION

[0006] Gold ethynyl complexes of formula I include divalent aryl group Ar² connected through a first ethynyl group to monovalent group Ar¹ and through a second ethynyl group to -AuPR₃. In many embodiments, the PR₃ ligand is PPh₃. Aryl group Ar¹ may be monovalent monocyclic or polycyclic aryl, unsubstituted or substituted with one or more alkyl, alkenyl, alkoxy, aryl, aryloxy, fluoro, fluoroalkyl, or perfluoroalkyl. Aryl group Ar² may be divalent monocyclic or polycyclic aryl, unsubstituted or substituted with one or more alkyl, alkenyl, alkoxy, aryl, aryloxy, fluoro, fluoroalkyl, or perfluoroalkyl. The monocyclic or polycyclic groups and substituents form are selected independently for Ar¹ and Ar².

[0007] In particular embodiments, Ar¹ and Ar² are independently monocyclic aryl, unsubstituted or substituted with one or more alkyl, alkenyl, alkoxy, aryl, aryloxy, fluoro, fluoroalkyl, or perfluoroalkyl. In some embodiments, Ar¹ is unsubstituted monocyclic aryl, particularly phenyl. In other embodiments, Ar¹ is unsubstituted polycyclic aryl, particularly fluorenyl. In yet other embodiments, Ar² is unsubstituted monocyclic aryl, particularly phenyl.

[0008] Specific examples of monodentate gold ethynyl complexes according the present invention are

and [0009] Compounds of formula I may be prepared by reacting a precursor ethynyl compound of formula II with a halo-(triphenylphosphine) gold(l) compound, as shown in Scheme 1 .

Scheme 1

Ar¹—≡≡≡— Ar² =≡ + X-Au— PPh₃ —► Ar¹— ^≡— Ar² ^≡ Au-PPh₃

wherein Ar¹ and Ar² are as defined above and X is chloro, bromo or fluoro.

The reaction may proceed at room temperature, typically under basic conditions.

[0010] Optoelectronic devices according to the present invention include, but are not limited to, organic light emitting diodes (OLEDs).

[001 1 ] An OLED device includes, in the simplest case, an anode layer and a corresponding cathode layer with an organic electroluminescent layer disposed between said anode and said cathode. When a voltage bias is applied across the electrodes, electrons are injected by the cathode into the electroluminescent layer while electrons are removed from (or "holes" are "injected" into) the electroluminescent layer from the anode. Light emission occurs as holes combine with electrons within the electroluminescent layer to form singlet or triplet excitons, light emission occurring as singlet and/or triplet excitons decay to their ground states via radiative decay.

[0012] Other components which may be present in an OLED in addition to the anode, cathode and light emitting material include a hole injection layer, an electron injection layer, and an electron transport layer. The electron transport layer need not be in direct contact with the cathode, and frequently the electron transport layer also serves as a hole locking layer to prevent holes migrating toward the cathode. Additional components which may be present in an organic light-emitting device include hole transporting layers, hole transporting emission (emitting) layers and electron transporting emission (emitting) layers.

[0013] The organic electroluminescent layer, i.e., the emissive layer, is a layer within an organic light emitting device which when in operation contains a significant concentration of both electrons and holes and provides sites for exciton formation and light emission. A hole injection layer is a layer in contact with the anode which promotes the injection of holes from the anode into the interior layers of the OLED; and an electron injection layer is a layer in contact with the cathode that promotes the injection of electrons from the cathode into the OLED; an electron transport layer is a layer which facilitates conduction of electrons from the cathode and/or the electron injection layer to a charge recombination site. During operation of an organic light emitting device comprising an electron transport layer, the majority of charge carriers (i.e. holes and electrons) present in the electron transport layer are electrons and light emission can occur through recombination of holes and electrons present in the emissive layer. A hole transporting layer is a layer which when the OLED is in operation facilitates conduction of holes from the anode and/or the hole injection layer to charge recombination sites and which need not be in direct contact with the anode. A hole transporting emission layer is a layer in which when the OLED is in operation facilitates the conduction of holes to charge recombination sites, and in which the majority of charge carriers are holes, and in which emission occurs not only through recombination with residual electrons, but also through the transfer of energy from a charge recombination zone elsewhere in the device. An electron transporting emission layer is a layer in which when the OLED is in operation facilitates the conduction of electrons to charge recombination sites, and in which the majority of charge carriers are electrons, and in which emission occurs not only through recombination with residual holes, but also through the transfer of energy from a charge recombination zone elsewhere in the device.

[0014] Materials suitable for use as the anode have a bulk conductivity of preferred about 1000 ohms per square, as measured by a four-point probe technique. Indium tin oxide (ITO) is frequently used as the anode because it is substantially transparent to light transmission and thus facilitates the escape of light emitted from electro- active organic layer. Other materials, which may be utilized as the anode layer, include tin oxide, indium oxide, zinc oxide, indium zinc oxide, zinc indium tin oxide, antimony oxide, and mixtures thereof.

[0015] Materials suitable for use as the cathode include general electrical conductors including, but not limited to metals and metal oxides such as ITO etc which can inject negative charge carriers (electrons) into the inner layer(s) of the OLED. Various metals suitable for use as the cathode include K, Li, Na, Cs, Mg, Ca, Sr, Ba, Al, Ag, Au, In, Sn, Zn, Zr, Sc, Y, elements of the lanthanide series, alloys thereof, and mixtures thereof. Suitable alloy materials for use as the cathode layer include Ag- Mg, Al-Li, In-Mg, Al-Ca, and Al-Au alloys. Layered non-alloy structures may also be employed in the cathode, for example, a thin layer of calcium metal such as calcium, or a metal fluoride, such as LiF, covered by a thicker layer of a metal, such as aluminum or silver. In particular, the cathode may be composed of a single metal, and especially of aluminum metal.

[0016] Materials suitable for use in the electron transport layer include poly(9,9- dioctyl fluorene), tris(8-hydroxyquinolato) aluminum (Alq₃), 2,9-dimethyl-4,7-diphenyl- 1 , 1 -phenanthroline, 4,7-diphenyl-1 , 10-phenanthroline, 2-(4-biphenylyl)-5-(4-t- butylphenyl)-1 ,3,4-oxadiazole, 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1 ,2,4- triazole, 1 ,3,4-oxadiazole-containing polymers, 1 ,3,4-triazole-containing polymers, quinoxaline-containing polymers, and cyano-PPV.

[0017] Materials suitable for use in hole transporting layers include 1 , 1 -bis((di-4- tolylamino) phenyl)cyclohexane, Ν,Ν'- bis(4-methylphenyl)-N,N'-bis(4-ethylphenyl)- (1 ,1 '-(3,3'-dimethyl)biphenyl)-4,4'-diamine, tetrakis-(3-methylphenyl)-N,N,N',N'-2,5- phenylenediamine, phenyl-4-N,N-diphenylaminostyrene, p-(diethylamino) benzaldehyde diphenylhydrazone, triphenylamine, 1-phenyl-3-(p-

(diethylamino)styryl)-5-(p-(diethylamino)phenyl)pyrazoline, 1 ,2-trans-bis(9H-carbazol- 9-yl)cyclobutane, N,N,N',N'-tetrakis(4-methylphenyl)-(1 , 1 '-biphenyl)-4,4'-diamine, copper phthalocyanine, polyvinylcarbazole, (phenylmethyl)polysilane; poly(3,4- ethylendioxythiophene) (PEDOT), polyaniline, polyvinylcarbazole, triaryldiamine, tetraphenyldiamine, aromatic tertiary amines, hydrazone derivatives, carbazole derivatives, triazole derivatives, imidazole derivatives, oxadiazole derivatives having an amino group, and polythiophenes as disclosed in U.S. Pat. No. 6,023,371 .

[0018] Materials suitable for use in the light emitting layer along with the compounds of formula I include electroluminescent polymers such as polyfluorenes, preferably poly(9,9-dioctyl fluorene) and copolymers thereof, such as poly(9,9'-dioctylfluorene- co-bis-N,N '-(4-butylphenyl)diphenylamine) (F8-TFB); poly(vinylcarbazole) and polyphenylenevinylene and their derivatives. Small molecule host materials such as N,N'-dicarbazolyl-3,5-benzene (mCP), N,N'-dicarbazolyl-4-4'-biphenyl (CBP), host materials disclosed in US201 1/0006670, publication date 13 January 201 1 , assigned to Konica Minolta Holdings, Inc., and silicon-containing materials described by Ren, et al. (Chemistry of Materials 2004 16 (23), 4743-4747) may also be used. The light emitting layer may include a blue, yellow, orange, green or red phosphorescent dye or metal complex, in addition to the gold ethynyl complexes of formula I, for example, tris(l -phenylisoquinoline) iridium (III) (red dye), tris(2-phenylpyridine) iridium (green dye) and Iridium (III) bis(2-(4,6-difluorephenyl)pyridinato-N,C2) (blue dye). Commercially available electrofluorescent and electrophosphorescent metal complexes from ADS (American Dyes Source, Inc.) may also be used. ADS green dyes include ADS060GE, ADS061 GE, ADS063GE, and ADS066GE, ADS078GE, and ADS090GE. ADS blue dyes include ADS064BE, ADS065BE, and ADS070BE. ADS red dyes include ADS067RE, ADS068RE, ADS069RE, ADS075RE, ADS076RE, ADS067RE, and ADS077RE.

EXAMPLE 1 : Preparation of 4'-(2-phenyl acetylene)phenyl acetylene gold triphenyl phosphine (PPh3-Au-PE2)

[0019] To a 100 mL round bottom flask was added 4'-(2-phenyl acetylene)phenyl acetylene ( 0.108 g, 0.535 mmoles) , chloro(triphenylphosphine) gold(l) ( 0.250 g, 0.504 mmoles) and 40 mL of methanol . This mixture was stirred at room temperature under nitrogen then 350mg of sodium hydroxide dissolved in 20 mL of methanol was added. The mixture became clear after 1 hour, then a white precipitate formed. After 18 hours, the reaction mixture stirring was stopped and the precipitate allowed to settle. The supernatant which contained the product was separated by decanting and the white solid washed with 20 mL of additional methanol. The liquid layers were combined and concentrated to provide an off white solid ( 0.30 g, 0.455 mmoles, 90%) which was pure by tic. 1 H NMR spectrum 7.31-7.38 complex multiplet, 3H and 7.41 -7.62 complex multiplet, 24H.

PPh3-Au-PE2 EXAMPLE 2: Preparation of 4-(2-thienyl)-phenyl acetylene gold triphenyl phosphine (Thiophene-Au)

[0020] The same method as Example 1 was used, starting with 4-(2-thienyl)phenyl acetylene as the alkyne. A pale yellow solid was isolated. 1 H NMR spectrum 7.03-7.10 dd, 1 H, 7.22-7.34 dd, 2H, 7.42-7.62 complex multiplet, 22 H

Thiophene-Au

EXAMPLE 3: Preparation of 4(2-fluorenyl acetylene)phenyl acetylene gold triphenyl phosphine

[0021 ] The same method as Example 1 was used, starting with 4-(2-fluorenyl acetylene)phenyl acetylene. However, the resulting solid was washed with 50 mL of warm solution of hexanes-ethyl acetate (90:10) to remove traces of starting material, resulting in an off white to cream colored solid. 1 H NMR spectrum 7.34, t 1 H, 7.41 t, 1 H, 7.42-7.60 complex multiplet 24 H, 7.71-7.62 multiplet , 3H.

EXAMPLE 4: Preparation of 2-(4-Nitrophenyl )acetylene gold triphenyl phosphine (N02-Au)

[0022] The same method as Example 1 was used, starting with 4-nitrophenyl acetylene. A pale yellow solid was isolated and then washed several times with methanol to yield a pale yellow solid. 1 H NMR spectrum 7.46-7.63 complex multiplet, 17H, 8.12-8.16 dd,2H.

N02-Au

EXAMPLE 5: Optoelectronic properties

[0023] Steady state photoluminescence of the gold-ethynyl compounds of Examples 1 (PPh3-Au-PE2), 2 (Thiophene-Au), and 4(N02-Au), and phenyl acetylene gold triphenyl phosphine (PPh3-Au-PE1 ) was measured using thin films formed from dispersions of the compounds in a polystyrene matrix.

PPh3-Au-PE1

All of the compounds had a broad emission spectrum ranging from 320nm to 650nm. Such broad emission spectrum corresponds to white light. Emission spectra are shown in FIG. 1. Delayed photoluminescence of the compound of Example 1 was studied under liquid nitrogen conditions to differentiate the emission from triplets and singlet excitons.

[0024] FIG. 2 shows a steady state photoluminescence (PL) spectrum and low temperature delayed PL spectrum for the gold ethynyl of Example 1 .

Phosphorescence lifetimes are in microsecond to millisecond range while fluorescence decay lifetime is in nanoseconds. The microsecond delayed fluorescence signal observed at 500nm was attributed to phosphorescence. The phosphorescence signal was also observed at room temperature implying that Au- ethynyl compounds demonstrate room temperature phosphorescence. Besides room temperature phosphorescence, room temperature fluorescence was observed at 350nm. This is advantageous because a single dye molecule can generate both blue and green light.

[0025] In the context of the present invention, alkyl is intended to include linear, branched, or cyclic hydrocarbon structures and combinations thereof, including lower alkyl and higher alkyl. Preferred alkyl groups are those of C₂₀ or below. Lower alkyl refers to alkyl groups of from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, and includes methyl, ethyl, n-propyl, isopropyl, and n-, s- and t- butyl. Higher alkyl refers to alkyl groups having seven or more carbon atoms, preferably 7-20 carbon atoms, and includes n-, s- and f-heptyl, octyl, and dodecyl. Cycloalkyl is a subset of alkyl and includes cyclic hydrocarbon groups of from 3 to 8 carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and norbornyl. Alkenyl and alkynyl refer to alkyl groups wherein two or more hydrogen atoms are replaced by a double or triple bond, respectively.

[0026] Aryl and heteroaryl mean a 5- or 6-membered aromatic or heteroaromatic ring containing 0-3 heteroatoms selected from nitrogen, oxygen or sulfur; a bicyclic 9- or 10-membered aromatic or heteroaromatic ring system containing 0-3 heteroatoms selected from nitrogen, oxygen or sulfur; or a tricyclic 13- or 14-membered aromatic or heteroaromatic ring system containing 0-3 heteroatoms selected from nitrogen, oxygen or sulfur. The aromatic 6- to 14-membered carbocyclic rings include, for example, benzene, naphthalene, indane, tetralin, and fluorene; and the 5- to 10- membered aromatic heterocyclic rings include, e.g., imidazole, pyridine, indole, thiophene, benzopyranone, thiazole, furan, benzimidazole, quinoline, isoquinoline, quinoxaline, pyrimidine, pyrazine, tetrazole and pyrazole.

[0027] Polycyclic aryl groups are those derived from polycyclic aromatic hydrocarbons (PAH), and particularly, fused systems (fused carbocycles), that is, having at least two rings of five or more members and containing only "ortho" or "ortho- and peri-" fusions. Examples of these include, but are not limited to, naphthalene, fluorene, phenanthrene, anthracene, pyrene and perylene. Likewise, polycyclic heteroaryl groups are those derived from polycyclic heteroaromatic compounds, particularly, fused systems (fused heterocycles), such as carbazole, phenothiazine, and thianthrene. [0028] Arylalkyl means an alkyl residue attached to an aryl ring. Examples are benzyl and phenethyl. Heteroarylalkyl means an alkyl residue attached to a heteroaryl ring. Examples include pyridinylmethyl and pyrimidinylethyl. Alkylaryl means an aryl residue having one or more alkyl groups attached thereto. Examples are tolyl and mesityl.

[0029] Alkoxy or alkoxyl refers to groups of from 1 to 8 carbon atoms of a straight, branched, cyclic configuration and combinations thereof attached to the parent structure through an oxygen. Examples include methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy, and cyclohexyloxy. Lower alkoxy refers to groups containing one to four carbons.

[0030] Acyl refers to groups of from 1 to 8 carbon atoms of a straight, branched, cyclic configuration, saturated, unsaturated and aromatic and combinations thereof, attached to the parent structure through a carbonyl functionality. One or more carbons in the acyl residue may be replaced by nitrogen, oxygen or sulfur as long as the point of attachment to the parent remains at the carbonyl. Examples include acetyl, benzoyl, propionyl, isobutyryl, f-butoxycarbonyl, and benzyloxycarbonyl. Lower-acyl refers to groups containing one to four carbons.

[0031 ] Heterocycle means a cycloalkyi or aryl residue in which one or two of the carbon atoms is replaced by a heteroatom such as oxygen, nitrogen or sulfur. Examples of heterocycles that fall within the scope of the invention include pyrrolidine, pyrazole, pyrrole, indole, quinoline, isoquinoline, tetrahydroisoquinoline, benzofuran, benzodioxan, benzodioxole (commonly referred to as methylenedioxyphenyl, when occurring as a substituent), tetrazole, morpholine, thiazole, pyridine, pyridazine, pyrimidine, thiophene, furan, oxazole, oxazoline, isoxazole, dioxane, and tetrahydrofuran.

[0032] Substituted refers to residues, including, but not limited to, alkyl, alkylaryl, aryl, arylalkyl, and heteroaryl, wherein up to three H atoms of the residue are replaced with lower alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, haloalkyl, alkoxy, carbonyl, carboxy, carboxalkoxy, carboxamido, acyloxy, amidino, nitro, halo, hydroxy, OCH(COOH)₂, cyano, primary amino, secondary amino, acylamino, alkylthio, sulfoxide, sulfone, phenyl, benzyl, phenoxy, benzyloxy, heteroaryl, or heteroaryloxy. [0033] Haloalkyi refers to an alkyl residue, wherein one or more H atoms are replaced by halogen atoms; the term haloalkyi includes perhaloalkyl. Examples of haloalkyi groups that fall within the scope of the invention include CH₂F, CHF₂, and CF_3.

[0034] While only certain features of the invention have been illustrated and described herein, many modifications and changes will occur to those skilled in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of the invention.

Claims

CLAIMS:

1. A monodentate gold ethynyl complex of formula I

Ar¹— =— Ar² = Au-PR₃

I wherein Ar¹ and Ar² are independently monocyclic or polycyclic aryl, unsubstituted or substituted with one or more alkyl, alkenyl, alkoxy, aryl, aryloxy, fluoro, fluoroalkyl, or perfluoroalkyl; and

R is substituted or unsubstituted aryl.

2. A monodentate gold ethynyl complex according to claim 1 , wherein Ar¹ and Ar² are independently monocyclic aryl, unsubstituted or substituted with one or more alkyl, alkenyl, alkoxy, aryl, aryloxy, fluoro, fluoroalkyl, or perfluoroalkyl.

3. A monodentate gold ethynyl complex according to claim 1 , wherein Ar¹ is unsubstituted monocyclic aryl.

4. A monodentate gold ethynyl complex according to claim 1 , wherein Ar¹ is phenyl.

5. A monodentate gold ethynyl complex according to claim 1 , wherein Ar¹ is unsubstituted polycyclic aryl.

6. A monodentate gold ethynyl complex according to claim 1 , wherein Ar¹ is fluorenyl.

7. A monodentate gold ethynyl complex according to claim 1 , wherein Ar² is unsubstituted monocyclic aryl.

8. A monodentate gold ethynyl complex according to claim 1 , wherein Ar² is phenyl.

9. A monodentate gold ethynyl complex according to claim 1 , of formula

10. A monodentate gold ethynyl complex according to claim 1 , of formula

1 1 . An optoelectronic device comprising a monodentate gold ethynyl complex having a gold-carbon bond and a gold-phosphorous bond

12. An optoelectronic device according to claim 1 1 , wherein the monodentate gold ethynyl complex is of formula I

Ar¹— =— Ar² = Au-PR₃

I

wherein Ar¹ and Ar² are independently monocyclic or polycyclic aryl, unsubstituted or substituted with one or more alkyl, alkenyl, alkoxy, aryl, aryloxy, fluoro, fluoroalkyl, or perfluoroalkyl; and

R is substituted or unsubstituted aryl.

13. An optoelectronic device according to claim 12, wherein Ar¹ and Ar² are independently monocyclic aryl, unsubstituted or substituted with one or more alkyl, alkenyl, alkoxy, aryl, aryloxy, fluoro, fluoroalkyl, or perfluoroalkyl.

14. An optoelectronic device according to claim 12, wherein Ar¹ is unsubstituted monocyclic aryl.

15. An optoelectronic device according to claim 12, wherein Ar¹ is phenyl.

16. An optoelectronic device according to claim 12, wherein Ar¹ is unsubstituted polycyclic aryl.

17. An optoelectronic device according to claim 12, wherein Ar¹ is fluorenyl.

18. An optoelectronic device according to claim 12, wherein Ar² is unsubstituted monocyclic aryl.

19. An optoelectronic device according to claim 12, wherein Ar² is phenyl.

20. An optoelectronic device according to claim 11 , wherein the gold ethynyl complex is of formula

21 . An optoelectronic device according to claim 11 , wherein the gold ethynyl complex is of formula

22. An optoelectronic device according to claim 11 , comprising an OLED device.