JP2008504371A - Organometallic compounds and devices formed with such compounds - Google Patents

Abstract

（式中、Ｌ¹はアリール−Ｎ−複素環配位子およびヘテロアリール−Ｎ−複素環配位子から選択され、Ｌ²はアニオン性配位子であり、Ｌ³はノニオン性配位子であり、Ｌ⁴はＬ¹およびＬ²から選択され、ＭはＲｅ、Ｒｕ、Ｏｓ、Ｒｈ、Ｉｒ、Ｐｄ、ＰｔおよびＡｕから選択される金属であり、Ｆｗは少なくとも２個の（Ｌ⁴−Ｙ_e）基を担持可能な部分であり、Ｙはアルキレン、ヘテロアルキレン、アルケニレン、ヘテロアルケニレンおよびアルキニレンから選択される基であり、ａは１および２から選択され、ｂは０および１から選択され、ｃは０、１および２から選択され、ｄは０および、１から８の整数から選択され、ｅは０および１から選択され、ｆは０および１から選択され、ｇは１から４の整数であり、ならびに、ｈは１および２から選択され、ただし、ａ、ｂ、およびｃは、ＭがＡｕ、Ｐｄ、またはＰｔであるとき金属は４配位であり、およびＭがＲｅ、Ｒｕ、Ｏｓ、ＲｈまたはＩｒであるとき金属は６配位であるよう選択され、ならびに、ただし、ｆ＝０であるとき、ｅ＝０であり、および少なくとも１個の置換基Ｒ¹が少なくとも１個の配位子にあり、ここでＲ¹は溶剤可溶化性である）The present invention relates generally to devices having organometallic compounds having Formula I, Formula II, or Formula III, and a layer comprising at least one of these compounds.
[Chemical 1]

Wherein L ¹ is selected from aryl-N-heterocyclic ligand and heteroaryl-N-heterocyclic ligand, L ² is an anionic ligand, and L ³ is a nonionic ligand L ⁴ is selected from L ¹ and L ² , M is a metal selected from Re, Ru, Os, Rh, Ir, Pd, Pt and Au, and Fw is at least two (L ⁴ − Y _e ) is a moiety capable of carrying a group, Y is a group selected from alkylene, heteroalkylene, alkenylene, heteroalkenylene and alkynylene, a is selected from 1 and 2, and b is selected from 0 and 1 , C is selected from 0, 1 and 2, d is selected from 0 and an integer from 1 to 8, e is selected from 0 and 1, f is selected from 0 and 1, and g is from 1 to 4 An integer, and h is 1 and Where a, b, and c are tetracoordinate when M is Au, Pd, or Pt, and when M is Re, Ru, Os, Rh, or Ir Selected to be hexacoordinate, and when f = 0, e = 0, and at least one substituent R ¹ is in at least one ligand, wherein R ¹ Is solvent solubilizing)

Description

  The present invention relates to organometallic compounds, and more particularly to electrically active organometallic compounds. The invention also relates to an electronic device in which the active layer comprises at least one such organometallic compound.

(Cross-reference of related applications)
This application claims priority from US Provisional Patent Application No. 60 / 545,596, filed June 9, 2004.

  Organic electronic devices that emit light, such as light emitting diodes that make up displays, are present in many different types of electronic equipment. In all such devices, an organic active layer is sandwiched between two electrical contact layers. At least one electrical contact layer is translucent and light can pass through the electrical contact layer. The organic active layer emits light through the translucent electrical contact layer when energized through the electrical contact layer.

  The use of organic electroluminescent compounds as active constituents in light-emitting diodes is well known. Simple organic molecules such as anthracene, thiadiazole derivatives, and coumarin derivatives are known to exhibit electroluminescence. For example, as disclosed in (Friend et al.), (Patent Document 1), (Heeger et al.), (Patent Document 2), and (Nakano et al.) (Patent Document 3). In addition, conjugated polymer semiconductors have also been used as electroluminescent components. For example, as disclosed in (Tang et al.), (US Pat. No. 5,637,097), a complex of 8-hydroxyquinolate with a trivalent metal ion (especially aluminum) is an electroluminescent component. Has been widely used.

Burrows and Thompson have reported that fac-tris (2-phenylpyridine) iridium can be used as an active component in organic light-emitting devices. ((Non-Patent Document 1)) This performance is maximized when an iridium compound is present in the host conductive material. Thompson is also a poly (N-vinylcarbazole) whose active layer is doped with fac-tris [2- (4 ′, 5′-difluorophenyl) pyridine-C ′ ² , N] iridium (III). The element which is is reported. ((Non-patent Document 2)) An electroluminescent iridium complex having a fluorinated phenylpyridine, phenylpyrimidine, or phenylquinoline ligand is disclosed in (Patent Document 5).

  However, there is a continuing need for electroluminescent compounds.

US Pat. No. 5,247,190 US Pat. No. 5,408,109 European Patent Application Publication No. 443 861 US Pat. No. 5,552,678 International Publication No. 02/02714 Pamphlet International Publication No. 0340256 Pamphlet British Patent 615523 Applied Physics Journal (Appl. Phys. Lett.) 1999, 75, 4 Polymer Preprints 2000, 41 (1), 770 Izv. AN USSR. Ser. Khim. 1980, 2827 Inorg. Chem. 1985, 24, 3680 Journal of Fluorine Chemistry (J. Fluorine Chem.) 2002, 117, 121 O. Lose, P.M. Thevenin, E.M. Waldvogel Synlett, 1999, pages 45-48. "Flexible light-emitting diode from solid conducting polymer", Nature 357, 477-479 (June 11, 1992) Kirk-Othmer Encyclopedia of Chemical Technology, 4th edition, volume 18, pages 837-860, 1996. Kirk-Othmer Encyclopedia of Chemical Technology

  The present invention relates to Formula I, Formula II, or Formula III

(Where
L ¹ is selected from aryl-N-heterocyclic ligands and heteroaryl-N-heterocyclic ligands;
L ² is an anionic ligand,
L ³ is a nonionic ligand,
L ⁴ is selected from L ¹ and L ²
M is a metal selected from Re, Ru, Os, Rh, Ir, Pd, Pt and Au;
FW is a moiety capable of supporting at least two (L ⁴ —Y _e ) groups;
Y is a group selected from alkylene, heteroalkylene, alkenylene, heteroalkenylene and alkynylene;
a is selected from 1 and 2,
b is selected from 0 and 1;
c is selected from 0, 1 and 2;
d is selected from an integer from 1 to 8;
e is selected from 0 and 1;
f is selected from 0 and 1,
g is an integer from 1 to 4 and h is selected from 1 and 2;
Provided that a, b, and c are tetracoordinate when M is Au, Pd, or Pt, and hexacoordinate when M is Re, Ru, Os, Rh, or Ir. And as long as f = 0, e = 0, and at least one substituent R ¹ is in at least one ligand, where R ¹ is solvent solubilizing Is)
It relates to a compound having

  In other embodiments, the composition comprises at least one of the above compounds of Formula I, II, or III.

  In another embodiment, an electronic device is provided that contains at least one active layer comprising at least one compound of the invention.

  In other embodiments, organic light emitting diodes (OLEDs) are provided that contain at least one active layer that includes at least one compound of the present invention.

  In another embodiment, an electroluminescent device is provided that contains at least one active layer comprising at least one compound of the invention.

  In a further embodiment, a method is provided for improving the solution processability of electroluminescent organometallic compounds. In one embodiment, such a method is performed by assembling monometallic groups into a multimetallic compound by covalently bonding at least two monometallic groups to a constituent tissue structure, wherein These monometallic groups are directly bonded to the structural structure through a ligand, or are bonded directly through a chain, thereby improving solution processability. In one embodiment, such a method is performed by attaching at least one solvent-solubilizing substituent to at least one ligand of the organomonometallic compound.

  The foregoing general description and the following detailed description are exemplary and explanatory only and are not intended to limit the invention, which is defined by the appended claims.

  The present invention is illustrated by way of example and is not limited in the accompanying figures.

  Provided are electronic devices containing compounds of formula I, II or III, compositions containing these compounds and at least one active layer comprising one of the above formulas. In one embodiment, an organic light emitting diode (OLED) is provided that contains at least one active layer comprising at least one compound of the above formula. In another embodiment, a photoactive device is provided that contains at least one active layer comprising a compound of the above formula.

  In the preparation of organic electronic devices, it is often desirable to form one or more layers using solution processing techniques. In the field of OLEDs, the formation of high-efficiency and long-life multilayer solution processed devices is a difficult task. Some problems faced in this area are the thermal and morphological stability of organic materials and the ability to form films. Of particular relevance is the solubility and film-forming ability of the materials used in the active layer (eg, radiation) layer. In certain embodiments, key device performance depends on the quality of the deposited film. In one OLED embodiment, the emissive layer comprises a host transport material doped with an electroluminescent material at <20% by weight. In one embodiment, there is excellent miscibility between the host and the electroluminescent material, and good quality films can be deposited by liquid phase growth techniques.

  The compounds of the invention have the formula I, formula II, or formula III described above.

M is a metal selected from Re, Ru, Os, Rh, Ir, Pd, Pt and Au. Pd, Pt, and Au have a +2 oxidation state and are typically tetracoordinate. The following L ¹ ligand occupies two of the coordination positions. The other two are occupied by L ^4, when L ⁴ is monodentate is also occupied by L ^3. Re, Ru, Os, Rh, and Ir have a +3 oxidation state and are typically hexacoordinate. The following L ¹ ligands occupy two or four of the coordination positions. Other positions are occupied by L ⁴ and, in some cases, combinations of L ² and L ³ . In one embodiment, M is selected from Os, Ir, and Pt.

L ¹ is selected from aryl-N-heterocyclic ligands and heteroaryl-N-heterocyclic ligands. The ligand has an aromatic or aromatic heterocycle connected to the N-aromatic heterocycle by a single bond. Aromatic or aromatic heterocycles can include monocyclic or fused ring systems. Examples of aromatic rings include, but are not limited to, phenyl, naphthyl, and anthracenyl. Examples of the aromatic heterocycle include, but are not limited to, a ring derived from thiophene and a ring derived from dithiolpyridine. N-aromatic heterocycles can include monocyclic or fused ring systems. Examples of N-heterocyclic aromatic compound groups include, but are not limited to, pyridine, pyrazine, pyrimidine, and quinoline. In one embodiment, L ¹ is selected from phenyl-pyridine, phenyl-pyrimidine, phenyl-quinoline, bipyridine and thienyl-pyridine. Ligand L ¹ is coordinated to the metal by two points of attachment, which is a monoanionic, bidentate ligand. The two points of attachment are to the aromatic or aromatic heterocyclic carbon via the nitrogen atom of the N-aromatic heterocyclic ring.

L ² is a monoanionic ligand. L ² can be monodentate, bidentate or tridentate. Examples of monodentate L ² ligands include, but are not limited to, H — (“hydride”) and ligands having C, O, or S as coordinating atoms. Coordinating groups include, but are not limited to, alkoxides, carboxylates, thiocarboxylates, dithiocarboxylates, sulfonates, thiolates, nitriles, aryls, carbamates, dithiocarbamates, thiocarbazone anions, sulfonamide anions, and the like. In some cases, ligands discussed below as bidentate, such as β-enolates and phosphinoalkoxides, can act as monodentate ligands. Monodentate ligands can also be coordination anions such as halides, nitrates, sulfates, hexahaloantimonates and the like. These ligands are generally commercially available.

The bidentate L ² ligand generally has N, O, P, or S as a coordination atom, and forms a 5-membered or 6-membered ring when coordinated to a metal. Suitable coordinating groups include amino, imino, amide, alkoxide, carboxylate, phosphino, thiolate and the like. Examples of suitable parent compounds for these ligands include, but are not limited to, β-dicarbonyl (β-enolate ligand) and their N and S analogs, aminocarboxylic acid (aminocarboxylate coordination) ), Pyridinecarboxylic acid (iminocarboxylate ligand), salicylic acid derivative (salicylate ligand), hydroxyquinoline (hydroxyquinolinate ligand) and their S analogs, and phosphinoalkanols (phosphinoalkoxides) Rank).

  This β-enolate ligand is generally of formula IV

Wherein R ² is the same or different at each occurrence. The R ² group can be hydrogen, halogen, substituted or unsubstituted alkyl, aryl, alkylaryl or heterocyclic group. Adjacent R ² and R ³ groups can be joined to form 5- and 6-membered rings that can be substituted. In one embodiment, the R ² group is C _n (H + F) _{2n + 1} , —C ₆ H ₅ , c—C ₄ H ₃ S, and c—C ₄ H ₃ O, where n is 1 to 20 Is an integer). The R ³ group can be H, substituted or unsubstituted, alkyl, aryl, alkylaryl, heterocyclic group or fluorine.

  Examples of suitable β-enolate ligands include the compounds listed below. Abbreviations for β-enolate foam are listed below in parentheses.

2,4-Pentandionate [acac]
1,3-diphenyl-1,3-propanedionate [DI]
2,2,6,6-tetramethyl-3,5-heptanedionate [TMH]
4,4,4-trifluoro-1- (2-thienyl) -1,3-butanedionate [TTFA]
7,7-dimethyl-1,1,1,2,2,3,3-heptafluoro-4,6-octanedionate [FOD]
1,1,1,3,5,5,5-heptafluoro-2,4-pentandionate [F7acac]
1,1,1,5,5,5-hexafluoro-2,4-pentandionate [F6acac]
1-phenyl-3-methyl-4-i-butyryl-pyrazolinonate [FMBP]

β-dicarbonyl parent compounds are generally commercially available. The parent compound 1,1,1,3,5,5,5-heptafluoro-2,4-pentanedione (CF ₃ C (O) CFHC (O) CF ₃ ) is obtained from perfluoropentene-2 and ammonia. It can be prepared using a reaction followed by a two-step synthesis based on a hydrolysis step according to the technique published in (Non-Patent Document 3). This compound is susceptible to hydrolysis and should be stored and reacted under anhydrous conditions.

Hydroxyquinolinate ligands can be substituted with groups such as alkyl or alkoxy groups, which may be partially or fully fluorinated. Examples of suitable hydroxyquinolinate ligands (abbreviations are provided in parentheses):
8-hydroxyquinolinate [8hq]
2-Methyl-8-hydroxyquinolinate [Me-8hq]
10-hydroxybenzoquinolinate [10-hbq]
Is mentioned.
The parent hydroxyquinoline compound is generally commercially available.

  The phosphinoalkoxide ligand generally has the formula V

(Where
R ⁴ may be the same or different at each occurrence and is selected from H and C _n (H + F) _{2n + 1} ;
R ⁵ may be the same or different at each occurrence and is selected from C _n (H + F) _{2n + 1} and C ₆ (H + F) ₅ , or C ₆ H _5-m (R ⁶ ) _m ;
R ⁶ = CF ₃ , C ₂ F ₅ , n-C ₃ F ₇ , i-C ₃ F ₇ , C ₄ F ₉ , CF ₃ SO ₂ and Φ are 2 or 3,
m is 0 or an integer from 1 to 5, and n is an integer from 1 to 20.

Examples of suitable phosphinoalkoxide ligands (abbreviations are provided in parentheses):
3- (diphenylphosphino) -1-oxypropane [dppO],
1,1-bis (trifluoromethyl) -2- (diphenylphosphino) -ethoxide [tfmdpeO],
1,1-bis (trifluoromethyl) -2- (bis (3′5′-ditrifluoromethylphenyl) phosphino) ethoxide [PO-2],
1,1-bis (trifluoromethyl) -2- (bis (4′-trifluoromethylphenyl) phosphino) ethoxide [PO-3], and 1,1-bis (trifluoromethyl) -2- (bis ( Pentafluorophenyl) phosphino) ethoxide [PO-4]
Is mentioned.

  Some of the parent phosphinoalkanol compounds are commercially available or prepared using known techniques such as those reported for tfmmdpeO in (Non-Patent Document 4) or (Non-Patent Document 5), for example. Can do.

In one embodiment, L ² is a ligand coordinated through a carbon atom that is part of an aromatic group. This ligand is of formula VI
_{Ar [- (CH 2) q} -Q] p (VI)

Wherein Ar is an aryl or heteroaryl group, Q is a group having a heteroatom that can be coordinated to a metal, q is 0 or an integer from 1 to 20, p is an integer from 1 to 5, and Further, here, one or more of the carbons in (CH ₂ ) _q can be replaced with heteroatoms, and one or more of the hydrogens in (CH ₂ ) _q are replaced with D or F. Can have).

In one embodiment, Q is N (R ⁷ ) ₂ , OR ⁷ , SR ⁷ , and P (R ⁸ ) ₂ , wherein R ⁷ may be the same or different at each occurrence, Is H, C _n H _{2n + 1} or C _n (H + F) _{2n + 1} , and R ⁸ may be the same or different at each occurrence, from H, R ⁷ , Ar and substituted Ar Selected).

In one embodiment, Ar is phenyl, q is 1, Q is P (Ar) ₂ and p is 1 or 2.

Tridentate L ² ligands are similar to bidentate ligands, but include additional nonionic groups that can coordinate to the metal. Examples of nonionic groups include, but are not limited to, amino, imino, and phosphino groups.

L ³ ligands can be nonionic and monodentate or bidentate. Examples of L ³ ligands include, but are not limited to, CO, monodentate- and bidentate phosphine ligands, isonitriles, imines, and diimines. The phosphine ligand is of formula VII or VIII
PAr ₃ (VII)
Ar ₂ P—Z—PAr ₂ (VIII)

  Wherein Ar represents an aryl or heteroaryl group and Z represents an alkylene, heteroalkylene, arylene or heteroarylene group. Ar groups may be unsubstituted or substituted with alkyl, heteroalkyl, aryl, heteroaryl, halide, carboxyl, sulfoxylate, or amino groups. Phosphine ligands are generally commercially available.

L ⁴ is an anionic ligand. In Formula I, when e = 1, and in Formulas II and III, L ⁴ is also bound to the central constituent tissue. L ⁴ can be an aryl N-heterocycle that is the same as or different from L ¹ . L ⁴ can be an anionic ligand for L ² as described above. In Formula I, when e = 1, it will be understood that in Formulas II and III, L ⁴ must be capable of both coordination to the metal and binding to the central constituent organization. In this case, L ⁴ cannot be a hydroxide, for example.

In one embodiment, the solution processability of the electrically active organometallic compound is increased by assembling monometallic groups into the multimetallic compound. Fw refers to the chemical structure to which one or more metal units can bind. A myriad of possible structural structures exist for use in the construction of the compounds of the present invention. The number of metal units that can bind to the constituent structure is shown as “d” in Formula I, “g” in Formula II, and “h” in Formula III. This number, type framework structure, the nature of the L ⁴ ligand, and varies depending on the nature of the other ligands on the metal. In some embodiments, the number of metal units bonded to the constituent structures varies from 2 to about 6. In other embodiments, the number of metal units bonded to the structure can be greater than 6 if a structure with branch points is used.

  In one embodiment, the constituent structure is a hydrocarbyl moiety having at least one aryl ring. Exemplary structural structures containing an aryl ring are defined below, where “------” indicates the point of attachment for the metal unit.

  In other embodiments, the constituent structure is a cyclic aliphatic moiety, such as a cyclohexyl ring.

  A wide variety of inorganic materials can also be used in the multimetallic complexes of the present invention as constituent structures. In one embodiment, the compound of the invention is a siloxane. In other embodiments, the structural structure is silsesquioxane. An exemplary silsesquioxane having an alkynylene linkage is represented by the formula

(Where "-------" indicates the point of attachment for the metal unit. In the above structure, Si-Si represents Si-O-Si).

  Any of the above structural structures can be further substituted. Examples of substituents include, but are not limited to, groups such as alkyl, aryl, heteroalkyl, heteroaryl, alkoxy, and aryloxy, where such groups are partially or fully fluorinated. It may be. “Fluorinated” means that one or more hydrogens in a group are replaced by fluorine.

Y represents an arbitrary linking group between the structural structure and the ligand L ⁴ to be bonded. When used in the compounds of the present invention, the linkage can be any group that does not adversely affect the desired properties of the metal compound. Examples include but are not limited to O, S, alkylene, heteroalkylene, alkenylene, heteroalkenylene, alkynylene, and heteroalkynylene. For example, for luminescent applications, the linking group should not perturb the emission properties of each of the electroluminescent metal centers that bind to the constituent tissue. The linkage can be selected so that each metal group is oriented in the void so that the electroluminescent efficiency is optimized. In some embodiments, the chain is an alkylene, alkenylene, alkynylene moiety, or having 1 to 6 carbons.

In one embodiment, solution processability is increased by incorporating at least one solvent solubilizing substituent, R ^1, into at least one aryl or heteroaryl group. In one embodiment, R ¹ is selected from alkyl, fluoroalkyl, aryl, fluoroaryl, alkylaryl, alkoxy, aryloxy, fluoroalkoxy, fluoroaryloxy, and hetero-analogs thereof. In one embodiment, R ¹ is selected from phenyl, fluorophenyl, alkylphenyl, fluoroalkylphenyl, alkoxyphenyl, and fluoroalkoxyphenyl. In one embodiment, R ¹ is an aryl substituted aryl group. In one embodiment, R ¹ is a tetraphenylphenyl group.

The structure defined below shows an exemplary β-enolate as an L ⁴ ligand linked to an aryl constituent structure via a CH ₂ linking group. In addition, examples of β-enolate ligands bonded to a cyclohexyl structural structure through oxygen atoms are shown below.

Illustrative compounds of the invention having Ir as the metal, phenyl-pyridine or phenyl-quinoline as L ¹ , β-enolate as the L ⁴ ligand, and an aryl ring as Fw are defined in FIG.

In one embodiment, the compound has e = f = 0 and at least one substituent, R ¹ is on at least one ligand, where R ¹ is solvent solubilizing. ) Having the formula I In one embodiment, R ¹ is selected from alkyl, fluoroalkyl, aryl, fluoroaryl, alkylaryl, alkoxy, aryloxy, fluoroalkoxy, fluoroaryloxy, and hetero-analogs thereof. In one embodiment, R ¹ is selected from phenyl, fluorophenyl, alkylphenyl, fluoroalkylphenyl, alkoxyphenyl, and fluoroalkoxyphenyl. In one embodiment, R ¹ is an aryl-substituted aryl group.

Exemplary compounds of the present invention having formula I with e = f = 0 and comprising Ir as the metal and phenyl-pyridine as L ¹ are described in FIGS.

  The organometallic compound of the present invention is nonionic. These can be formed into films by any conventional means. They can be formed into pure films or can be combined with other materials in the film. Low molecular weight compounds can in some cases be sublimed without treatment. Thin films of these materials can be obtained by vacuum deposition. However, it is often advantageous to deposit the compound by solution processing. Any of the known liquid phase growth techniques can be used. Liquid media for solution processing of novel organometallic compounds can be either organic or partially organic liquids in which the compounds can be dissolved or dispersed. In general, the liquid medium is non-aqueous. Examples of suitable organic liquids that can be used as the liquid medium include, but are not limited to, toluene, fluorinated toluene, xylene, fluorinated xylene, chlorinated hydrocarbons, ethyl acetate, and 4-hydroxy-4-methyl-2- Mention may be made of pentanone and mixtures thereof.

  Novel organometallic compounds can be synthesized in a variety of ways using organic synthesis techniques and organometallic synthesis techniques well known to those skilled in the art. Some exemplary syntheses of compounds where M is Ir are defined below. Analog reactions can be performed on other metals.

Step A and Step B describe the synthesis of an aryl organization structure having ^four suitable bidentate, monoanionic ligands L ⁴ . The reaction of 2,4-pentanedione with 1,2,4,5-tetra-bromomethylbenzene in the presence of a strong base such as lithium diisopropylamide (“LDA”) is 1,2,4,5- This results in tetra- (3,5-dioxo-hexyl) benzene. This structural structure has four β-dicarbonyl moieties suitable for coordination of up to four monometallic groups after deprotonation to form β-dienolate. This is achieved, for example, as shown in step B. The structural structure with four β-dicarbonyl moieties reacts with NaH to produce the acetylacetonate moiety, L ⁴ , which then reacts with the precursor Ir complex to give compounds of the invention Form an example.

  The precursor organometallic complex is

Wherein L is the same or different and is typically a ligand of type L ¹ and Z is Cl or OR ⁹ where R ⁹ is H, CH ₃ or C ₂ H ₅ in which) can be prepared via the intermediate dimers such. The iridium dimer can generally be prepared by ^first reacting iridium trichloride hydrate with the ligand L ¹ and optionally adding NaOR ⁹ .

A compound having the formula I (where e = f = 0, a = 2, and L ⁴ = L ¹ ) is obtained from iridium trichloride hydrate, excess ligand, trifluoro It can be prepared by reaction with silver acetate.

  Aryl-N-heterocyclic and heteroaryl-N-heterocyclic ligands can generally be prepared using Suzuki coupling of constituent groups as described in (Non-Patent Document 6).

The compounds of the invention can be isolated, purified, and fully characterized by elemental analysis, ¹ H and ¹⁹ F NMR spectral data, and single crystal X-ray diffraction for suitable crystalline compounds. In some cases, a mixture of isomers is obtained. In many cases, the mixture can be used without isolating the individual isomers. If individual isomers are desired, they are often separable by liquid chromatography on silica or alumina media using standard techniques.

(Electronic element)
Another embodiment is a novel organic electronic device comprising at least one layer comprising the organometallic compound. The organometallic compound can be in a separate layer or can be combined with other active or inactive materials in the device.

  One example of an organic electronic device structure is shown in FIG. The element 100 has an anode layer 110 and a cathode layer 150. Adjacent to the anode is a layer 120 containing a hole transport material. Adjacent to the cathode is a layer 140 containing an electron transport material. There is a photoactive layer 130 between the hole transport layer and the electron transport layer.

Depending on the application of the device 100, the photoactive layer 130 is a light emitting layer (such as a light emitting diode or light emitting electrochemical cell, one in a light emitting display) that is activated by an applied voltage, responsive to radiant energy, and an applied bias voltage. It can be a layer of material (such as in a light receiver) that produces a signal with or without an applied bias voltage. As an electronic device having utility for the compounds disclosed in the present specification,
(1) An element that converts electrical energy into radiation (eg, a light emitting diode, a light emitting diode display, or a diode laser), (2) An element that detects a signal through electronic processing (eg, a light receiver (eg, a photoconductive cell) , Photoresistors, optical switches, phototransistors, phototubes, IR detectors), (3) elements that convert radiation into electrical energy (eg, photovoltaic elements or solar cells), and (4) one or more Devices (eg, transistors or diodes) that include one or more electronic components including the organic semiconductor layer.

  The compounds of the present invention are particularly useful as photoactive materials in layer 130 or as electron transport materials in layer 130 or layer 140. In one embodiment, the compounds of the invention are used as luminescent materials in diodes. In one embodiment, a layer with more than 20% by weight of new compounds and less than 100% of new compounds, based on the total weight of the layer, can be used as the emissive layer. Additional materials may be present in the emissive layer with the compounds of the present invention. For example, fluorescent dyes can be present to change the color of the radiation. Diluents may also be added, and such diluents can be charge transport materials or inactive matrices. Diluents can include polymeric materials, small molecules, or mixtures thereof. The diluent can act as a processing aid, can improve the physical or electrical properties of the film containing the metal compound, can reduce self-quenching in the metal compounds described herein, and / or Aggregation of the metal compounds described herein can be reduced.

  In certain embodiments, the novel compounds described herein are present as guest materials in the host material. The term “guest material” refers to the electronic characteristics of a layer or the target wavelength of radiation emission, reception or filtering in the layer containing the host material, the electronic characteristics or radiation of the layer in the absence of such material. It is intended to mean a material that changes as compared to the wavelength of radiation, reception, or filtering. The term “host material” is intended to mean a material that is usually in the form of a layer to which a guest material may or may not be added. The host material may or may not have electronic features, or may or may not be capable of emitting, receiving or filtering radiation.

  Non-limiting examples of suitable polymeric host materials include poly (N-vinylcarbazole), conjugated polymers, and polysilanes, and mixtures thereof. Non-limiting examples of suitable small molecule host materials include 4,4′-N, N′-dicarbazole biphenyl (CBP), bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (BAlQ ) Or tertiary aromatic amines and mixtures thereof. Examples of suitable conjugated polymers include polyarylene vinylene, polyfluorene, polyoxadiazole, polyaniline, polythiophene, polyphenylene, copolymers thereof and combinations thereof. The conjugated polymer can be a copolymer having non-conjugated moieties such as, for example, acrylic, methacrylic, or vinyl monomer units. In one embodiment, the diluent includes homopolymers and copolymers of fluorene and substituted fluorenes. When diluents are used, the compounds of the invention are generally present in small amounts. In one embodiment, the metal compound is less than 20% by weight, based on the total weight of the layer. In one embodiment, the metal compound is less than 10% by weight, based on the total weight of the layer.

  In some cases, compounds of the present invention may exist in more than one isomeric form, or a mixture of different complexes may exist. In the above discussion of OLEDs, it will be understood that the term “compounds of the invention” is intended to include mixtures of compounds and / or isomers.

  In order to realize a high-efficiency LED, the hole transport material HOMO (highest occupied molecular orbital) should be aligned with the work function of the anode, and the electron transport material LUMO (lowest unoccupied molecular orbital) It should be aligned with the work function of the cathode. Chemical affinity and material sublimation temperature are also important requirements in the selection of electron and hole transport materials.

  The other layers in the OLED can be formed from any material known to be useful in such layers. The anode 110 is a particularly efficient electrode for injecting positive charge carriers. This can be formed, for example, from materials containing metals, mixed metals, alloys, metal oxides or mixed-metal oxides, or it can be a conductive polymer. Suitable metals include Group 11 metals, Group 4, 5, and 6 metals, and Group 8-10 transition metals. Where the anode should be translucent, mixed-metal oxides of Group 12, 13 and 14 metals such as indium-tin-oxide are generally used. The IUPAC numbering scheme has been used consistently, where families from the periodic table are numbered 1 to 18 from left to right (CRC Handbook of Chemistry and Physics), 81, 2000). The anode 110 may also include an organic material such as polyaniline as described in (Non-Patent Document 7). At least one of the anode and the cathode should be at least partially transparent so that the generated light can be observed.

  Examples of hole transport materials for layer 120 are, for example, Y. (Y. Wang) (Non-Patent Document 8). Both hole transport molecules and polymers can be used. Commonly used hole transport molecules are N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD), 4, 4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB, NPD), 1,1-bis [(di-4-tolylamino) phenyl] cyclohexane (TAPC), N, N'- Bis (4-methylphenyl) -N, N′-bis (4-ethylphenyl)-[1,1 ′-(3,3′-dimethyl) biphenyl] -4,4′-diamine (ETPD), tetrakis- (3-methylphenyl) -N, N, N ′, N′-2,5-phenylenediamine (PDA), a-phenyl-4-N, N-diphenylaminostyrene (TPS), p- (diethylamino) benzaldehyde Zife Ruhydrazone (DEH), triphenylamine (TPA), bis [4- (N, N-diethylamino) -2-methylphenyl] (4-methylphenyl) methane (MPMP), 1-phenyl-3- [p- ( Diethylamino) styryl] -5- [p- (diethylamino) phenyl] pyrazolin (PPR or DEASP), 1,2-trans-bis (9H-carbazol-9-yl) cyclobutane (DCZB), N, N, N ′, N′-tetrakis (4-methylphenyl)-(1,1′-biphenyl) -4,4′-diamine (TTB) and porphyrin compounds such as copper phthalocyanine. Commonly used hole transporting polymers are polyvinylcarbazole, (phenylmethyl) polysilane, and polyaniline. It is also possible to obtain hole transporting polymers by doping hole transporting molecules such as those mentioned above into polymers such as polystyrene and polycarbonate.

Examples of other electron transport materials for layer 140 include tris (8-hydroxyquinolato) aluminum (Alq ₃ ), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA) or Phenanthroline-based compounds such as 4,7-diphenyl-1,10-phenanthroline (DPA) and 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole Metal chelated oxinoid compounds such as azole compounds such as (PBD) and 3- (4-biphenylyl) -4-phenyl-5- (4-t-butylphenyl) -1,2,4-triazole (TAZ). It is done. Layer 140 can function both to facilitate electron transport and also serve as a buffer or confinement layer to prevent quenching of excitation at the layer interface. Preferably, this layer promotes electron mobility and reduces excitation quenching.

  The cathode 150 is an electrode that is particularly efficient for the injection of electrons or negatively applied carriers. The cathode can be any metal or nonmetal having a lower work function than the anode. The material for the cathode can be selected from Group 1 alkali metals (eg, Li, Cs), Group 2 (alkaline earth) metals, Group 12 metals including rare earth elements and lanthanides, and actinides. Materials such as aluminum, indium, calcium, barium, samarium and magnesium, and combinations can be used. Li-containing organometallic compounds can also be deposited between the organic layer and the cathode layer to reduce the operating voltage.

  It is known that organic electronic devices have other layers. For example, an additional layer (not shown) is provided between the anode layer 110 and the active layer 130 to facilitate positive charge transport and / or bandgap matching of the layers, or to function as a protective layer. There may be. Similarly, an additional layer (not shown) is interposed between the active layer 130 and the cathode layer 150 to facilitate negative sign transport and / or band gap matching between layers, or to function as a protective layer. There may be. Layers that are well known in the art can be used. In addition, any of the above layers can be formed of two or more layers. Alternatively, some or all of the inorganic anode layer 110, hole transport layer 120, active layer 130, and cathode layer 150 may be surface treated to increase charge carrier transport efficiency. The selection of materials for each component layer is preferably determined by a balance with the goal of providing a device with high device efficiency.

  It is understood that each functional layer can be composed of two or more layers.

  The device can be prepared by sequentially depositing the individual layers on a suitable substrate. Substrates such as glass and polymer films can be used. Conventional vapor deposition techniques such as thermal evaporation, chemical vapor deposition and the like can be used. Alternatively, the organic layer can be coated from solution or dispersion in a suitable solvent using any conventional coating technique. Usually the different layers will have the following thickness ranges: Anode 110, 500-5000Å, preferably 1000-2000Å, hole transport layer 120, 50-1000Å, preferably 200-800Å, light emitting layer 130, 10-1000Å, preferably 100-800Å, electron transport layer 140, 50- 1000Å, preferably 200-800Å, cathode 150, 200-10000Å, preferably 300-5000Å. The location of the electron-hole recombination zone in the device, and thus the emission spectrum of the device, can be affected by the relative thickness of each layer. Therefore, the thickness of the electron transport layer should be selected so that the electron-hole recombination zone is in the light emitting layer. The desired ratio of layer thickness will depend on the exact nature of the material used.

  It will be appreciated that the efficiency of devices formed with the compounds of the present invention can be further improved by optimizing other layers in the device. For example, a more efficient cathode such as Ca, Ba or LiF can be used. Novel hole transport materials that result in molded substrates and reduced operating voltage or increased quantum efficiency are also applicable. Additional layers can also be added to adjust the various layer energy levels and to promote electroluminescence.

  The compounds of the present invention are often phosphorescent and glitter and can be useful in applications other than OLEDs. For example, phosphorescent organometallic compounds have been used as oxygen sensitive indicators, as phosphorescent indicators in bioassays, and as catalysts.

  As used herein, the term “compound” is intended to mean an electrically uncharged material formed from a molecule, where the molecule further comprises an atom (wherein the atoms are separated by physical methods). Can not). The term “ligand” is intended to mean a molecule, ion, or atom that is bound to the coordination sphere of a metal ion. The term “complex”, when used as a noun, is intended to mean a compound having at least one metal ion and at least one ligand. The term “monodentate ligand” refers to a ligand that occupies one coordination site in the coordination sphere of a metal ion. Similarly, the terms “bidentate ligand” and “tridentate ligand” refer to ligands that occupy two and three coordination sites, respectively, in the coordination sphere of the metal ion.

  The term “group” is intended to mean a moiety of a compound such as a substituent in an organic compound or a ligand in a complex. The term “hexacoordinated” is intended to mean that six groups or points of attachment are coordinated to the central metal. The term “tetracoordinate” is intended to mean that four groups or points of attachment are coordinated to the central metal. The phrase “adjacent to” when used to refer to a layer in a device does not necessarily imply that one layer directly follows another. On the other hand, the phrase “adjacent R groups” is used to refer to R groups that are adjacent to one another in a chemical formula (ie, R groups connected by a bond to an atom).

  The term “photoactive” is intended to mean either an electroluminescent or photosensitive material.

  The terms “active” or “electrically active”, when referring to a layer or material, are intended to mean a layer or material that exhibits electronic or electron irradiation properties. The active layer material can emit radiation or exhibit a change in concentration of electron-hole pairs when receiving radiation.

  In the formula, the symbols L, M, Q, R, Y, Z and Fw are used to refer to atoms or groups as defined herein. All other symbols are used to refer to conventional atomic symbols.

  As used herein, “liquid or solution processing or solution deposition” refers to the formation of a uniform film from a liquid medium. In one embodiment, the film is robust. Deposition techniques include either continuous or discontinuous methods of depositing material in the form of a liquid medium. The term “layer” is used interchangeably with the term “film” and refers to a coating covering a desired area. The term is not limited by size. For example, in some embodiments, the region may be as large as the entire device. In other embodiments, the area may be as small as a particular functional area, such as an actual visual display, or as small as a single subpixel. In addition, the region may be continuous or non-continuous. The layer can be formed by any of the conventional deposition techniques including, but not limited to, vapor deposition, liquid phase growth, and thermal transfer. For example, in some embodiments, the layer is spin coated, gravure coated, curtain coated, dip coated, slot-die coated, spray coated, continuous nozzle coated, and ink jet printed, contact printed (gravure printed, screen printed, etc. Etc.), or indeed other techniques that are effective to materialize the layer.

  As used herein, the term “alkyl” is intended to mean a group derived from an aliphatic hydrocarbon having one point of attachment, which group can be linear, branched or cyclic. The term “alkylene” is intended to mean a group derived from an alkyl group and having two or more points of attachment.

  As used herein, the term “alkenyl” is intended to mean a group derived from a hydrocarbon having one or more carbon-carbon double bonds and having one point of attachment, May be linear, branched or cyclic. The term “alkenylene” is intended to mean a group derived from an alkenyl group, having one or more carbon-carbon double bonds and having two or more points of attachment.

  As used herein, the term “alkynyl” is intended to mean a group having one point of attachment, derived from a hydrocarbon having one or more carbon-carbon triple bonds. It can be linear, branched or cyclic. The term “alkynylene” is intended to mean a group derived from an alkynyl group and having two or more points of attachment.

  As used herein, the term “aryl” is intended to mean a group derived from an aromatic hydrocarbon having one point of attachment. The term “arylene” is intended to mean a group derived from an aryl group and having two points of attachment.

  As used herein, the term “arylalkylene” is intended to mean a group derived from an alkyl group having an aryl substituent.

  As used herein, the term “arylene alkylene” is intended to mean a group having both an aryl group and an alkyl group, with one point of attachment on the aryl group and one point of attachment on the alkyl group. Is done.

  As used herein, “hydrocarbyl” refers to a moiety that is composed primarily of carbon and hydrogen atoms. As used herein, a “hydrocarbyl” moiety may also contain heteroatoms such as N, O, P, and the like.

  As used herein, “inorganic” refers to a moiety that is composed primarily of atoms other than carbon.

  As used herein, the term “solvent solubilization” indicates that the solubility or dispersibility of the material in at least one organic solvent has been increased.

  As used herein, the prefix “fluoro” refers to one or more hydrogens replaced by fluorine, including fully hydrogenated, partially fluorinated and perfluorinated substituents. Is meant to mean

  As used herein, the prefix “hetero” indicates that at least one carbon atom forming the group is replaced by a heteroatom. Examples of such heteroatoms include N, O, and P.

  See page 16. Unless otherwise indicated, all groups can be unsubstituted or substituted.

  As used herein, the terms "include", "include", "include", "include", "have", "have", or any other variation thereof Intended to encompass non-exclusive inclusions. For example, a process, method, article, or device that includes an enumeration of factors is not necessarily limited to only those factors, and is not explicitly listed or intrinsic to such a process, method, article, or device. Certain other factors may be included. Further, unless expressly stated to the contrary, “or” refers to generic or does not refer to exclusive or. For example, condition A or B is satisfied by one of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and A and B Both are true (or exist).

  Also, the use of the singular ("a" or "an") is used to describe the factors and components of the invention. This is done merely to provide convenience and a general idea of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

  Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. All publications, patent applications, patents and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control.

  In addition, the materials, methods, and examples are illustrative only and not intended to be limiting. In the context of individual embodiments, it should be appreciated that certain features of the invention described above and below for clarity may also be provided in combination in a single embodiment. Conversely, the various features of the invention described in the context of a single embodiment for the sake of brevity may also be provided separately or in any subcombination. Further, references to values specified in the range include each and every value within that range.

  The following examples illustrate certain features and benefits of the present invention. These are illustrative of the invention and are not intended to be limiting. All percentages are by weight unless otherwise specified.

Example 1
This example illustrates the preparation of a novel organometallic compound, compound 1, having the formula I, where d = 4.

An aryl structural structure with acetylacetonate (acac) as ligand (Y) was prepared as follows. N ₂ - in the filled glovebox was charged with THF of 2,4-pentanedione and 35cc of 3.20 g (32 eq) in 100cc glass pot equipped with a dropping funnel, rubber-coated stoppers and stir bar. A glass bottle equipped with a septum seal was charged with 1.83 g (4.17 eq) 1,2,4,5-tetra-bromomethylbenzene and 25 cc THF. A glass syringe equipped with a bulb was charged with 35 cc of 2M (70 eq) LDA (lithium diisopropylamide) in ethylbenzene / THF / heptane. The pot, bottle and syringe were transferred to a fume hood, the pot was clamped in place, and an N ₂ purge was placed at the top of the addition funnel. The pot was cooled using a dry ice-acetone cooling bath and stirring was started. After 15 minutes, the solution was transferred from the bottle to the pot using low pressure N ₂ with a cannula. The solution in the syringe was poured into the pot with stirring over about 15 minutes. Stirring was continued for 1 hour with dry ice-acetone cooling. The solution in the addition funnel was added to the pot over a period of 10-15 minutes with stirring and dry ice-acetone cooling and continued for an additional time. Cooling was changed to wet ice and stirring was continued for 3 hours. The wet ice was gradually dissolved overnight with continued stirring. A quench solution was prepared from 45 cc ice water and 15 cc concentrated HCl. The contents of the pot were slowly poured into the quench solution and the resulting mixture was subsequently shaken in a separatory funnel. The reaction mixture was extracted three times with about 50 cc aliquots of methylene chloride, dried over MgSO ₄ and vacuum stripped to give 2.67 g of crude product. A 1.03 g portion of the crude product was purified by elution on a 2 cm diameter x 4 cm column of silica gel using methylene chloride, methylene chloride / ethyl acetate (50/50), ethyl acetate, and finally methanol. did. Upon evaporation of the solvent, methylene chloride yielded 0.062 g of final product and the methylene chloride / ethyl acetate fraction eluted 0.233 g of final product. The combined yield of 0.295 g of final product was 28% based on the starting 1,2,4,5-tetra-bromomethylbenzene. ¹ H NMR (CD ₂ Cl ₂ , 20 ° C.), δ: 6.8 (4H), 5.4 (1H), 3.5 (2H), 2.8 (2H), 2.5 (2H), 2.1 (3H), and 1.9 (3H).

An aryl structure with a bonded ligand (L ⁴ ) can be transformed into an organometallic Ir compound (which already has two ligands (L ¹ ) coordinated to it) as follows: It was complexed. 0.11 g (about 0.21 eq) 1,2,4,5-tetra- (3,5-dioxo-hexyl) benzene (as prepared above) and 0.21 g (0.87 eq) of NaH and mixtures of 1,2-dimethoxyethane in 25cc and stirred under N _2. Ten minutes later, 0.594 g (0.42 equivalents) of bis-2- (4-fluorophenyl) -5-trifluoromethylpyridine-iridium-chloride bridge formed according to the procedure in US Pat. Mold dimer was added and stirred at 85 ° C. (oil bath) overnight. Next, 0.10 g (0.72 equivalents) of K ₂ CO ₃ and 0.050 cc of H ₂ O were added to the mixture. Stirring and heating at 85 ° C. was continued overnight. The resulting mixture of clear orange solution and pale yellow solid was filtered and the filtrate was evaporated to yield 0.59 g of orange solid. A sample of 0.142 g of orange solid was purified by eluting with a 2 cm diameter x 7 cm column of silica gel with methylene chloride followed by methylene chloride / methanol (50/50). An early fraction of the methylene chloride eluent was evaporated to yield 0.075 g of a yellow solid. The overall yield of tetra-Ir-substituted compound was 46% based on the starting 1,2,4,5-tetra- (3,5-dioxo-hexyl) benzene (compound E103291-125). ¹ H NMR (CD ₂ Cl ₂ , 20 ° C.), ¹ H NMR (CD ₂ Cl ₂ , 20 ° C.), δ: 8.6 (2H), 7.9 (2H), 7.75 (2H), 7 .6 (2H), 7.45 (4H), 6.6 (2H), 6.45 (1H), 5.85 (2H), 2.3 (2H), 2.0 (2H), and 1 .7 (3H). ¹⁹ FNMR (CD ₂ Cl ₂ , 20 ° C.), 109.3 (1F), 63.2 (3F) and 63.0 (3F).

(Example 2)
This example illustrates the preparation of a novel organometallic compound, compound 2, having the formula I, where e = f = 0.

2- (3-Bromophenyl) -pyridine as the fac-type isomer, in which all three nitrogens are adjacent, i.e. in the corner of one side of the octahedron around Ir, is palladium tetrakis of 2-bromopyridine. Prepared using standard Suzuki coupling conditions via condensation with 3-bromophenylboronic acid in ethylene glycol dimethyl ether in the presence of triphenylphosphine catalyst. The isolated yield after distillation was 40%. A second Suzuki coupling of this first material, also using a palladium phosphine catalyst with 3-trifluoromethylphenylboronic acid, gave the desired L ¹ ligand in 98% yield.

0.9 g of the above phenylpyridine compound and 0.38 g of iridium chloride were mixed in 2 mL 2-ethoxyethanol and 0.5 mL water with 0.75 g silver trifluoroacetate. The mixture was stirred and refluxed under nitrogen for 4 hours and then cooled to room temperature. The solution was evaporated to dryness by gentle heating in a stream of nitrogen, and the resulting solid was extracted into methylene chloride (large volume) and filtered to remove the dark solid containing silver. The residue was washed with additional methylene chloride until no further yellow color eluted. The bright yellow solution was evaporated to dryness and examined by TLC. The yellow solid was purified by chromatography on silica gel using toluene as the eluent, and the yellow band that flowed out the fastest was collected. The collected yellow solution was evaporated and recrystallized from methanol / methylene chloride 1: 1. NMR of this yellow crystal in methylene chloride showed the expected spectrum (at ¹⁹ F1 doublet-63.25 ppm) for the desired material as the fac isomer. The recovered solid was quite soluble in toluene, methylene chloride, ethyl acetate and the like. Yield 35%.

(Example 3)
This example illustrates a novel organometallic compound, compound 3, having the formula I, where e = f = 0.

(Compound 3a, R = 4-F)
This was prepared in the same manner as described for Compound 2 above, replacing 3-trifluoromethylboronic acid with 4-fluorophenylboronic acid in the ligand synthesis. NMR of the final product showed it to be the desired compound as the fac isomer (at ¹⁹ F triplet triplet-118.65 ppm).

(Compound 3b, R = 4-n-butyl)
This was prepared in the same manner as described for compound 2 above, replacing 3-trifluoromethylboronic acid with 4-n-butyl-phenylboronic acid in the ligand synthesis. NMR of the final product shows that it is the desired compound as the fac isomer ( ¹ H: δ: 7.9 (1H) d, 7.8 (1H) d, 7.55 (1H) t, 7.52 ( 1H) d, 7.42 (2H) d, 7.11 (2H) d, 7.0 (1H) d, 6.85 (2H) m, 2.52 (2H) m, 1.50 (2H) m, 1.25 (2H) m, 0.90 (3H) t.).

(Compound 3c, R = 4-t-butyl)
This was prepared in the same manner as described for Compound 2 above, replacing 3-trifluoromethylboronic acid with 4-t-butyl-phenylboronic acid in the ligand synthesis. NMR of the final product shows that it is the desired compound as the fac isomer ( ¹ Hδ: 7.9 (1H) d, 7.78 (1H) d, 7.55 (1H) t, 7.50 (1H) d, 7.40 (2H) d, 7.23 (2H) d, 6.93 (1H) d, 6.80 (2H) m, 1.19 (9H) s.).

(Compound 3d, R = 3,5-CF ₃ )
This was prepared in the same manner as described for Compound 2 above, replacing 3-trifluoromethylboronic acid with 3,5-bis-trifluoromethylphenylboronic acid in the ligand synthesis. NMR of the final product showed it to be the desired compound as the fac isomer ( ¹⁹ F1 doublet at 63.56 ppm).

Example 4
This example illustrates the preparation of a novel organometallic compound, compound 4, having the formula I, where e = f = 0.

  In the formula, r is 1 or 2.

  1.0 g of the phenylpyridine ligand 2- (3-phenyl) -phenylpyridine (prepared as in Example 2 above, except that 3-trifluoromethylboronic acid was replaced with phenylboronic acid) Combined with 76 g iridium chloride in 10 mL 2-ethoxyethanol and 1 mL water. The mixture was refluxed for 30 minutes under nitrogen, then cooled to room temperature and evaporated to dryness in a stream of nitrogen. The yellow solid was extracted into methylene chloride and filtered. The resulting yellow solution was evaporated to dryness to isolate the chloro dimer in 85% yield.

  Chlorodimer (0.69 g) was converted to 2 equivalents (0.58 g) of ligand 2- (3- (4-t-butylphenyl))-phenylpyridine prepared in Example 3c above and 1q trimethyl. Mixed in silver 2-fluoroethanol with silver fluoroacetate. The mixture was refluxed for 2 hours, then evaporated to dryness and extracted into methylene chloride. Chromatography on silica using methylene chloride as the eluent produced a green emission band that flowed quickly. Recovery of this band, evaporation and recrystallization from methylene chloride / methanol resulted in a bright yellow powdery solid. NMR in methylene chloride shows a mixture of fac isomers of two materials of the structure it showed (where r = 1 (compound 4a) and r = 2 (compound 4b) It was an approximate ratio of 10).

(Example 5)
This example illustrates the preparation of the intermediate structure-ligand, compound 5.

  A solution of methyl tert-butyl ketone in anhydrous THF (10 mL) (0.907 g, 9.08 mmol) was added to 50 mL anhydrous THF of NaH (0.218 g, 9.08 mmol) and dimethyl-1,4-cubanedicarboxylate. The mixture was added dropwise to the refluxing mixture and then refluxed for 16 hours. The orange mixture was cooled to room temperature and poured into ice / water with stirring, followed by extraction with ethyl ether (2 × 100 mL). The aqueous layer was acidified resulting in a white precipitate. The solid extracted with ether was washed with water, brine and dried over magnesium sulfate. The dry ether solution was evaporated under vacuum to give compound 5 as a tan solid in 46% yield (740 mg).

(Example 6)
This example illustrates the preparation of a novel organometallic compound, compound 6, having the formula I, where d = 2.

Under an inert atmosphere of nitrogen, the acetylacetonate ligand from Example 5 (0.120 g, 0.34 mmol) and [IrOH {1- (4-tert-butyl-phenyl) -isoquinoline} ₂ ] ₂ ( 0.500 g, 0.340 mmol) in 25 mL anhydrous THF was refluxed for 3 days. Volatiles were removed by evaporation to give a dark residue. The residue was washed with hexane to give a dark red powder which was further purified by flash chromatography (silica, ethyl acetate) to give the desired product (0.213 g, 35% yield).

(Example 7)
This example illustrates the formation of a novel organometallic compound, compound 7, having the formula I, where d = 2.

Using the procedure outlined in Example 6, [IrOH {2- (4-Fluoro-phenyl)-(5-trifluoromethyl) pyridine} ₂ ] ₂ (0.500 g, 0.353 mmol) and the Examples Starting with an acetylacetonate ligand from 1 (0.126 g, 0.353 mmol). The desired iridium compound was obtained as a yellow powder (0.107 g, 17.5% yield) by flash chromatography (silica, CH ₂ Cl ₂ ) ¹⁹ F NMR (CD ₂ Cl ₂ ): −63.13 (F), -109.9 (CF ₃₎ was isolated after purification using.

(Example 8)
This example illustrates the preparation of the constituent-ligand precursor, compound 8.

To a cooled (−78 ° C.) solution of 2,4-pentanedione (2.13 mL, 20.82 mmol) in THF (35 mL) was added 2.0 M lithium diisopropylamide (20.8 mL, 41.6 mmol) under nitrogen. Slowly added. The mixture was stirred at −78 ° C. for 1 hour, then dibromo-p-xylene (2.199 g, 8.33 mmol) in THF (25 mL). The reaction was maintained at −78 ° C. for 30 minutes and gradually warmed to room temperature. The mixture was quenched with 4M HCl, extracted with Et ₂ O, and dried over sodium sulfate. The product was purified by distillation and by using flash chromatography to give the product as an oil in 32% yield (0.8 grams).

Example 9
This example illustrates the preparation of a novel organometallic compound, compound 9, having the formula I, where d = 2.

The procedure for Example 6 is described as [IrOH {1- (4-tert-butyl-phenyl) -isoquinoline} ₂ ] ₂ (0.483 g, 0.33 mmol) and the acetylacetonate ligand from Example 8. (0.100 g, 0.33 mmol). The crude product was purified by crystallization from CH ₂ Cl ₂ / hexanes to give the product as a dark red solid (0.125 g, 22% yield).

(Example 10)
This example illustrates the preparation of a novel organometallic compound, compound 10, having the formula I, where d = 2.

The procedure for Example 6 was determined using [IrOH {2- (4-fluoro-phenyl)-(5-trifluoromethyl) pyridine} ₂ ] ₂ (0.456 g, 0.33 mmol) and acetyl from Example 8. Used with acetonate ligand (0.100 g, 0.33 mmol). The crude product was purified by chromatography (CH ₂ Cl ₂ ) to give the product as a yellow powder (0.270 g, 50% yield). ^{_{19 FNMR (CD 2 Cl 2,}} 376.8MHz) δ-63.04 (CF 3), - 63.22 (CF 3), 109.45 (F).

(Example 11)
This example illustrates the preparation of a novel organometallic compound, compound 11, having the formula I, where e = f = 0.

Under a nitrogen atmosphere, {IrCl [4-t-Bu-phenyl) -isoquinoline] ₂ } ₂ (3.00 g, 2.01 mmol) ethoxy synthesized according to the procedure outlined in (Patent Document 6) Synthesized by a reaction of ethanol (50 mL) and Na (5-ethyl-nonane-2,4-dione) (NaH and 5-ethyl-nonane-2,4-dione (Patent Document 7)). 867 g, 4.21 mmol) was stirred at 120 ° C. for 45 minutes. The mixture is allowed and the residue evaporated to dryness was dissolved in CH ₂ Cl ₂ to and passed through a pad of silica using CH ₂ Cl ₂ as the eluting solvent. The crude product was isolated by evaporation and then further purified using chromatography (silica, CH ₂ Cl ₂ ) to give the product in 54% yield (1.95 g). ¹ H NMR (CD ₂ Cl ₂ , 500 MHz) δ 0.44 (3H), 0.58 (3H), 0.92 (9H), 1.03 (9H), 1.03-1.25 (12H), 5.25 (1H), 6.16 (1H), 6.52 (1H), 7.03 (2H), 7.50 (2H), 7.73 (4H), 7.93 (2H), 8 .12 (2H), 8.47 (2H), 8.94 (2H).

(Example 12)
This example illustrates the preparation of a novel organometallic compound, compound 12, having the formula I, where e = f = 0.

The procedure for Example 11 was synthesized according to the procedure outlined in {IrCl [2-phenylquinoline] ₂ } ₂ (Patent Document 6), 2.25 g, 3.5 mmol) and Na (5- Using ethyl-nonane-2,4-dione) (1.08 g, 5.25 mmol, synthesized by reaction of NaH with 5-ethyl-nonane-2,4-dione (Patent Document 7)) ,Using. Compound 12 was isolated as a bright red crystalline solid in 68% yield (1.86 g).

(Example 13)
This example illustrates the preparation of a new organometallic compound, compound 13, having the formula I, where d = 2.

The procedure for Example 6 is described as [IrOH {2- (4-Fluoro-phenyl)-(5-trifluoromethyl) pyridine} ₂ ] ₂ (0.250 g, 0.171 mmol) and acetylacetonate ligand. A (0.065 g, 0.171 mmol, synthesized according to the procedure outlined in Example 8). The crude product was purified by flash chromatography using methylene chloride / hexane (9: 1) to give the desired product as a red powder in 30.5% yield (0.094 g).

(Example 14)
This example illustrates the preparation of a new organometallic compound, compound 14, having the formula I, where d = 2.

Using the procedure outlined in Example 6, [IrOH {2- (4-fluoro-phenyl)-(5-trifluoromethyl) pyridine} ₂ ] ₂ (0.250 g, 0.177 mmol) and acetylacetate Starting with the Nate ligand A (0.067 g, 0.177 mmol, synthesized according to the procedure outlined in Example 8). The desired iridium compound was isolated as a yellow-orange powder (0.100 g, 32% yield) by crystallization from CH ₂ Cl ₂ / hexane. ¹⁹ FNMR (CD ₂ Cl ₂ , 376.8 MHz) δ-63.04, −63.08, −63.18, −63.19, 109.45. Analytical calculation: C, 49.18, H, 2.76, N, 3.17. Found: C, 50.17, H, 2.86, N, 3.49.

(Example 15)
This example illustrates the preparation of a novel organometallic compound, compound 15, having the formula I, where d = 2.

Using the procedure outlined in Example 6, [IrOH {2- (4-fluoro-phenyl)-(5-trifluoromethyl) pyridine} ₂ ] ₂ (0.250 g, 0.177 mmol) and acetylacetate Starting with the Nate ligand C (synthesized according to the procedure outlined in Example 8, 0.074 g, 0.177 mmol). The desired iridium compound was isolated as a yellow-orange powder (0.214 g, 67% yield) by crystallization from CH ₂ Cl ₂ / hexane. ¹⁹ FNMR (CD ₂ Cl ₂ , 376.8 MHz) δ-63.1, 109.44. Analytical calculated values: C, 50.03, H, 3.03, N, 3.11. Actual value: C, 50.27, H, 2.88, N, 3.00.

(Example 16)
This example illustrates the preparation of an organic light emitting diode (OLED) using a multi-metallic red emitting material (compound 9 from Example 9, exemplified below) as a dopant in a poly (fluorene) matrix. The resulting blend is used as an active red-emitting layer in an OLED. The electrical performance of this device is similar to that of the same OLED except that the second device contains a similar single metal compound (compound 11 from Example 11, exemplified below) as a red dopant instead of a multimetallic compound. Compare.

(OLED with multi-metallic red emitting compound)
All organic film constituents in this OLED example were solution treated. The element assembly is as follows. The ITO / glass substrate (applied film) was patterned (device active area = 25 mm ² whole) and cleaned ultrasonically with an aqueous cleaner followed by isopropanol. The substrate was then further cleaned by placing it in a 300 W oxygen plasma oven for 15 minutes. A poly (ethylenedioxythiophene) -poly (styrene sulfonic acid) (PEDOT-PSSA, Bayer Corp.) buffer layer (ie hole transport / injection layer) was then spin coated to a thickness of 60 nm. . The film was dried on a hot plate at 200 ° C. for 3 minutes. The substrate was then transferred to a nitrogen-filled glove box, at which point poly (fluorene) solution (75 mg), red emitting polymetallic compound (1.5 mg), and anhydrous toluene (7.5 mL) at a thickness of 70 nm. Spin-coated on the substrate. The substrate was then transferred to a high vacuum chamber where LiF (2.0 nm) followed by Ca (20.0 nm) and then Al (400 nm) was thermally deposited at 2.0 × 10 ⁻⁶ torr. The resulting OLED device was then sealed from the air by bonding a glass slide to the top of the cathode using a UV curable epoxy resin.

The device was fully characterized by obtaining current-voltage, brightness-voltage, brightness-current, efficiency-voltage, and efficiency-current profiles. This was accomplished through the use of a computer operated (Labview software) Keithley Source-Measurement Unit and a photodiode. This photodiode outputs integrated light over the entire active area of 25 mm ² . An electroluminescence spectrum was also acquired and showed that the light output from this OLED had color coordinates u ′ = 0.49, v ′ = 0.52. The average performance from 7 separate elements is as follows. Power on (at 10 cd / m ² ) = 5.0 V, operating voltage (at 200 cd / m ² ) = 5.9 V, efficiency = 2.0 cd / A, 200 cd / m ² .

(OLEDs with similar single metal red emitting compounds)
All organic film constituents in this OLED example were solution treated. The element assembly is as follows. The ITO / glass substrate (applied film) was patterned (device active area = 25 mm ² whole) and cleaned ultrasonically with an aqueous cleaner followed by isopropanol. The substrate was then further cleaned by placing it in a 300 W oxygen plasma oven for 15 minutes. A poly (ethylenedioxythiophene) -poly (styrene sulfonic acid) (PEDOT-PSSA, Bayer Corp.) buffer layer (ie hole transport / injection layer) was then spin coated to a thickness of 60 nm. The film was dried on a hot plate at 200 ° C. for 3 minutes. The substrate was then transferred to a nitrogen-filled glove box, at which point poly (fluorene) solution (75 mg), red emitting monometallic compound (1.5 mg), and anhydrous toluene (7.5 mL) at a thickness of 70 nm. Spin-coated on the substrate. The substrate was then transferred to a high vacuum chamber where LiF (2.0 nm) followed by Ca (20.0 nm) and then Al (400 nm) was thermally deposited at 2.0 × 10 ⁻⁶ torr. The resulting OLED device was then sealed from the air by bonding a glass slide to the top of the cathode using a UV curable epoxy resin.

The device was fully characterized by obtaining current-voltage, brightness-voltage, brightness-current, efficiency-voltage, and efficiency-current profiles. This was accomplished through the use of a computer operated (Labview software) Keithley Source-Measurement Unit and a photodiode. This photodiode outputs integrated light over the entire active area of 25 mm ² . An electroluminescence spectrum was also acquired and showed that the light output from this OLED had color coordinates u ′ = 0.49, v ′ = 0.52. The average performance from 7 separate elements is as follows. Power on (at 10 cd / m ² ) = 4.6V, operating voltage (at 200 cd / m ² ) = 5.3V, efficiency = 1.9 cd / A, 200 cd / m ² .

(Example 17)
This example illustrates the preparation of a novel organometallic compound, compound 17, having the formula I, where e = f = 0 and a = 3.

Iridium (III) tris (2- (5′-bromophenyl) pyridinato-N, C ^{2 ′} ) (0.250 g, 0.28 mmol), 4- (N-butoxyphenyl) boronic acid (0.181 g, 0. 93 mmol), a 2M solution of potassium carbonate (20.5 mL) and Pd (PPh ₃ ) ₄ (0.024 g, 0.021 mmol) in THF (34 mL), toluene (27 mL) and ethanol (10 mL). Place under nitrogen and heat under reflux for 24 hours. The mixture was diluted with CH ₂ Cl ₂ (25 mL) and water (25 mL), and the yellow organic layer was separated and washed twice with water, dried over magnesium sulfate, filtered and dried. The crude material was passed through a short silica column with 75% CH ₂ Cl ₂ / hexanes, concentrated and dried under reduced pressure to give compound 17 (85 mg, 27%) as a yellow powder.

(Example 18)
This example illustrates the preparation of a novel organometallic compound, compound 18, having Formula I, where e = f = 0 and a = 2.

The procedure used for the synthesis of compound 178 is the same as iridium (III) tris (2- (5′-bromophenyl) pyridinato-N, C ^{2 ′} ) (0.015 g, 0.016 mmol), 3,5-di (2 -Ethylhexyloxy) phenylboronic acid (0.029 g, 0.054 mmol), 2M solution of potassium carbonate (0.6 mL) and Pd (PPh ₃ ) ₄ (0.126 g, 0.011 mmol) were used . Compound 18 was isolated as a colorless oil in 89% yield (31 mg).

Examples of some compounds of the invention are given. Examples of some compounds of the invention are given. Examples of some compounds of the invention are given. Examples of some compounds of the invention are given. Examples of some compounds of the invention are given. Examples of some compounds of the invention are given. Examples of some compounds of the invention are given. Examples of some compounds of the invention are given. FIG. 2 is a schematic diagram of an example light emitting device.

Claims (23)

Formula I, Formula II, or Formula III

(Where
L ¹ is selected from aryl-N-heterocyclic ligands and heteroaryl-N-heterocyclic ligands;
L ² is an anionic ligand,
L ³ is a nonionic ligand,
L ⁴ is selected from L ¹ and L ²
M is a metal selected from Re, Ru, Os, Rh, Ir, Pd, Pt and Au;
FW is a moiety capable of supporting at least two (L ⁴ —Y _e ) groups;
Y is a group selected from alkylene, heteroalkylene, alkenylene, heteroalkenylene and alkynylene;
a is selected from 1 and 2,
b is selected from 0 and 1;
c is selected from 0, 1 and 2;
d is selected from an integer from 1 to 8;
e is selected from 0 and 1;
f is selected from 0 and 1,
g is selected from an integer from 1 to 4, and h is selected from 1 and 2,
Provided that a, b, and c are tetracoordinate when M is Au, Pd, or Pt, and hexacoordinate when M is Re, Ru, Os, Rh, or Ir. And when f = 0, e = 0 and at least one substituent R ¹ is in at least one ligand, where R ¹ is solvent solubilizing Is)
An organic electronic device comprising at least one layer comprising a compound having a formula selected from:   The device of claim 1 wherein M is selected from Os, Ir, and Pt. L ¹ is phenyl - pyridine, phenyl - pyrimidine, phenyl - quinoline, bipyridine, and thienyl - element according to claim 1, characterized in that it is selected from pyridine. The device of claim 1 having the formula I, a = 2, b = 0, c = 0, and L ⁴ is a bidentate monoanionic ligand. L ⁴ is β-enolate ligand, N analog of β-enolate ligand, S analog of β-enolate ligand, aminocarboxylate ligand, iminocarboxylate ligand, salicylate ligand, 5. A device according to claim 4, wherein the device is selected from hydroxyquinolinate ligands, S analogs of hydroxyquinolinate ligands and phosphinoalkoxide ligands. There is at least one R ¹ substituent on the aryl or heteroaryl ring, and R ¹ is alkyl, fluoroalkyl, aryl, fluoroaryl, alkylaryl, alkoxy, aryloxy, fluoroalkoxy, fluoroaryloxy, heteroalkyl, fluoro The device of claim 1, wherein the device is selected from heteroalkyl, heteroaryl, fluoroheteroaryl, heteroalkylaryl, heteroalkoxy, heteroaryloxy, fluoroheteroalkoxy, and fluoroheteroaryloxy. Having formula I, e = 0, f = 0, and R ¹ is alkyl, fluoroalkyl, aryl, fluoroaryl, alkylaryl, alkoxy, aryloxy, fluoroalkoxy, fluoroaryloxy, heteroalkyl, fluorohetero The device of claim 1, wherein the device is selected from alkyl, heteroaryl, fluoroheteroaryl, heteroalkylaryl, heteroalkoxy, heteroaryloxy, fluoroheteroalkoxy, and fluoroheteroaryloxy. Device according to claim 7 wherein R ¹ is phenyl, fluorophenyl, alkylphenyl, fluoroalkyl phenyl, characterized in that it is selected from alkoxyphenyl, and fluoroalkoxy phenyl. The device of claim 7, wherein a = 2, b = 0, c = 0, and L ⁴ = L ¹ . a = 2, b = 0, c = 0, and L ⁴ is β-enolate ligand, N analog of β-enolate ligand, S analog of β-enolate ligand, aminocarboxylate coordination Characterized in that it is selected from ligands, iminocarboxylate ligands, salicylate ligands, hydroxyquinolinate ligands, S analogs of hydroxyquinolinate ligands, and phosphinoalkoxide ligands. The device according to claim 7.   The device according to claim 1, wherein the at least one layer is a light emitting layer.   The device of claim 11, wherein the light emitting layer further includes a diluent.   The device of claim 12, wherein the diluent includes a polymer or a low-molecular material, or a mixture thereof.

A compound characterized in that it is selected from:

A compound characterized in that it is selected from:

A compound characterized in that it is selected from:   An organic electronic device comprising at least one layer containing the compound according to claim 14.   An organic electronic device comprising at least one layer containing the compound according to claim 15.   An organic electronic device comprising at least one layer containing the compound according to claim 16.   A composition comprising at least one compound according to claim 1.   21. The composition of claim 20, further comprising a host.   The composition of claim 21, wherein the host is selected from poly (N-vinylcarbazole), conjugated polymers, polysilanes, tertiary aromatic amines, and mixtures thereof.   21. The composition of claim 20, wherein the host is selected from polyarylene vinylene, polyfluorene, polyoxadiazole, polyaniline, polythiophene, polyphenylene, copolymers thereof, and mixtures thereof.

Images