Gold complexes for OLED applications

Abstract

Gold(III) emitters showing high emission quantum efficiency and stable in thermal deposition process are described. High performance OLEDs can be fabricated from these emitters.

Claims

1. A gold(III)-based compound having one of the following structures ##STR00032## ##STR00033## ##STR00034##

2. A light-emitting device comprising at least one OLED emitter comprising a gold(III)-based compound having a structure that is recited in claim 1 as the emitting material(s).

3. The device of claim 2, wherein the device consists of one emissive layer.

4. The device of claim 2, wherein the device consists of more than one emissive layer.

5. An OLED emitter comprising a gold(III)-based compound, wherein the gold(III)-based compound has one of the following structures: ##STR00035## ##STR00036## ##STR00037##

6. The OLED emitter of claim 5, wherein the gold(III)-based compound has one of the following structures: ##STR00038## ##STR00039##

7. A method of making the gold(III)-based compound of claim 1, comprising: reacting a halo-substituted biphenyl compound with n-butyl lithium and then adding SnBu.sub.2Cl.sub.2 to provide a dialkyl-biphenyl tin intermediate; reacting the dialkyl-biphenyl tin intermediate Intermediate with gold chloride hydrate to provide a multiphenyl dichloro bi-gold complex intermediate; and reacting the multiphenyl dichloro bi-gold complex intermediate with a deprotonated emission turn-on unit to provide the gold(III)-based compound of claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 depicts the Synthetic Scheme of making the Emitter 100.

(2) FIG. 2 is an ORTEP diagram of 102 with ellipsoids shown at 30% probability level with hydrogen atoms and solvents molecules omitted for clarity.

(3) FIG. 3 is an ORTEP diagram of 104 with ellipsoids shown at 30% probability level with hydrogen atoms and solvents molecules omitted for clarity.

(4) FIG. 4 is an ORTEP diagram of 107 with ellipsoids shown at 30% probability level with hydrogen atoms and solvents molecules omitted for clarity.

(5) FIG. 5 is an ORTEP diagram of 109 with ellipsoids shown at 30% probability level with hydrogen atoms and solvents molecules omitted for clarity.

(6) FIG. 6 depicts a graph of Cyclic voltammograms of Emitters 103, 105, 107, 108 and 109 shown in descending order.

(7) FIG. 7 depicts a TGA thermogram of Emitter 102.

(8) FIG. 8 depicts a TGA thermogram of Emitter 103.

(9) FIG. 9 depicts a TGA thermogram of Emitter 107.

(10) FIG. 10 depicts the Emission spectra of Emitter 101 in degassed CH.sub.2Cl.sub.2 (conc.: 210.sup.5 M), 77 K glass (EtOH:MeOH=4:1) and solid at 298 K and 77 K respectively.

(11) FIG. 11 depicts the Emission spectra of Emitter 102 in degassed CH.sub.2Cl.sub.2 (conc.: 210.sup.5 M), 77 K glass (EtOH:MeOH=4:1) and solid at 298 K and 77 K respectively.

(12) FIG. 12 depicts the EL spectra of VDOLEDs and SPOLEDs fabricated by Emitter 102.

(13) FIG. 13 depicts the EQE-luminance characteristics of VDOLEDs and SPOLEDs fabricated by Emitter 102.

DETAILED DESCRIPTION

Definitions

(14) To facilitate the understanding of the subject matter disclosed herein, a number of terms, abbreviations or other shorthand as used herein are defined below. Any term, abbreviation or shorthand not defined is understood to have the ordinary meaning used by a skilled artisan contemporaneous with the submission of this application.

(15) Amino refers to a primary, secondary, or tertiary amine which may be optionally substituted. Specifically included are secondary or tertiary amine nitrogen atoms which are members of a heterocyclic ring. Also specifically included, for example, are secondary or tertiary amino groups substituted by an acyl moiety. Some non-limiting examples of an amino group include NRR wherein each of R and R is independently H, alkyl, aryl, aralkyl, alkaryl, cycloalkyl, acyl, heteroalkyl, heteroaryl or heterocycyl.

(16) Alkyl refers to a fully saturated acyclic monovalent radical containing carbon and hydrogen, and which may be branched or a straight chain. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-heptyl, n-hexyl, n-octyl, and n-decyl.

(17) Alkylamino means a radical NHR or NR.sub.2 where each R is independently an alkyl group. Representative examples of alkylamino groups include, but are not limited to, methylamino, (1-methylethyl)amino, methylamino, dimethylamino, methylethylamino, and di(1-methylethyl)amino.

(18) The term hydroxyalkyl means an alkyl radical as defined herein, substituted with one or more, preferably one, two or three hydroxy groups. Representative examples of hydroxyalkyl include, but are not limited to, hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-(hydroxymethyl)-2-methylpropyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 2-hydroxy-1-hydroxymethylethyl, 2,3-dihydroxybutyl, 3,4-dihydroxybutyl and 2-(hydroxymethyl)-3-hydroxy-propyl, preferably 2-hydroxyethyl, 2,3-dihydroxypropyl, and 1-(hydroxymethyl)2-hydroxyethyl.

(19) The term alkoxy, as used herein, refers the radical OR.sub.x. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, and propoxy.

(20) Aryl refers to optionally substituted carbocyclic aromatic groups. In some embodiments, the aryl group includes phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl or substituted naphthyl. In other embodiments, the aryl group is phenyl or substituted phenyl.

(21) Aralkyl refers to an alkyl group which is substituted with an aryl group. Some non-limiting examples of aralkyl include benzyl and phenethyl.

(22) Acyl refers to a monovalent group of the formula C(O)H, C(O)-alkyl, C(O)-aryl, C(O)-aralkyl, or C(O)-alkaryl.

(23) Halogen refers to fluorine, chlorine, bromine and iodine.

(24) Styryl refers to a univalent radical C.sub.6H.sub.5CHCH derived from styrene.

(25) Substituted as used herein to describe a compound or chemical moiety refers to that at least one hydrogen atom of that compound or chemical moiety is replaced with a second chemical moiety. Non-limiting examples of substituents are those found in the exemplary compounds and embodiments disclosed herein, as well as halogen; alkyl; heteroalkyl; alkenyl; alkynyl; aryl; heteroaryl; hydroxy; alkoxyl; amino; nitro; thiol; thioether; imine; cyano; amido; phosphonato; phosphine; carboxyl; thiocarbonyl; sulfonyl; sulfonamide; ketone; aldehyde; ester; oxo; haloalkyl (e.g., trifluoromethyl); carbocyclic cycloalkyl, which can be monocyclic or fused or non-fused polycyclic (e.g., cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl) or a heterocycloalkyl, which can be monocyclic or fused or non-fused polycyclic (e.g., pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl or thiazinyl); carbocyclic or heterocyclic, monocyclic or fused or non-fused polycyclic aryl (e.g., phenyl, naphthyl, pyrrolyl, indolyl, furanyl, thiophenyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridinyl, quinolinyl, isoquinolinyl, acridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, benzimidazolyl, benzothiophenyl or benzofuranyl); amino (primary, secondary or tertiary); o-lower alkyl; o-aryl, aryl; aryl-lower alkyl; CO.sub.2CH.sub.3; CONH.sub.2; OCH.sub.2CONH.sub.2; NH.sub.2; SO.sub.2NH.sub.2; OCHF.sub.2; CF.sub.3; OCF.sub.3; NH(alkyl); N(alkyl).sub.2; NH(aryl); N(alkyl)(aryl); N(aryl).sub.2; CHO; CO(alkyl); CO(aryl); CO.sub.2(alkyl); and CO.sub.2(aryl); and such moieties can also be optionally substituted by a fused-ring structure or bridge, for example OCH.sub.2O. These substituents can optionally be further substituted with a substituent selected from such groups. All chemical groups disclosed herein can be substituted, unless it is specified otherwise. For example, substituted alkyl, alkenyl, alkynyl, aryl, hydrocarbyl or heterocyclo moieties described herein are moieties which are substituted with a hydrocarbyl moiety, a substituted hydrocarbyl moiety, a heteroatom, or a heterocyclo. Further, substituents may include moieties in which a carbon atom is substituted with a heteroatom such as nitrogen, oxygen, silicon, phosphorus, boron, sulfur, or a halogen atom. These substituents may include halogen, heterocyclo, alkoxy, alkenoxy, alkynoxy, aryloxy, hydroxy, protected hydroxy, keto, acyl, acyloxy, nitro, amino, amido, cyano, thiol, ketals, acetals, esters and ethers.

(26) Gold(III) Emitters

(27) In one aspect, the subject matter herein provides gold(III) emitters. In one embodiment, an organometallic emitter represented by Structure I is provided. The gold center in Structure I is in the +3 oxidation state and has a square planar geometry. The coordination sites of the gold center are occupied by two bidentate ligands: a biphenyl type ligand and an emission turn on unit. The biphenyl type ligand featuring with a 5 fused membered ring coordinates to the gold center through two metal-carbon bonds.

(28) The emission turn on unit featuring with a 5 or 6 fused membered ring coordinates to the gold center through two metal-oxygen bonds or one metal-oxygen and one metal-nitrogen bond or one metal-phosphorus bond. It is important to have this unit because gold(II) complexes with biphenyl type ligands were found non-emissive in solution at room temperature when this unit is lacking.

(29) In one embodiment, the emission turn on unit contains from 2 to 26 carbon atoms and at least one oxygen atom. In another embodiment, the emission turn on unit contains from 4 to 25 carbon atoms and at least one oxygen atom.

(30) The biphenyl type ligand must in 2 oxidation state and the emission turn on unit must in 1 oxidation to obtain an overall charge neutral emitter.

(31) In one embodiment, the gold(III) emitters have the chemical structures of Structure I:

(32) ##STR00003##
wherein R.sub.1-R.sub.8 are independently hydrogen, halogen, hydroxyl, an unsubstituted alkyl, a substituted alkyl, alkylamino, cycloalkyl, an unsubstituted aryl, a substituted aryl, acyl, alkoxy, acyloxy, amino, nitro, acylamino, aralkyl, cyano, carboxyl, thio, styryl, aminocarbonyl, carbamoyl, aryloxycarbonyl, phenoxycarbonyl, or an alkoxycarbonyl group. Each pair of adjacent R groups of R.sub.1-R.sub.8 can be independently form 5-8 member ring(s) with 2 or 4 carbon atoms in the phenyl ring(s) showed in Structure I;

(33) ##STR00004##
is an emission turn on group.

(34) In one embodiment, R.sub.1-R.sub.8 is independently hydrogen, halogen, hydroxyl, an unsubstituted alkyl containing from 1 to 10 carbon atoms, a substituted alkyl containing from 1 to 20 carbon atoms, cycloalkyl containing from 4 to 20 carbon atoms, an unsubstituted aryl containing from 6 to 20 carbon atoms, a substituted aryl containing from 6 to 20 carbon atoms, acyl containing from 1 to 20 carbon atoms, alkoxy containing from 1 to 20 carbon atoms, acyloxy containing from 1 to 20 carbon atoms, amino, nitro, acylamino containing from 1 to 20 carbon atoms, aralkyl containing from 1 to 20 carbon atoms, cyano, carboxyl containing from 1 to 20 carbon atoms, thiol, styryl, aminocarbonyl containing from 1 to 20 carbon atoms, carbamoyl containing from 1 to 20 carbon atoms, aryloxycarbonyl containing from 1 to 20 carbon atoms, phenoxycarbonyl containing from 1 to 20 carbon atoms, or an alkoxycarbonyl group containing from 1 to 20 carbon atoms.

(35) In one embodiment, X is an oxygen atom.

(36) In one embodiment, the emission turn-on unit is:

(37) ##STR00005##

(38) In one embodiment, the emission turn-on unit is:

(39) ##STR00006##

(40) In one embodiment, the emission turn-on unit is:

(41) ##STR00007##

(42) In one embodiment, the emission turn-on unit is:

(43) ##STR00008##

(44) In one embodiment, X is a nitrogen atom.

(45) In one embodiment, the emission turn-on unit is:

(46) ##STR00009##

(47) In one embodiment, the emission turn-on unit is:

(48) ##STR00010##

(49) In one embodiment, X is a phosphorus atom.

(50) In one embodiment, the emission turn-on unit is:

(51) ##STR00011##

(52) Certain specific, non-limiting examples for the gold(III) emitters with structure I are shown as follows:

(53) ##STR00012## ##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017##
Preparation of Gold(III) Emitter

(54) The gold (III) emitter with Structure I can be prepared by a series of reactions depicted in FIG. 1.

(55) According to FIG. 1, Intermediate 410 is prepared from Ligand 300 through Reaction 510. Afterward, it is transformed to Intermediate 420 with reaction 520. Finally, Emitter 100 is prepared from Intermediate 420 by Reaction 530.

(56) In one embodiment, Reaction 510 is reacting Ligand 300 (such as a halo-substituted biphenyl compound) with n-butyl lithium at a suitable temperature and time, such as 77K for 2 hours, and then adding SnBu.sub.2Cl.sub.2 at room temperature.

(57) In one embodiment, Reaction 520 is reacting Intermediate 410 (for example a dialkyl-biphenyl tin intermediate) with HAuCl.sub.4.3H.sub.2O in a suitable solvent or mix solvent.

(58) In one embodiment, Reaction 530 is reacting Intermediate 420 (such as a multiphenyl dichloro bi-gold complex intermediate) with the deprotonated emission turn-on unit in a suitable solvent or mix solvent to provide the emitter.

(59) The following examples illustrate the subject invention. Unless otherwise indicated in the following examples and elsewhere in the specification and claims, all parts and percentages are by weight, all temperatures are in degrees Centigrade, and pressure is at or near atmospheric pressure.

Example 601Preparation of Intermediate 411

(60) ##STR00018##
Under N.sub.2 at 77 K, n-BuLi (2.7 mL, 6.48 mmol) was added to Ligand 301 (1 g, 3.21 mmol) dissolved in 30 mL dry ether. The reaction mixture was immediately warmed to room temperature and stirred for 2 hours. Dibutyltin dichloride (0.98 g, 3.23 mmol) dissolved in 3 mL dry ether was syringed into the reaction mixture. The pale yellow blurred solution turned white milky after addition. After stirring at room temperature overnight, H.sub.2O was added and the organic layer was extracted. Removal of solvent yielded a pale yellow solid. Subsequent column chromatography with pure hexane yielded pure product as a white solid. Yield: 0.72 g (58.3%). .sup.1H NMR (400 MHz, CDCl.sub.3): 7.96 (d, 2H, J=7.82 Hz), 7.63 (d, 2H, .sup.118Sn satellite, J=7.82 Hz, J.sub.HPt=35.0 Hz), 7.40 (t, 2H, J=7.62 Hz), 7.28 (d, 2H, J=7.06 Hz), 1.58-1.66 (m, 4H), 1.31-1.39 (m, 8H), 0.87 (t, 6H, J=7.29 Hz).

Example 602Preparation of Intermediate 412

(61) ##STR00019##
The procedure is similar to that of example 601 except that Ligand 302 (1.4 g, 3.31 mmol) was used instead of Ligand 301. Yield: 0.70 g (42.6%). .sup.1H NMR (400 MHz, CDCl.sub.3): 7.84 (d, 2H, J=8.28 Hz), 7.62 (d, 2H, .sup.118Sn satellite, J=1.97 Hz, J.sub.HPt=36.1 Hz), 7.39 (dd, 2H, J=8.25 Hz, J=2.10 Hz), 1.64-1.69 (m, 4H), 1.31-1.42 (m, 26H), 0.89 (t, 6H, J=7.31 Hz).

Example 603Preparation of Intermediate 421

(62) ##STR00020##
HAuCl.sub.4.3H.sub.2O (200 mg, 0.508 mmol) was dissolved in 20 mL MeCN. Intermediate 411 (200 mg, 0.52 mmol) was added. The mixture was heated to 80 C. and reacted overnight. The off-white precipitates were filtered and washed thoroughly with MeCN and CHCl.sub.3. Yield: 77 mg (38.7%).

Example 604Preparation of Intermediate 422

(63) ##STR00021##
The procedure was similar to that of Intermediate 421 except that Intermediate 412 (252 mg, 0.507 mmol) was used. Yield: 128 mg (50.5%).

Example 605Preparation of Emitter 101

(64) ##STR00022##
Na(acac) (10 mg, 0.08 mmol) was dissolved in a minimal amount of EtOH. 10 mL CHCl.sub.3 was added. To the mixture, Intermediate 421 (30 mg, 0.039 mmol) was added and the temperature was raised to 50 C. The blurred solution became clearer overnight. Solvent was then evaporated under reduced pressure. The crude was re-dissolved in CHCl.sub.3 and filtered through a celite plug. Precipitation of the product in MeOH afforded the product as a white solid. Yield: 16 mg (44.3%). .sup.1H NMR (400 MHz, CDCl.sub.3): 7.67 (d, 2H, J=7.69 Hz), 7.32 (d, 2H, J=7.53 Hz), 7.19 (t, 2H, J=7.41 Hz), 7.00 (t, 2H, J=7.55 Hz), 5.52 (s, 1H), 2.19 (s, 6H). Elemental analysis Calcd for C.sub.17H.sub.15AuO.sub.2: C, 45.55; H, 3.37; O, 7.14. Found: C, 46.38; H, 3.50.

Example 606Preparation of Emitter 102

(65) ##STR00023##
K(OPPh.sub.2).sub.2N (61 mg, 0.130 mmol) was dissolved in a minimal amount of EtOH. 10 mL CHCl.sub.3 was added. To the mixture, Intermediate 421 (50 mg, 0.065 mmol) was added and the temperature was raised to 50 C. and allowed to react for 2 h. The colorless solution with some metallic deposit was filtered through a celite plug. Solvent was then evaporated under reduced pressure. Precipitation of the product in MeOH afforded the product as a white solid. Recrystallization in CHCl.sub.3/hexane yielded Emitter 102 as colorless crystals. Yield: 45 mg (45.2%). MS (FAB) m/z: 765.8 [M.sup.+]. .sup.1H NMR (400 MHz, CDCl.sub.3): 7.84-7.90 (m, 8H), 7.72 (d, 2H, J=7.78 Hz), 7.38-7.41 (m, 4H), 7.33-7.36 (m, 8H), 7.27-7.32 (m, 2H), 7.17 (t, 2H, J=7.47 Hz), 6.98 (t, 2H, J=7.58 Hz); .sup.31P NMR (162 MHz, CDCl.sub.3): 28.8; .sup.13C NMR (150 MHz, CDCl.sub.3): 121.4, 126.6, 128.2, 128.3 (J.sub.CP=13.64 Hz) 128.4, 129.5, 131.1, 131.2, 136.0 (.sup.3J.sub.CP=3.24 Hz), 136.9 (.sup.3J.sub.CP=3.24 Hz) 148.1, 151.7. Elemental analysis Calcd for C.sub.36H.sub.28AuNO.sub.2P.sub.2: C, 56.48; H, 3.69; N, 1.83. Found: C, 56.45; H, 3.61; N, 1.93.

Example 607Preparation of Emitter 103

(66) ##STR00024##
K.sub.2CO.sub.3 powder (25 mg, 0.18 mmol) was suspended in small amount of EtOH was added to 1-(3-hydroxybenzo[b]thiophen-2-yl)ethanone (17.6 mg, 0.092 mmol) dissolved in 10 mL CHCl.sub.3. The mixture was heated to 50 C. followed by the addition of Intermediate 421 (35 mg, 0.046 mmol). After reaction overnight, the yellow suspension was filtered and re-dissolved in THF. The THF solution was filtered through celite. Recrystallization in THF/hexane afforded Emitter 103 as a yellow solid. Yield: 22 mg (37.1%). .sup.1H NMR (400 MHz, CDCl.sub.3): 7.84-7.90 (m, 8H), 7.72 (d, 2H, J=7.78 Hz), 7.35-7.43 (m, 12H), 7.27-7.32 (m, 2H), 7.17 (t, 2H, J=7.47 Hz), 6.98 (t, 2H, J=7.58 Hz). Elemental analysis Calcd for C.sub.22H.sub.15AuO.sub.2S: C, 48.9; H, 2.8. Found: C, 49.06; H, 2.80.

Example 608General Procedure for Emitter 104-106

(67) K.sub.2CO.sub.3 powder (4 eq.) was suspended in EtOH. It was added to ROH (2 eq.) dissolved in CHCl.sub.3. The mixture was heated to 50 C. for 10 minutes after which Intermediate 421 (1 eq.) was added. The mixture was allowed to react overnight. Solvent was then evaporated under reduced pressure. The crude was re-dissolved in CHCl.sub.3 and filtered through a celite plug. Removal of solvents yielded products. Subsequent purifications by recrystallization were required.

Example 609Preparation of Emitter 104

(68) ##STR00025##
Followed Example 608 using 5,7-Dimethyl-8-quinolinol as ROH. Yield: 66.4%. MS (FAB) m/z: 521.1 [M.sup.+]. .sup.1H NMR (400 MHz, CDCl.sub.3): 9.04 (d, 1H, J=4.88 Hz), 8.52 (d, 1H, J=8.38 Hz), 8.13 (d, 1H, J=7.7 Hz), 7.61-7.64 (m, 1H), 7.57 (d, 1H, J=7.67 Hz), 7.44 (d, 1H, J=7.50 Hz), 7.36-7.38 (m, 2H), 7.21-7.25 (m, 2H), 7.05-7.13 (m, 2H), 2.61 (s, 1H), 2.59 (s, 1H). Elemental analysis Calcd for C.sub.23H.sub.18AuNO: C, 52.99; H, 3.48; N, 2.69. Found: C, 52.91; H, 3.53; N, 2.80.

Example 609Preparation of Emitter 105

(69) ##STR00026##
Followed Example 608 using 1-nitrosonaphthalen-2-ol as ROH. Yield: 54.1%. MS (FAB) m/z: 522.3 [M.sup.+]. .sup.1H NMR (400 MHz, CDCl.sub.3): 9.35 (d, 1H, J=8.32 Hz), 8.20 (d, 1H, J=8.05 Hz), 7.89 (d, 1H, J=9.38 Hz), 7.62-7.72 (m, 3H), 7.49 (t, 1H, J=7.43 Hz), 7.31 (d, 2H, J=7.48 Hz), 7.17-7.22 (m, 2H), 7.07-7.12 (m, 2H), 7.00 (t, 1H, J=7.46 Hz). Elemental analysis Calcd for C.sub.22H.sub.14AuNO.sub.2: C, 50.69; H, 2.71; N, 2.69. Found: C, 50.65; H, 2.74; N, 2.82.

Example 610Preparation of Emitter 106

(70) ##STR00027##
Followed Example 608 using 2,4-di-tert-butyl-6-(diphenylphosphino)phenol as ROH. Yield: 47.1%. MS (FAB) m/z: 734 [M.sup.+]. .sup.1H NMR (400 MHz, CDCl.sub.3): 8.23 (t, 1H, J=7.94 Hz), 7.69-7.74 (m, 4H), 7.34-7.54 (m, 9H), 7.18-7.24 (m, 3H), 7.11 (t, 1H, J=7.49 Hz), 6.89 (dd, 1H, J=2.24 Hz; J=10.4 Hz), 6.69 (t, 1H, J=7.52 Hz), 1.59 (s, 9H), 1.22 (s, 9H). Elemental analysis Calcd for C.sub.38H.sub.38AuOP: C, 61.79; H, 5.19. Found: C, 61.75; H, 5.16.

Example 611Preparation of Emitter 107

(71) ##STR00028##
Na(acac) (12.2 mg, 0.1 mmol) was dissolved in a minimal amount of EtOH. 10 mL CHCl.sub.3 was added. To the mixture, Intermediate 422 (50 mg, 0.05 mmol) was added and the temperature was raised to 50 C. The blurred solution turned clearer quickly. After heating overnight, solvent was evaporated under reduced pressure. The crude was re-dissolved in CHCl.sub.3 and filtered through a celite plug. Precipitation of the product in MeOH afforded the product as a white solid. Yield: 45 mg (79.8%). MS (FAB) m/z: 560.3 [M.sup.+]. .sup.1H NMR (400 MHz, CDCl.sub.3): 7.70 (s, 2H), 7.20 (s, 4H), 5.51 (s, 1H), 2.19 (s, 6H), 1.35 (s, 18H). Elemental analysis Calcd for C.sub.25H.sub.31AuO.sub.2: C, 53.57; H, 5.57. Found: C, 53.24; H, 5.59.

Example 612Preparation of Emitter 108

(72) ##STR00029##
K(OPPh.sub.2).sub.2N (47 mg, 0.10 mmol) was dissolved in a minimal amount of EtOH. 10 mL CHCl.sub.3 was added. To the mixture, Intermediate 422 (50 mg, 0.05 mmol) was added and the temperature was raised to 50 C. and allowed to react for 2 h. The colorless solution with some metallic deposit was filtered through a celite plug. Solvent was then evaporated under reduced pressure. Precipitation of the product in MeOH afforded the product as a white solid. Recrystallization in CHCl.sub.3/hexane yielded a pure colorless crystal. Yield: 73 mg (82.6%). MS (FAB) m/z: 878.5 [M.sup.+]. .sup.1H NMR (400 MHz, CDCl.sub.3): 7.86-7.91 (m, 8H), 7.78 (s, 2H), 7.31-7.41 (m, 12H), 7.15 (s, 4H), 1.34 (s, 18H); .sup.31P NMR (CDCl.sub.3): 28.6. Elemental analysis Calcd for C.sub.44H.sub.44AuNO.sub.2P.sub.2: C, 60.21; H, 5.05; N, 1.60. Found: C, 60.08; H, 5.07; N, 1.75.

Example 613Preparation of Emitter 109

(73) ##STR00030##
K.sub.2CO.sub.3 powder (22 mg, 0.159 mmol) was suspended in 2 mL EtOH. It was added to 2-acetyl-3-hydroxybenzo[b]thiophene (15.4 mg, 0.080 mmol) dissolved in 10 mL CHCl.sub.3. The mixture was heated to 50 C. for 10 minutes after which Intermediate 422 (40 mg, 0.040 mmol) was added. The mixture becomes clear within 2 h. Solvent was then evaporated under reduced pressure. The crude was re-dissolved in CHCl.sub.3 and filtered through a celite plug. Removal of solvents yielded products. Recrystallization in CHCl.sub.3/hexane mixture yielded pure yellow solids. Yield: 35 mg (66.6%). MS (FAB) m/z: 652.3 [M.sup.+]. .sup.1H NMR (300 MHz, CDCl.sub.3): 8.08 (d, 1H, J=7.86 Hz), 7.96 (s, 1H), 7.78 (s, 1H), 7.66 (d, 1H, J=7.94 Hz), 7.59 (t, 1H, J=7.40 Hz), 7.23 (s, 2H), 7.22 (s, 2H), 2.63 (s, 3H), 1.44 (s, 9H), 1.38 (s, 9H). Elemental analysis Calcd for C.sub.30H.sub.31AuO.sub.2S: C, 55.21; H, 4.79. Found: C, 55.19; H, 4.79.

Example 614Preparation of Emitter 110

(74) ##STR00031##
K.sub.2CO.sub.3 powder (17 mg, 0.123 mmol) was suspended in 2 mL EtOH. It was added to salicylaldehyde (8 mg, 0.065 mmol) dissolved in THF. The mixture was heated to 50 C. for 10 minutes after which Intermediate 422 (30 mg, 0.030 mmol) was added. The mixture becomes clear within 2 hours. Solvent was then evaporated under reduced pressure. The crude was re-dissolved in THF and filtered through a celite plug. Precipitation induced by MeOH in a concentrated THF solution yielded yellow solids. Yield: 13 mg (37.0%). MS (FAB) m/z: 582.2 [M.sup.+]. .sup.1H NMR (400 MHz, CDCl.sub.3): 9.47 (s, 1H), 7.87 (s, 1H), 7.70 (s, 1H), 7.64 (t, 1H, J=7.72 Hz), 7.46 (d, 1H, J=8.20 Hz), 7.19-7.22 (m, 4H), 7.05 (d, 1H, J=8.80 Hz), 6.72 (t, 1H, J=7.40 Hz), 1.39 (s, 18H).

Example 615Summary of Interplanar Distance and Au . . . Au Distance Between Adjacent Molecules of Emitters 102, 104, 107 and 109

(75) TABLE-US-00001 Emitter Interplanar distance/ Au . . . Au distance/ 102 n/a n/a 104 3.36 4.3998(4) 107 3.31 3.4083(4) 109 ca. 3.4 3.4530(5)

Example 616Selected Bond Lengths and Angles of Emitters 102, 104, 107 and 109

(76) TABLE-US-00002 102 104 107 Au1C1 1.992(4) Au1C1 2.024(6) Au1C1 2.002(8) Au1C12 2.003(4) Au1C12 2.001(7) Au1C12 1.994(8) Au1O1 2.122(3) Au1O1 2.054(4) Au1O1 2.074(5) Au1O2 2.132(2) Au1N1 2.137(6) Au1O2 2.070(5) C1C6 1.405(5) C1C6 1.417(9) C1C6 1.41(1) C7C12 1.410(5) C7C12 1.395(9) C7C12 1.41(1) O1P1 1.522(2) O1C21 1.329(8) O1C22 1.280(9) O2P2 1.525(3) N1C17 1.370(9) O2C24 1.266(9) N1P1 1.591(3) N1P2 1.596(3) C1Au1C12 81.6(2) C1AuC12 80.6(3) C1Au1C12 81.3(3) O1Au1O2 92.6(1) O1Au1N1 80.0(2) O1Au1O2 91.7(2) C1Au1O2 175.6(1) C1Au1O1 173.5(2) C1Au1O2 174.5(3) C12Au1O1 172.3(1) C12Au1N1 172.8(2) C12Au1O1 174.4(3) Au1O1P1 125.4(1) Au1N1C17 110.5(4) Au1O1C22 123.3(5) Au1O2P2 125.1(1) Au1O1C21 113.3(4) Au1O2C24 123.5(5) P1N1P2 124.4(2) Au1C1C6 114.2(5) C22C23C24 127.8(8) C6C1Au1 115.6(3) Au1C12C7 116.4(5) C6C1Au1 115.7(5) C7C12Au1 114.8(3) C7C12Au1 115.0(5) 109 109A Au1C1 2.008(9) Au1C1 2.006(9) Au1C12 2.012(8) Au1C12 1.981(8) Au1O1 2.081(6) Au1O1 2.095(6) Au1O2 2.070(6) Au1O2 2.070(6) C1C6 1.41(1) C1C6 1.40(1) C7C12 1.38(1) C7C12 1.41(1) O1C22 1.28(1) O1C22 1.27(1) O2C24 1.28(1) O2C24 1.29(1) C1Au1C12 81.0(3) C1Au1C12 81.5(4) O1Au1O2 91.4(2) O1Au1O2 91.6(2) C1Au1O2 174.6(3) C1Au1O2 174.8(3) C12Au1O1 174.6(5) C12Au1O1 174.9(3) Au1O1C22 126.2(5) Au1O1C22 125.6(5) Au1O2C24 123.2(5) Au1O2C24 122.0(5) C22C23C24 128.2(8) C22C23C24 127.6(8) C6C1Au1 115.4(6) C6C1Au1 115.1(6) C7C12Au1 115.0(6) C7C12Au1 116.3(6)

Example 617Crystal Data of Emitters 102, 104, 107 and 109

(77) TABLE-US-00003 Emitter 102 104 107 109 Empirical formula C36H28AuNO2P2 C23H18AuNO C25H31AuO2 C.sub.30H.sub.31AuO.sub.2S Formula weight 765.5 521.35 560.46 652.57 Temperature/K 100 100 100 100 Crystal system monoclinic monoclinic monoclinic monoclinic Space group P21/n P21/n C2/c P2.sub.1/c a/ 13.1302(9) 9.7011(5) 28.6707(16) 12.1735(7) b/ 11.4856(8) 8.5183(4) 7.4093(4) 14.2572(9) c/ 19.8929(14) 20.9099(10) 20.8800(12) 29.3295(18) / 90 90 90 90.00 / 98.741(2) 93.282(2) 90.804(2) 100.8420(15) / 90 90 90 90.00 Volume/.sup.3 2965.2(4) 1725.09(15) 4435.1(4) 4999.6(5) Z 4 4 8 8 p.sub.calcg/cm.sup.3 1.715 2.007 1.679 1.734 /mm.sup.1 10.616 16.105 12.586 12.032 F(000) 1504 1000 2208 2576.0 Crystal size/mm.sup.3 0.3 0.05 0.05 0.1 0.04 0.03 0.3 0.03 0.03 0.04 0.03 0.01 Radiation CuK ( = 1.54178) CuK ( = 1.54178) CuK ( = 1.54178) CuK ( = 1.54178) 2 range for data 7.58 to 135.66 8.48 to 131.16 6.16 to 132.78 6.92 to 130.16 collection/ Index ranges 15 h 13, 11 h 8, 31 h 34, 14 h 14, 13 k 13, 10 k 8, 8 k 8, 16 k 15, 17 l 23 24 l 23 24 l 24 34 l 34 Reflections collected 40194 20901 22304 41130 Independent reflections 5317 [Rint = 0.0654, 2876 [Rint = 0.0693, 3889 [Rint = 0.0925, 8462 [R.sub.int = 0.0819, Rsigma = 0.0356] Rsigma = 0.0382] Rsigma = 0.0623] R.sub.sigma = 0.0635] Data/restraints/parameters 5317/0/379 2876/0/237 3889/0/243 8462/0/357 Goodness-of-fit on F.sup.2 1.172 1.092 1.026 1.063 Final R indexes [I >= 2 (I)] R1 = 0.0319, R1 = 0.0358, R1 = 0.0604, R.sub.1 = 0.0779, wR2 = 0.0882 wR2 = 0.0943 wR2 = 0.1545 wR.sub.2 = 0.2000 Final R indexes [all data] R1 = 0.0320, R1 = 0.0375, R1 = 0.0660, R.sub.1 = 0.0803, wR2 = 0.0883 wR2 = 0.0958 wR2 = 0.1614 wR.sub.2 = 0.2045 Largest diff. peak/hole/e .sup.3 0.89/1.57 1.24/1.11 2.56/2.30 2.08/2.65
The ORETP diagrams are depicted in FIG. 2-FIG. 5

Example 618Electrochemical Data of Emitters 101, 102, 103, 105, 107, 108 and 109

(78) TABLE-US-00004 E.sub.pa or E.sub.1/2 E.sub.pc or E.sub.1/2 HOMO/LUMO E.sub.gap Emitter [V] [V] [eV] [eV] 101 ** ** ** ** 102 ** ** ** ** 103 1.03 2.15 5.83/2.65 3.18 105 1.04 1.12*, 2.18 5.84/3.79, 2.83 na 107 0.99* 2.60 5.65/2.47 3.18 108 1.06* 2.43 5.58/2.73 2.85 109 1.01, 1.28 2.12 5.66, 5.84/2.84 2.81 CH.sub.2Cl.sub.2 at 298K with 0.1M nBu.sub.4NPF.sub.6; scan rate 100 mV s.sup.1 Value versus Ag/AgNO.sub.3 (0.1M in CH.sub.3CN) reference electrode *For quasi-reversible process E.sub.1/2 = (E.sub.pa + E.sub.pc)/2 The HOMO and LUMO levels are estimated from onset potentials using Cp.sub.2Fec.sup.0/+ value of 4.8 eV below the vacuum level. ** redox process not observed in the scan range
The Cyclic voltammograms are depicted in FIG. 6 in descending order (Emitter 103 in the uppermost position while Emitter 109 is in the lowermost position).

Example 619TGA Data of Emitters 102, 103 and 107

(79) TABLE-US-00005 Decomposition Emitter Temperature/ C. 102 305 103 280 107 280
The TGA thermograms are depicted in FIGS. 7-9.

Example 619Photophysical Data of Emitters 101 and 102

(80) TABLE-US-00006 Emission UV/Vis absorption.sup.[a] Quantum Emitter .sub.abs [nm] ( [mol.sup.1dm.sup.3cm.sup.1]) Medium.sup.[a],[b] .sub.max [nm] ( [s]) k.sub.nr efficiency 101 274 (10700), 285 (13200), 306 (18000), CH.sub.2Cl.sub.2 466, 500, 534 (51) 1.49 10.sup.4 0.24 311 (17900), 350 (br, 800) Glass 77K 461, 496, 525 (123.9) 102 266 (9800), 273 (9800), 282 (10000), CH.sub.2Cl.sub.2 467, 501, 533 (53) 1.36 10.sup.4 0.28 294 (8900), 313 (7000), 350 (br, 1400) Glass 77K 461, 496, 525 (121.6) PMMA (5%) 467, 502, 535 0.35 .sup.[a]Measurements performed at 298K unless specified. .sup.[b]EtOH:MeOH = 4:1 solution were used for glass measurements at 77K. [c]Solution emission quantum yield measured using [Ru(bpy).sub.3][PF.sub.6].sub.2 in degassed acetonitrile as the standard ( = 0.062)
The emission spectra are depicted in FIGS. 10 and 11.

Example 620OLED Fabrication of Emitter 102

(81) In order to investigate the electroluminescent (EL) properties of Emitter 102, organic light-emitting devices (OLEDs) fabricated by both vacuum deposition (VDOLEDs) and solution process (SPOLEDs) techniques have been studied. Considering the high triplet energy (E.sub.t.sup.2.7 eV) of 102, the host and charge transporting materials with higher E.sub.t than 2.7 eV is necessary to effectively confine the triplet excitons in the emitting layer (ETL) and block the back energy transfer to the host and/or charge transporting material(s). The ineffective confinement of triplet excitons and the back energy transfer would severely lower the device efficiency. With this device design strategy, 9-(4-tertbutylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole (CzSi, E.sub.t=3.02 eV), and diphenylphosphine oxide-4-(triphenylsilyl)phenyl (TSPO1, E.sub.t=3.36 eV) have been used as the host and electron-transporting/hole-blocking layer (ETL/HBL), respectively, in the VDOLED. The device structure of the VDOLEDs was ITO/MoO.sub.3 (2 nm)/TAPC (40 nm)/TCTA (10 nm)/CzSi (3 nm)/CzSi: 102 (20 nm)/TSPO1 (10 nm)/TPBi (40 nm)/LiF (1.2 nm)/Al (150 nm). Besides CzSi and TSPO1 mentioned above, di-[4-(N,N-ditolyl-amino)-phenyl]cyclohexane (TAPC) was used as hole-transporting layer (HTL), 4,4,4-tris(carbazole-9-yl)triphenylamine (TCTA) as hole-transporting/electron-blocking layer (HTL/EBL), 2,2,2-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi) as ETL. Similarly, high-E.sub.t materials 2,6-dicarbazolo-1,5-pyridine (PYD2, E.sub.t=2.93 eV) and bis{2-[di(phenyl)phosphino]-phenyl}ether oxide (DEPEO, 3.00 eV) have been respectively used as host and ETL/HBL in SPOLED with 102 as the emitting dopant. The device architecture of SPOLEDs was ITO/PEDOT:PSS/PYD2:102 (40 nm)/DEPEO (5 nm)/TPBi (40 nm)/LIF (1.2 nm)/Al (Al). The doping concentration of 102 was 4 wt % or 10 wt % in both VDOLEDs or SPOLEDs.

Example 620Key Performance Parameters of OLEDs with Emitter 102

(82) TABLE-US-00007 V.sub.on.sup.c Max. CE Max. PE Max. EQE CIE.sup.d Device type (V) (cd A.sup.1) (lm W.sup.1) (%) (x, y) VD.sup.a-4 wt % 4.1 6.57 5.16 2.12 (0.33, 0.54) VD.sup.a-10 wt % 3.8 18.98 14.91 6.05 (0.32, 0.54) SP.sup.b-4 wt % 6.3 1.61 0.69 0.55 (0.29, 0.50) SP.sup.b-10 wt % 7.1 9.07 3.71 3.12 (0.28, 0.50) .sup.aOLED fabricated by vacuum deposition. .sup.bOLED fabricated by solution process. .sup.cTurn-on voltage (luminance = 1 cd m.sup.2). .sup.dCIE coordinates at 100 cd m.sup.2.

(83) The EL spectra and EQE-luminance characteristics of VDOLEDs and SPOLEDs are depicted in FIGS. 12 and 13.

(84) With respect to any figure or numerical range for a given characteristic, a figure or a parameter from one range may be combined with another figure or a parameter from a different range for the same characteristic to generate a numerical range.

(85) Other than in the operating examples, or where otherwise indicated, all numbers, values and/or expressions referring to quantities of ingredients, reaction conditions, etc., used in the specification and claims are to be understood as modified in all instances by the term about.

(86) While the invention has been explained in relation to certain embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.