ORGANIC ELECTROLUMINESCENT MATERIALS AND DEVICES

Abstract

A method of making an osmium(II) complex having Formula I, L.sup.1-Os-L.sup.2, wherein L.sup.1 and L.sup.2 are independently a biscarbene tridentate ligand, wherein L.sup.1 and L.sup.2 can be same or different is disclosed. The method includes (a) reacting a precursor of ligand L.sup.1 with an osmium precursor to form an intermediate product, wherein the osmium precursor having the formula OsH.sub.x(PR.sub.3).sub.y, wherein x is an integer from 2 to 6 and y is an integer from 2 to 5, and R is selected from the group consisting of aryl, alkyl and cycloalkyl; and (b) reacting a precursor of ligand L.sup.2 with said intermediate product.

Claims

1. A compound having a structure according to Formula I:
L.sup.1-Os-L.sup.2; wherein L.sup.1 and L.sup.2 are different; wherein L.sup.1 and L.sup.2 are independently selected from ligands having Formula II: ##STR00219## wherein: 1) for L.sup.1, Y.sup.1, Y.sup.2 and Y.sup.3 comprise C and, for L.sup.2, either (i) Y.sup.1 and Y.sup.3 comprises C and Y.sup.2 is N, or (ii) Y.sup.1 and Y.sup.3 are N, and Y.sup.2 comprises C, or 2) for L.sup.1, Y.sup.1 and Y.sup.3 comprises C and Y.sup.2 is N, and, for L.sup.2, Y.sup.1 and Y.sup.3 are N, and Y.sup.2 comprises C; wherein R.sup.3 and R.sup.4 may represent mono-, or di-substitutions, or no substitution; wherein R.sup.5 may represent mono-, di-, or tri-substitutions, or no substitution; wherein R.sup.1 and R.sup.2 are independently selected from the group consisting of alkyl and cycloalkyl; wherein R.sup.3, R.sup.4 and R.sup.5 are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof; wherein any two adjacent substituents of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are optionally joined to condense into a fused ring; and wherein the dash lines show the connection points to osmium.

2. The compound of claim 1, wherein, for L.sup.2, Y.sup.1 and Y.sup.3 comprise C, and Y.sup.2 is N.

3. The compound of claim 1, wherein, for L.sup.2, Y.sup.1 and Y.sup.3 are N, and Y.sup.2 comprise C.

4. The compound of claim 1, wherein each R.sup.1 and R.sup.2 is independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and partially or fully deuterated variants thereof.

5. The compound of claim 1, wherein each R.sup.1 and R.sup.2 is independently selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, partially or fully deuterated variants thereof, and combinations thereof.

6. The compound of claim 1, wherein L.sup.1 and L.sup.2 are independently selected from ligands having Formula III: ##STR00220## wherein each X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6, X.sup.7 and X.sup.8 independently comprises C or N.

7. The compound of claim 1, wherein each X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6, X.sup.7 and X.sup.8 comprises C.

8. The compound of claim 1, wherein ligand L.sup.1 is selected from the group consisting of: ##STR00221## ##STR00222## ##STR00223## ##STR00224## ##STR00225## ##STR00226## ##STR00227## ##STR00228## ##STR00229## ##STR00230## ##STR00231## ##STR00232## ##STR00233## ##STR00234## ##STR00235## ##STR00236##

9. The compound of claim 1, wherein R.sup.5 of L.sup.1 is different from R.sup.5 of L.sup.2.

10. The compound of claim 1, wherein, for L.sup.1, Y.sup.1, Y.sup.2 and Y.sup.3 comprise C, and, for L.sup.2, Y.sup.1 and Y.sup.3 comprises C and Y.sup.2 is N

11. The compound of claim 1, wherein, for L.sup.1, Y.sup.1, Y.sup.2 and Y.sup.3 comprise C, and, for L.sup.2, Y.sup.1 and Y.sup.3 are N, and Y.sup.2 comprises C.

12. The compound of claim 1, wherein for L.sup.1, Y.sup.1 and Y.sup.3 comprises C and Y.sup.2 is N, and, for L.sup.2, Y.sup.1 and Y.sup.3 are N, and Y.sup.2 comprises C.

13. A first device comprising a first organic light emitting device, the first organic light emitting device comprising: an anode; a cathode; and an organic layer, disposed between the anode and the cathode, comprising a compound having the structure according Formula I
L.sup.1-Os-L.sup.2; wherein L.sup.1 and L.sup.2 are different; wherein L.sup.1 and L.sup.2 are independently selected from ligands having Formula II: ##STR00237## wherein: 1) for L.sup.1, Y.sup.1, Y.sup.2 and Y.sup.3 comprise C and, for L.sup.2, either (i) Y.sup.1 and Y.sup.3 comprises C and Y.sup.2 is N, or (ii) Y.sup.1 and Y.sup.3 are N, and Y.sup.2 comprises C, or 2) for L.sup.1, Y.sup.1 and Y.sup.3 comprises C and Y.sup.2 is N, and, for L.sup.2, Y.sup.1 and Y.sup.3 are N, and Y.sup.2 comprises C; wherein R.sup.3 and R.sup.4 may represent mono-, or di-substitutions, or no substitution; wherein R.sup.5 may represent mono-, di-, or tri-substitutions, or no substitution; wherein R.sup.1 and R.sup.2 are independently selected from the group consisting of alkyl and cycloalkyl; wherein R.sup.3, R.sup.4 and R.sup.5 are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof, wherein any two adjacent substituents of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are optionally joined to condense into a fused ring; and wherein the dash lines show the connection points to osmium.

14. The first device of claim 13, wherein the first device is a consumer product selected from the group consisting of light panels, flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads up displays, fully transparent displays, flexible displays, laser printers, telephones, cell phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicles, large area walls, theater or stadium screens, and signs.

15. The first device of claim 13, wherein the first device is an organic light emitting device.

16. The first device of claim 13, wherein the organic layer is an emissive layer and the compound is an emissive dopant or a non-emissive dopant.

17. The first device of claim 13, wherein the organic layer further comprises a host material.

18. The first device of claim 17, wherein the host material comprises a triphenylene containing benzo-fused thiophene or benzo-fused furan; wherein any substituent in the host material is an unfused substituent independently selected from the group consisting of C.sub.nH.sub.2n+1, OC.sub.nH.sub.2n+1, OAr.sub.1, N(C.sub.nH.sub.2n+1).sub.2, N(Ar.sub.1)(Ar.sub.2), CH═CH—C.sub.nH.sub.2n+1, C≡CC.sub.nH.sub.2n+1, Ar.sub.1, Ar.sub.1—Ar.sub.2, and C.sub.nH.sub.2n—Ar.sub.1; wherein n is from 1 to 10; and wherein Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.

19. The first device of claim 17, wherein the host material comprises at least one chemical group selected from the group consisting of carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

20. The first device of claim 17, wherein the host material is selected from the group consisting of: ##STR00238## ##STR00239## and combinations thereof.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0022] FIG. 1 shows an organic light emitting device.

[0023] FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.

[0024] FIG. 3 shows molecular diagram of complex monohydride with X-ray diffraction analysis characterization.

[0025] FIG. 4 shows molecular diagram of Complex A with X-ray diffraction analysis characterization.

DETAILED DESCRIPTION

[0026] Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.

[0027] The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.

[0028] More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), which are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.

[0029] FIG. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporated by reference.

[0030] More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F.sub.4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.

[0031] FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an “inverted” OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides one example of how some layers may be omitted from the structure of device 100.

[0032] The simple layered structure illustrated in FIGS. 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to FIGS. 1 and 2.

[0033] Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in FIGS. 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties.

[0034] Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and OVJD. Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processibility than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

[0035] Devices fabricated in accordance with embodiments of the present invention may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.

[0036] Devices fabricated in accordance with embodiments of the invention may be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads up displays, fully transparent displays, flexible displays, laser printers, telephones, cell phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicles, a large area wall, theater or stadium screen, or a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 degrees C.), but could be used outside this temperature range, for example, from −40 degree C. to +80 degree C.

[0037] The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.

[0038] The terms halo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic group, aryl, aromatic group, and heteroaryl are known to the art, and are defined in U.S. Pat. No. 7,279,704 at cols. 31-32, which are incorporated herein by reference.

[0039] As used herein, “substituted” indicates that a substituent other than H is bonded to the relevant carbon. Thus, where R.sup.2 is monosubstituted, then one R.sup.2 must be other than H. Similarly, where R.sup.3 is disubstituted, then two of R.sup.3 must be other than H. Similarly, where R.sup.2 is unsubstituted R.sup.2 is hydrogen for all available positions.

[0040] In the present disclosure, novel heteroleptic bistridentate Os(II) complexes and a novel method for synthesizing both homoleptic and heteroleptic bistridentate Os(II) complexes is provided. Heteroleptic osmium complexes provide great freedom of tuning emission color, electrochemical energy levels, and improving evaporation properties.

[0041] Osmium (II) complexes have been investigated for OLED applications. The octahedral ligand arrangement of the Os(II) complexes resembles that of Ir(III) complexes. Os(II) complexes generally exhibit low oxidation potential, i.e. shallow HOMO energy level than Ir(III) complexes. The inventors have discovered that bistridentate Os(II) carbene complexes offer performance advantages for OLED applications. Without being bound to a theory, the inventors believe that the rigid nature of the tridentate ligands are providing narrow emission line widths and short excited state lifetimes, which can result in better color purity and longer device lifetime, making them suitable for display applications.

[0042] US2005260449 and WO2009046266 disclosed bistridentate Os(II) complexes. Examples of homoleptic Os(II) complexes were provided. The two tridentate ligands binding to Os(II) metal are identical. It may be beneficial to incorporate two different ligands to Os(II) metal to form a heterlopetic complex. For example, the thermal properties, electrochemical properties, and photophysical properties can be tuned by selecting two proper ligands. It offers more flexibility for materials design than two identical ligands.

[0043] The synthesis of homoleptic complexes, however, has been challenging; let alone the heteroleptic complexes. The synthesis method used in WO2009046266 generated very low yield, typically 2-5%. In a later application, US2012215000, the yield was significantly improved to over 30% using a new osmium precursor. In theory, both of these methods should work for synthesis of heteroleptic bistridentate Os(II) complexes by introducing two different ligands at the complexation stage and isolating the desired heteroleptic complex from the reaction mixture. The synthesis will be extremely inefficient and impractical.

[0044] The inventors have developed a new stepwise complexation method. This method is suitable for making both homoleptic and heteroleptic bistridentate Os(II) complexes. As shown in the scheme below, an osmium precursor was first reacted with a bistridentate ligand to generate an intermediate that has one tridentate ligand coordinated to the metal. The intermediate was then treated with another tridentate ligand to generate the final complex. Depending on the structure of the second ligand, homoleptic or heteroleptic complexes can be synthesized. In addition, the yield was improved. One example of the inventive synthetic method is shown below:

##STR00003##

[0045] In describing the novel synthesis method of the inventors, all reactions were carried out with rigorous exclusion of air using Schlenk-tube techniques. Solvents, except DMF and acetonitrile that were dried and distilled under argon, were obtained oxygen- and water-free from an MBraun solvent purification apparatus. .sup.1H .sup.31P{.sup.1H}, .sup.19F and .sup.13C{.sup.1H} NMR spectra were recorded on Bruker 300 ARX, Bruker Avance 300 MHz, and Bruker Avance 400 MHz instruments. Chemical shifts (expressed in parts per million) are referenced to residual solvent peaks (.sup.1H, .sup.13C{.sup.1H}) or external 85% H.sub.3PO.sub.4 (.sup.31P{.sup.1H}), or external CFCl.sub.3 (.sup.19F). Coupling constants J and N are given in hertz. Attenuated total reflection infrared spectra (ATR-IR) of solid samples were run on a Perkin-Elmer Spectrum 100 FT-IR spectrometer. C, H, and N analyses were carried out in a Perkin-Elmer 2400 CHNS/O analyzer. High-resolution electrospray mass spectra were acquired using a MicroTOF-Q hybrid quadrupole time-of-flight spectrometer (Bruker Daltonics, Bremen, Germany). OsH.sub.6(P.sup.iPr.sub.3).sub.2 was prepared by the method published in Aracama, M.; Esteruelas, M. A.; Lahoz, F. J.; López, J. A.; Meyer, U.; Oro, L. A.; Werner, H. Inorg. Chem. 1991, 30, 288.

[0046] Preparation of Dihydride-BF4

##STR00004##

A solution of OsH.sub.6(P.sup.iPr.sub.3).sub.2 (261 mg, 0.505 mmol) in dimethylformamide (DMF) (5 mL) was treated with 1,3-bis[(1-methyl)benzylimidazolium-3-yl]benzene diiodide (300 mg, 0.505 mmol). The resulting mixture was refluxed for 20 min, getting a very dark solution. After cooling at room temperature the solvent was removed in vacuo, affording a dark residue. The residue was dissolved in acetonitrile (10 mL) and AgBF.sub.4 (98.3 mg, 0.505 mmol) was added. After stirring protected from the light for 30 min the resulting suspension was filtered through Celite to remove the silver salts. The solution thus obtained was evaporated to ca. 0.5 mL and diethyl ether (10 mL) was added to afford a beige solid, that was washed with further portions of diethyl ether (2×2 mL) and dried in vacuo. Yield: 240 mg (50%). Analytical Calculation for C.sub.40H.sub.61BF.sub.4N.sub.4OsP.sub.2: C, 51.28; H, 6.56; N, 5.98. Found: C, 51.55; H, 6.70; N, 5.62. HRMS (electrospray, m/z): calcd for C.sub.40H.sub.61N.sub.4OsP.sub.2 [M].sup.+: 851.3983; found: 851.4036. IR (cm.sup.−1): ν(Os—H) 2104 (w), ν(BF.sub.4) 1080-1000 (vs). .sup.1H NMR (300 MHz, CD.sub.3CN, 298K): δ 8.31 (m, 2H, CH bzm), 7.98 (d, J.sub.H—H=7.9, 2H, CH Ph), 7.70 (m, 2H, CH bzm), 7.57 (t, J.sub.H—H=7.9, 1H, CH Ph), 7.54-7.50 (m, 4H, CH bzm), 4.32 (s, 6H, CH.sub.3), 1.54 (m, 6H, PCH(CH.sub.3).sub.2), 0.67 (dvt, J.sub.HH=6.2, N=13.2, 36H, PCH(CH.sub.3).sub.2), −6.25 (t, J.sub.H—P=13.6, 2H, Os—H). .sup.13C{.sup.1H} NMR (75.42 MHz, CD.sub.3CN, 293K): δ 189.4 (t, J.sub.C—P=7.5, NCN), 161.3 (Os—C), 146.9 (s, C Ph), 137.3 (s, C Bzm), 132.8 (s, C Bzm), 124.9 (s, CH Bzm), 124.5 (s, CH Bzm), 124.2 (s, CH Ph), 112.8 (s, CH Bzm), 111.9 (s, CH Bzm), 109.2 (s, CH Ph), 38.9 (s, CH.sub.3), 29.3 (t, N=27, PCH(CH.sub.3).sub.2), 18.5 (s, PCH(CH.sub.3).sub.2). .sup.31P{.sup.1H} NMR (121.4 MHz, CD.sub.3CN, 293K): δ 4.5 (s).

[0047] Preparation of complex monohydride, shown below:

##STR00005##

This monohydride compound can be prepared by using two different methods. Method (A): A solution of OsH.sub.6(P.sup.iPr.sub.3).sub.2 (261 mg, 0.505 mmol) in DMF (5 mL) was treated with 1,3-bis[(1-methyl)benzylimidazolium-3-yl]benzene diiodide (300 mg, 0.505 mmol). The resulting mixture was refluxed for 20 min, getting a very dark solution. After cooling at room temperature the solvent was removed in vacuo, affording a dark residue. The dark residue was dissolved in 10 mL of tetrahydrofuran (THF) and K.sup.tBuO (142 mg, 1.263 mmol) was added to the solution. After stirring at room temperature for 10 min the resulting suspension was filtered through Celite to remove the potassium salts. The solution thus obtained was evaporated to dryness to afford a yellow residue. Addition of pentane afforded a yellow solid, which was washed with pentane (1×2 mL) and dried in vacuo to obtain a yellow solid. Yield: 378 mg (88%). Method (B): A solution of dihydride-BF4 (200 mg, 0.213 mmol) in THF (5 mL) was treated with K.sup.tBuO (28.6 mg, 0.255 mmol). After stirring at room temperature for 10 min the resulting suspension was filtered through Celite to remove the potassium salts. The solution thus obtained was evaporated to dryness to afford a yellow residue. Addition of pentane afforded a yellow solid, which was washed with pentane (1×2 mL) and dried in vacuo obtain a yellow solid. Yield: 163 mg (90%). Anal. Calcd. for C.sub.40H.sub.60N.sub.4OsP.sub.2: C, 56.58; H, 7.12; N, 6.60. Found: C, 56.00; H, 6.69; N, 6.76. HRMS (electrospray, m/z): calcd. For [M+H].sup.+ 851.3983; found: 851.3979. IR (cm.sup.−1): ν(Os—H) 1889 (w). .sup.1H NMR (300 MHz, C.sub.6D.sub.6, 298K): δ 8.17 (d, J.sub.H—H=7.7, 2H, CH Ph), 8.06 (d, J.sub.H—H=7.7, 2H, CH bzm), 7.60 (t, J.sub.H—H=7.7, 1H, CH Ph), 7.20 (td, J.sub.H—H=7.9, J.sub.H—H=1.0, 2H, CH bzm), 7.14-7.03 (m, 4H CH bzm), 3.92 (s, 6H, CH.sub.3), 1.55 (m, 6H, PCH(CH.sub.3).sub.2), 0.67 (dvt, J.sub.H.H=6.9, N=12.3, 36H, PCH(CH.sub.3).sub.2), −9.55 (t, J.sub.H—P=33.6, 1H, Os—H). .sup.13C{.sup.1H} NMR (75.42 MHz, C.sub.6D.sub.6, 293K): δ 197.6 (t, J.sub.C—P=9.2, Os—NCN), 173.2 (t, J.sub.C—P=2.9, Os—C), 148.4 (s, C Ph), 137.3 (s, C Bzm), 134.4 (s, C Bzm), 121.5 (s, CH Bzm), 121.2 (s, CH Bzm), 117.9 (s, CH Ph), 109.6 (s, CH Bzm), 108.5 (s, CH Bzm), 105.8 (s, CH Ph), 37.9 (s, CH.sub.3), 31.0 (t, N=24.2, PCH(CH.sub.3).sub.2), 19.7 (s, PCH(CH.sub.3).sub.2). .sup.31P{.sup.1H} NMR (121.4 MHz, C.sub.6D.sub.6, 293K): δ 20.6 (s, doublet under off resonance conditions). FIG. 3 shows the molecular structure of complex monohydride with the X-ray diffraction analysis characterization. Selected bond lengths (Å) and angles (°) were: Os—P(1)=2.3512(18), Os—P(2)=2.3529(17), Os—C(1)=2.052(6), Os—C(9)=2.036(3), Os—C(15)=2.035(6); P(1)-Os—P(2)=152.86(6), C(1)-Os—C(9)=75.5(2), C(9)-Os—C(15)=75.4(2), C(1)-Os(C15)=150.9(2).

[0048] Preparation of Complex Monohydride-CF3:

##STR00006##

Method (A):

[0049] A solution of dihydride-CF3-BF4 (200 mg, 0.2 mmol) in THF (5 mL) was treated with K.sup.tBuO (26.8 mg, 0.24 mmol). After stirring at room temperature for 10 min the resulting suspension was filtered through Celite to remove the potassium salts. The solution thus obtained was evaporated to dryness to afford a yellow residue. Addition of pentane afforded a yellow solid, which was washed with pentane (1×2 mL) and dried in vacuo obtain a yellow solid. Yield: 240 mg (50%). Anal. Calcd. for C.sub.41H.sub.59F.sub.3N.sub.4OsP.sub.2: C, 53.69; H, 6.48; N, 6.11. Found: C, 53.20; H, 6.33; N, 6.18. IR (cm.sup.−1): ν(Os—H) 1842 (w). .sup.1H NMR (300 MHz, C.sub.6D.sub.6, 298K): δ 8.53 (s, 2H, CH Ph-CF.sub.3), 8.18 (m, 2H, CH bzm), 7.15-6.98 (m, 6H, CH bzm), 3.86 (s, 6H, CH.sub.3), 1.49 (m, 6H, PCH(CH.sub.3).sub.2), 0.60 (dvt, J.sub.H.H=6.6, N=12.9, 36H, PCH(CH.sub.3).sub.2), −9.29 (t, J.sub.H—P=34.0, 1H, Os—H). .sup.13C{.sup.1H} NMR (75.42 MHz, C.sub.6D.sub.6, 293K): δ 197.4 (t, J.sub.C—P=9.0, Os—NCN), 173.2 (t, J.sub.C—P=3.6, Os—C), 148.0 (s, C Ph), 137.2 (s, C Bzm), 133.9 (s, C Bzm), 128.2 (q, J.sub.C—F=270.0, CF.sub.3), 122.0 (s, CH Bzm), 121.7 (s, CH Bzm), 118.9 (q, J.sub.C—F=30.8, C—CF.sub.3), 109.8 (s, CH Bzm), 108.7 (s, CH Bzm), 102.0 (q, J.sub.C—F=4.0 CH Ph), 37.9 (s, CH.sub.3), 30.9 (t, N=24.8, PCH(CH.sub.3).sub.2), 19.5 (s, PCH(CH.sub.3).sub.2). .sup.31P{.sup.1H} NMR (121.4 MHz, C.sub.6D.sub.6, 293K): δ 21.4 (s, doublet under off resonance conditions). .sup.19F NMR 282 MHz, C.sub.6D.sub.6, 293K): δ −60.10 (CF.sub.3). Method (B): A solution of OsH.sub.6(P.sup.iPr.sub.3).sub.2 (235 mg, 0.455 mmol) in DMF (5 mL) was treated with 1,3-bis[(1-methyl)benzylimidazolium-3-yl]-5-trifluoromethyl-benzene diiodide (300 mg, 0.455 mmol). The resulting mixture was refluxed for 20 min, getting a very dark solution. After cooling at room temperature the solvent was removed in vacuo, affording a dark residue. The addition of 4 mL of toluene caused the precipitation of a brown solid that was washed with further portions of diethyl ether (2×4 mL). The brown solid was dissolved in THF (10 mL) and K.sup.tBuO (102 mg, 0.906 mmol) was added. After stirring for 20 min the resulting suspension was filtered through Celite to remove the iodide salts. The solution thus obtained was evaporated to dryness and pentane (4 mL) was added to afford an orange solid that was washed with further portions of pentane (1×3 mL) and dried in vacuo. This orange solid was suspended in diethyl ether (10 mL) and treated with HBF.sub.4:Et.sub.2O (93 μL, 0.680 mmol) getting a white suspension. This solid was decanted, washed with further portions of diethyl ether (2×4 mL) and dried in vacuo. Yield: 405 mg (89%) Anal. Calcd. for C.sub.41H.sub.60BF.sub.7N.sub.4OsP.sub.2: C, 49.00; H, 6.02; N, 5.58. Found: C, 49.21; H, 5.79; N, 5.69. HRMS (electrospray, m/z): calcd for [M].sup.+: 919.3857; found: 919.4035. IR (cm.sup.−1): ν(Os—H) 2097 (w), ν(BF.sub.4) 1080-1000 (vs). .sup.1H NMR (300 MHz, CD.sub.3CN, 298K): δ 9.60 (m, 2H, CH bzm), 9.41 (s, 2H, CH Ph), 8.96 (m, 2H, CH bzm), 8.80 (m, 4H, CH bzm), 5.57 (s, 6H, CH.sub.3), 2.80 (m, 6H, CH.sub.P), 1.91 (dvt, 36H, J.sub.HH=7.1, N=13.5, CH.sub.3-P), −4.70 (t, 2H, J.sub.H—P=13.5, H.sub.hyd); .sup.13C{.sup.1H} NMR (75.42 MHz, CD.sub.3CN, 293K): δ 189.6 (t, J.sub.C—P=7.5, NCN), 169.6 (t, J.sub.C—P=5.7, Os—C), 146.7 (s, C Ph), 137.4 (s, C Bzm), 132.6 (s, C Bzm), 126.7 (q, J.sub.C—F=270, CF.sub.3), 126.3 (q, J.sub.C—F=28.6, CCF.sub.3), 125.4 (s, CH Bzm), 125.1 (s, CH Bzm), 113.2 (s, CH Bzm), 112.3 (s, CH Bzm), 105.6 (q, J.sub.C—F=3.9, CH Ph), 39.1 (s, CH.sub.3), 29.5 (t, N=13.5, PCH(CH.sub.3).sub.2), 19.6 (s, PCH(CH.sub.3).sub.2). .sup.31P{.sup.1H} NMR (121.4 MHz, CD.sub.3CN, 293K): δ 5.2 (s). .sup.19F{.sup.1H} NMR (282 MHz, CD.sub.3CN, 293K): δ −60.21 (s, CF.sub.3); −151.7 (broad signal, BF.sub.4)

[0050] Preparation of Complex A:

##STR00007##

Monohydride (250 mg, 0.294 mmol) and 1,3-bis[(1-methyl)benzylimidazolium-3-yl]benzene ditetrafluoroborate (181 mg, 0.353 mmol) were dissolved in 5 mL of DMF and triethyl amine (0.6 mL, 4.4 mmol) was added to the solution. The resulting mixture was refluxed for 1.5 h and then it was cooled to room temperature. The solvent was evaporated under vacuum to afford a brown residue. Addition of acetonitrile afforded a bright yellow solid that was washed with acetonitrile (1×2 mL) and dried in vacuo. Yield: 153 mg (60%). HRMS (electrospray, m/z): calcd for C.sub.44H.sub.34N.sub.8Os [M].sup.+: 867.2562; found: 867.2597. .sup.1H NMR (300 MHz, C.sub.6D.sub.6, 293K): δ 8.29 (d, J.sub.H—H=7.7, 4H, CH Ph), 8.18 (d, J.sub.H—H=7.9, 4H, CH bzm), 7.81 (t, J.sub.H—H=7.7, 2H, CH Ph), 7.08 (td, J.sub.H—H=7.9, J.sub.H—H=1.0, 4H, CH bzm), 6.80 (td, J.sub.H—H=7.9, J.sub.H—H=1.0, 4H, CH bzm), 6.18 (d, J.sub.H—H=7.9, 4H, CH bzm), 2.25 (s, 12H, CH.sub.3). .sup.13C{.sup.1H} NMR (75.42 MHz, C.sub.6D.sub.6, 293K): δ 192.6 (s, Os—NCN), 171.1 (s, Os—C), 146.8 (s, C Ph), 137.2 (s, C Bzm), 133.4 (s, C Bzm), 121.43 (s, CH Bzm), 121.03 (s, CH Bzm), 117.8 (s, CH Ph), 109.9 (s, CH Bzm), 109.0 (s, CH Bzm), 106.4 (s, CH Ph), 32.7 (s, CH.sub.3). FIG. 4 shows molecular diagram of Complex A with X-ray diffraction analysis characterization. The structure has two chemically equivalent but crystallographically independent molecules in the asymmetric unit. Selected bond lengths (Å) and angles (°): Os(1)-C(10)=2.048(7), 2.057(7), Os(1)-C(32)=2.045(7), 2.049(8), Os(1)-C(15)=2.026(8), 2.032(8), Os(1)-C(1)=2.042(8), 2.037(7), Os(1)-C(23)=2.049(7), 2.037(8), Os(1)-C(37)=2.043(7), 2.051(8); C(15)-Os(1)-C(1)=149.6(3), 149.9(3), C(23)-Os(1)-C(37)=150.0(3), 150.6(3), C(10)-Os(1)-C(32)=177.8(3), 178.6(3).

[0051] Preparation of Complex A-CF.sub.3:

##STR00008##

Monohydride (250 mg, 0.294 mmol) and 1,3-bis[(1-methyl)benzylimidazolium-3-yl]-5-trifluoromethyl-benzene ditetrafluoroborate (170 mg, 0.294 mmol) were dissolved in 5 mL of DMF and triethyl amine (0.6 mL, 4.4 mmol) was added to the solution. The resulting mixture was refluxed for 1.5 h and then it was cooled to room temperature. The solvent was evaporated under vacuum to afford a brown residue. Addition of acetonitrile afforded a bright yellow solid that was washed with acetonitrile (1×2 mL) and dried in vacuo. Yield: 147 mg (53%). HRMS (electrospray, m/z): calcd for C.sub.45H.sub.33F.sub.3N.sub.8Os [M].sup.+: 934.2392; found: 934.2398. .sup.1H NMR (300 MHz, C.sub.6D.sub.6, 293K): δ 8.75 (s, 2H, CH Ph-CF.sub.3), 8.24 (d, J.sub.H—H=7.8, 2H, CH Ph), 8.16 (d, J.sub.H—H=7.8, 2H, CH bzm), 8.14 (d, J.sub.H—H=7.8, 2H, CH bzm), 7.78 (t, J.sub.H—H=7.8, 1H, CH Ph), 7.08 (t, J.sub.H—H=7.8, 2H, CH bzm), 6.99 (t, J.sub.H—H=7.8, 2H, CH bzm), 6.81 (t, J.sub.H—H=7.9, 2H, CH bzm), 6.78 (t, J.sub.H—H=7.9, 2H, CH bzm), 6.21 (d, J.sub.H—H=7.8, 2H, CH bzm), 6.14 (d, J.sub.H—H=7.8, 2H, CH bzm), 2.22 (s, 6H, CH.sub.3), 2.11 (s, 6H, CH.sub.3). .sup.13C{.sup.1H} NMR (100.63 MHz, C.sub.6D.sub.6, 293K): δ 192.4 (s, Os—NCN), 192.1 (s, Os—NCN), 179.0 (s, Os—C), 170.1 (s, Os—C), 146.7 (s, C Ph), 146.5 (s, C Ph), 137.2 (s, C Bzm), 137.1 (s, C Bzm), 133.4 (s, C Bzm), 133.2 (s, C Bzm), 128.4 (q, J.sub.C—F=270.4 Hz, CF.sub.3) 122.0 (s, CH Bzm), 121.8 (s, CH Bzm), 121.7 (s, CH Bzm), 121.4 (s, CH Bzm), 119.0 (q, J.sub.C—F=30.7 Hz, CCF.sub.3) 118.5 (s, CH Ph), 110.14 (s, CH Bzm), 110.08 (s, CH Bzm), 109.30 (s, CH Bzm), 109.28 (s, CH Bzm), 107.0 (s, CH Ph), 103.1 (q, J.sub.C—F=3.8 Hz, CH Ph), 32.8 (s, CH.sub.3), 32.7 (s, CH.sub.3). .sup.19F NMR (282 MHz, C.sub.6D.sub.6, 293K): δ −57.1 (CF.sub.3).

[0052] According to an aspect of the present disclosure, a method of making an osmium(II) complex having Formula I

[0053] L.sup.1-Os-L.sup.2, wherein L.sup.1 and L.sup.2 are independently a biscarbene tridentate ligand, wherein L.sup.1 and L.sup.2 can be same or different is disclosed. The method comprises: (a) reacting a precursor of ligand L.sup.1 with an osmium precursor to form an intermediate product, wherein the osmium precursor having the formula OsH.sub.x(PR.sub.3).sub.y, wherein x is an integer from 2 to 6 and y is an integer from 2 to 5, and R is selected from the group consisting of aryl, alkyl and cycloalkyl; and (b) reacting a precursor of ligand L.sup.2 with said intermediate product.

[0054] In one embodiment of the method, L.sup.1 and L.sup.2 are monoanionic ligands. In some embodiments, L.sup.1 and L.sup.2 are independently selected from ligands having Formula II:

##STR00009##

wherein Y.sup.1, Y.sup.2 and Y.sup.3 comprise C or N; wherein R.sup.3 and R.sup.4 may represent mono-, or di-substitutions, or no substitution; wherein R.sup.5 may represent mono-, di-, or tri-substitutions, or no substitution; wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein any two adjacent substituents of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are optionally joined to form a ring; and wherein the dash lines show the connection points to osmium.

[0055] In one embodiment of the method, Y.sup.1, Y.sup.2 and Y.sup.3 comprise C. In one embodiment, Y.sup.1 and Y.sup.3 comprise C, and Y.sup.2 is N. In one embodiment, Y.sup.1 and Y.sup.3 are N, and Y.sup.2 comprise C. In one embodiment, R.sup.1 and R.sup.2 are independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and partially or fully deuterated variants thereof. In one embodiment, R.sup.1 and R.sup.2 are independently selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, partially or fully deuterated variants thereof, and combinations thereof.

[0056] In one embodiment of the method, the osmium precursor having the formula OsH.sub.6(PR.sub.3).sub.2. In another embodiment, R in the osmium precursor having the formula OsH.sub.x(PR.sub.3).sub.y is selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, cyclohexyl, phenyl, 2,6-dimethylphenyl, and 2-methylphenyl. In other embodiment, R is 1-methylethyl.

[0057] In another embodiment, the ligands having Formula II are selected from the group consisting of:

##STR00010## ##STR00011## ##STR00012## ##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025##

[0058] According to an embodiment, a compound having a structure according to Formula I, L.sup.1-Os-L.sup.2 is provided, wherein L.sup.1 and L.sup.2 are different; wherein L.sup.1 and L.sup.2 are independently selected from ligands having Formula II,

##STR00026##

In Formula II, Y.sup.1, Y.sup.2 and Y.sup.3 comprise C or N; wherein R.sup.3 and R.sup.4 may represent mono-, or di-substitutions, or no substitution; wherein R.sup.5 may represent mono-, di-, or tri-substitutions, or no substitution; wherein R.sup.1 and R.sup.2 are independently selected from the group consisting of alkyl and cycloalkyl; wherein R.sup.3, R.sup.4 and R.sup.5 are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof; wherein any two adjacent substituents of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are optionally joined to condense into a fused ring; and wherein the dash lines show the connection points to osmium.

[0059] In an embodiment of the compound, Y.sup.1, Y.sup.2 and Y.sup.3 comprise C. In one embodiment of the compound, Y.sup.1 and Y.sup.3 comprise C, and Y.sup.2 is N. In some embodiments, Y.sup.1 and Y.sup.3 are N, and Y.sup.2 comprise C. In one embodiment, R.sup.1 and R.sup.2 are independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and partially or fully deuterated variants thereof. In one embodiment, R.sup.1 and R.sup.2 are independently selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, partially or fully deuterated variants thereof, and combinations thereof.

[0060] In some embodiments of the compound, L.sup.1 and L.sup.2 are independently selected from ligands having Formula III:

##STR00027##

wherein X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6, X.sup.7 and X.sup.8 comprise C or N. In one embodiment, X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6, X.sup.7 and X.sup.8 comprise C.

[0061] In some embodiments, the ligands having Formula II are selected from the group consisting of: L.sup.101 to L.sup.159 defined herein.

[0062] In some embodiments, the compound having a structure according to Formula I, L.sup.1-Os-L.sup.2 is selected from the group consisting of Compounds 1 to 1159 defined in Table 1 below:

TABLE-US-00001 TABLE 1 Compound Number L.sup.1 L.sup.2 1. L.sup.101 L.sup.102 2. L.sup.101 L.sup.103 3. L.sup.101 L.sup.104 4. L.sup.101 L.sup.105 5. L.sup.101 L.sup.106 6. L.sup.101 L.sup.107 7. L.sup.101 L.sup.108 8. L.sup.101 L.sup.109 9. L.sup.101 L.sup.110 10. L.sup.101 L.sup.111 11. L.sup.101 L.sup.112 12. L.sup.101 L.sup.113 13. L.sup.101 L.sup.114 14. L.sup.101 L.sup.115 15. L.sup.101 L.sup.116 16. L.sup.101 L.sup.117 17. L.sup.101 L.sup.118 18. L.sup.101 L.sup.119 19. L.sup.101 L.sup.120 20. L.sup.101 L.sup.121 21. L.sup.101 L.sup.122 22. L.sup.101 L.sup.123 23. L.sup.101 L.sup.124 24. L.sup.101 L.sup.125 25. L.sup.101 L.sup.126 26. L.sup.101 L.sup.127 27. L.sup.101 L.sup.128 28. L.sup.101 L.sup.129 29. L.sup.101 L.sup.130 30. L.sup.101 L.sup.131 31. L.sup.101 L.sup.132 32. L.sup.101 L.sup.133 33. L.sup.101 L.sup.134 34. L.sup.101 L.sup.135 35. L.sup.101 L.sup.136 36. L.sup.101 L.sup.137 37. L.sup.101 L.sup.138 38. L.sup.101 L.sup.139 39. L.sup.101 L.sup.140 40. L.sup.101 L.sup.141 41. L.sup.101 L.sup.142 42. L.sup.101 L.sup.143 43. L.sup.101 L.sup.144 44. L.sup.101 L.sup.145 45. L.sup.101 L.sup.146 46. L.sup.101 L.sup.147 47. L.sup.101 L.sup.148 48. L.sup.101 L.sup.149 49. L.sup.101 L.sup.150 50. L.sup.101 L.sup.151 51. L.sup.101 L.sup.152 52. L.sup.101 L.sup.153 53. L.sup.101 L.sup.154 54. L.sup.101 L.sup.155 55. L.sup.101 L.sup.156 56. L.sup.101 L.sup.157 57. L.sup.101 L.sup.158 58. L.sup.101 L.sup.159 59. L.sup.102 L.sup.103 60. L.sup.102 L.sup.104 61. L.sup.102 L.sup.105 62. L.sup.102 L.sup.106 63. L.sup.102 L.sup.107 64. L.sup.102 L.sup.108 65. L.sup.102 L.sup.109 66. L.sup.102 L.sup.110 67. L.sup.102 L.sup.111 68. L.sup.102 L.sup.112 69. L.sup.102 L.sup.113 70. L.sup.102 L.sup.114 71. L.sup.102 L.sup.115 72. L.sup.102 L.sup.116 73. L.sup.102 L.sup.117 74. L.sup.102 L.sup.118 75. L.sup.102 L.sup.119 76. L.sup.102 L.sup.120 77. L.sup.102 L.sup.121 78. L.sup.102 L.sup.122 79. L.sup.102 L.sup.123 80. L.sup.102 L.sup.124 81. L.sup.102 L.sup.125 82. L.sup.102 L.sup.126 83. L.sup.102 L.sup.127 84. L.sup.102 L.sup.128 85. L.sup.102 L.sup.129 86. L.sup.102 L.sup.130 87. L.sup.102 L.sup.131 88. L.sup.102 L.sup.132 89. L.sup.102 L.sup.133 90. L.sup.102 L.sup.134 91. L.sup.102 L.sup.135 92. L.sup.102 L.sup.136 93. L.sup.102 L.sup.137 94. L.sup.102 L.sup.138 95. L.sup.102 L.sup.139 96. L.sup.102 L.sup.140 97. L.sup.102 L.sup.141 98. L.sup.102 L.sup.142 99. L.sup.102 L.sup.143 100. L.sup.102 L.sup.144 101. L.sup.102 L.sup.145 102. L.sup.102 L.sup.146 103. L.sup.102 L.sup.147 104. L.sup.102 L.sup.148 105. L.sup.102 L.sup.149 106. L.sup.102 L.sup.150 107. L.sup.102 L.sup.151 108. L.sup.102 L.sup.152 109. L.sup.102 L.sup.153 110. L.sup.102 L.sup.154 111. L.sup.102 L.sup.155 112. L.sup.102 L.sup.156 113. L.sup.102 L.sup.157 114. L.sup.102 L.sup.158 115. L.sup.102 L.sup.159 116. L.sup.103 L.sup.104 117. L.sup.103 L.sup.105 118. L.sup.103 L.sup.106 119. L.sup.103 L.sup.107 120. L.sup.103 L.sup.108 121. 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L.sup.112 L.sup.130 602. L.sup.112 L.sup.131 603. L.sup.112 L.sup.132 604. L.sup.112 L.sup.133 605. L.sup.112 L.sup.134 606. L.sup.112 L.sup.135 607. L.sup.112 L.sup.136 608. L.sup.112 L.sup.137 609. L.sup.112 L.sup.138 610. L.sup.112 L.sup.139 611. L.sup.112 L.sup.140 612. L.sup.112 L.sup.141 613. L.sup.112 L.sup.142 614. L.sup.112 L.sup.143 615. L.sup.112 L.sup.144 616. L.sup.112 L.sup.145 617. L.sup.112 L.sup.146 618. L.sup.112 L.sup.147 619. L.sup.112 L.sup.148 620. L.sup.112 L.sup.149 621. L.sup.112 L.sup.150 622. L.sup.112 L.sup.151 623. L.sup.112 L.sup.152 624. L.sup.112 L.sup.153 625. L.sup.112 L.sup.154 626. L.sup.112 L.sup.155 627. L.sup.112 L.sup.156 628. L.sup.112 L.sup.157 629. L.sup.112 L.sup.158 630. L.sup.112 L.sup.159 631. L.sup.113 L.sup.114 632. L.sup.113 L.sup.115 633. L.sup.113 L.sup.116 634. L.sup.113 L.sup.117 635. L.sup.113 L.sup.118 636. L.sup.113 L.sup.119 637. L.sup.113 L.sup.120 638. L.sup.113 L.sup.121 639. L.sup.113 L.sup.122 640. L.sup.113 L.sup.123 641. L.sup.113 L.sup.124 642. L.sup.113 L.sup.125 643. L.sup.113 L.sup.126 644. L.sup.113 L.sup.127 645. L.sup.113 L.sup.128 646. L.sup.113 L.sup.129 647. L.sup.113 L.sup.130 648. L.sup.113 L.sup.131 649. L.sup.113 L.sup.132 650. L.sup.113 L.sup.133 651. L.sup.113 L.sup.134 652. L.sup.113 L.sup.135 653. L.sup.113 L.sup.136 654. L.sup.113 L.sup.137 655. L.sup.113 L.sup.138 656. L.sup.113 L.sup.139 657. L.sup.113 L.sup.140 658. L.sup.113 L.sup.141 659. L.sup.113 L.sup.142 660. L.sup.113 L.sup.143 661. L.sup.113 L.sup.144 662. L.sup.113 L.sup.145 663. L.sup.113 L.sup.146 664. L.sup.113 L.sup.147 665. L.sup.113 L.sup.148 666. L.sup.113 L.sup.149 667. L.sup.113 L.sup.150 668. L.sup.113 L.sup.151 669. L.sup.113 L.sup.152 670. L.sup.113 L.sup.153 671. L.sup.113 L.sup.154 672. L.sup.113 L.sup.155 673. L.sup.113 L.sup.156 674. L.sup.113 L.sup.157 675. L.sup.113 L.sup.158 676. L.sup.113 L.sup.159 677. L.sup.114 L.sup.115 678. L.sup.114 L.sup.116 679. L.sup.114 L.sup.117 680. L.sup.114 L.sup.118 681. L.sup.114 L.sup.119 682. L.sup.114 L.sup.120 683. L.sup.114 L.sup.121 684. L.sup.114 L.sup.122 685. L.sup.114 L.sup.123 686. L.sup.114 L.sup.124 687. L.sup.114 L.sup.125 688. L.sup.114 L.sup.126 689. L.sup.114 L.sup.127 690. L.sup.114 L.sup.128 691. L.sup.114 L.sup.129 692. L.sup.114 L.sup.130 693. L.sup.114 L.sup.131 694. L.sup.114 L.sup.132 695. L.sup.114 L.sup.133 696. L.sup.114 L.sup.134 697. L.sup.114 L.sup.135 698. L.sup.114 L.sup.136 699. L.sup.114 L.sup.137 700. L.sup.114 L.sup.138 701. L.sup.114 L.sup.139 702. L.sup.114 L.sup.140 703. L.sup.114 L.sup.141 704. L.sup.114 L.sup.142 705. L.sup.114 L.sup.143 706. L.sup.114 L.sup.144 707. L.sup.114 L.sup.145 708. L.sup.114 L.sup.146 709. L.sup.114 L.sup.147 710. L.sup.114 L.sup.148 711. L.sup.114 L.sup.149 712. L.sup.114 L.sup.150 713. L.sup.114 L.sup.151 714. L.sup.114 L.sup.152 715. L.sup.114 L.sup.153 716. L.sup.114 L.sup.154 717. L.sup.114 L.sup.155 718. L.sup.114 L.sup.156 719. L.sup.114 L.sup.157 720. L.sup.114 L.sup.158 721. L.sup.114 L.sup.159 722. L.sup.115 L.sup.116 723. L.sup.115 L.sup.117 724. L.sup.115 L.sup.118 725. L.sup.115 L.sup.119 726. L.sup.115 L.sup.120 727. L.sup.115 L.sup.121 728. L.sup.115 L.sup.122 729. L.sup.115 L.sup.123 730. L.sup.115 L.sup.124 731. L.sup.115 L.sup.125 732. L.sup.115 L.sup.126 733. L.sup.115 L.sup.127 734. L.sup.115 L.sup.128 735. L.sup.115 L.sup.129 736. L.sup.115 L.sup.130 737. L.sup.115 L.sup.131 738. L.sup.115 L.sup.132 739. L.sup.115 L.sup.133 740. L.sup.115 L.sup.134 741. L.sup.115 L.sup.135 742. L.sup.115 L.sup.136 743. L.sup.115 L.sup.137 744. L.sup.115 L.sup.138 745. L.sup.115 L.sup.139 746. L.sup.115 L.sup.140 747. L.sup.115 L.sup.141 748. L.sup.115 L.sup.142 749. L.sup.115 L.sup.143 750. L.sup.115 L.sup.144 751. L.sup.115 L.sup.145 752. L.sup.115 L.sup.146 753. L.sup.115 L.sup.147 754. L.sup.115 L.sup.148 755. L.sup.115 L.sup.149 756. L.sup.115 L.sup.150 757. L.sup.115 L.sup.151 758. L.sup.115 L.sup.152 759. L.sup.115 L.sup.153 760. L.sup.115 L.sup.154 761. L.sup.115 L.sup.155 762. L.sup.115 L.sup.156 763. L.sup.115 L.sup.157 764. L.sup.115 L.sup.158 765. L.sup.115 L.sup.159 766. L.sup.116 L.sup.117 767. L.sup.116 L.sup.118 768. L.sup.116 L.sup.119 769. L.sup.116 L.sup.120 770. L.sup.116 L.sup.121 771. L.sup.116 L.sup.122 772. L.sup.116 L.sup.123 773. L.sup.116 L.sup.124 774. L.sup.116 L.sup.125 775. L.sup.116 L.sup.126 776. L.sup.116 L.sup.127 777. L.sup.116 L.sup.128 778. L.sup.116 L.sup.129 779. L.sup.116 L.sup.130 780. L.sup.116 L.sup.131 781. L.sup.116 L.sup.132 782. L.sup.116 L.sup.133 783. L.sup.116 L.sup.134 784. L.sup.116 L.sup.135 785. L.sup.116 L.sup.136 786. L.sup.116 L.sup.137 787. L.sup.116 L.sup.138 788. L.sup.116 L.sup.139 789. L.sup.116 L.sup.140 790. L.sup.116 L.sup.141 791. L.sup.116 L.sup.142 792. L.sup.116 L.sup.143 793. L.sup.116 L.sup.144 794. L.sup.116 L.sup.145 795. L.sup.116 L.sup.146 796. L.sup.116 L.sup.147 797. L.sup.116 L.sup.148 798. L.sup.116 L.sup.149 799. L.sup.116 L.sup.150 800. L.sup.116 L.sup.151 801. L.sup.116 L.sup.152 802. L.sup.116 L.sup.153 803. L.sup.116 L.sup.154 804. L.sup.116 L.sup.155 805. L.sup.116 L.sup.156 806. L.sup.116 L.sup.157 807. L.sup.116 L.sup.158 808. L.sup.116 L.sup.159 809. L.sup.117 L.sup.118 810. L.sup.117 L.sup.119 811. L.sup.117 L.sup.120 812. L.sup.117 L.sup.121 813. L.sup.117 L.sup.122 814. L.sup.117 L.sup.123 815. L.sup.117 L.sup.124 816. L.sup.117 L.sup.125 817. L.sup.117 L.sup.126 818. L.sup.117 L.sup.127 819. L.sup.117 L.sup.128 820. L.sup.117 L.sup.129 821. L.sup.117 L.sup.130 822. L.sup.117 L.sup.131 823. L.sup.117 L.sup.132 824. L.sup.117 L.sup.133 825. L.sup.117 L.sup.134 826. L.sup.117 L.sup.135 827. L.sup.117 L.sup.136 828. L.sup.117 L.sup.137 829. L.sup.117 L.sup.138 830. L.sup.117 L.sup.139 831. L.sup.117 L.sup.140 832. L.sup.117 L.sup.141 833. L.sup.117 L.sup.142 834. L.sup.117 L.sup.143 835. L.sup.117 L.sup.144 836. L.sup.117 L.sup.145 837. L.sup.117 L.sup.146 838. L.sup.117 L.sup.147 839. L.sup.117 L.sup.148 840. L.sup.117 L.sup.149 841. L.sup.117 L.sup.150 842. L.sup.117 L.sup.151 843. L.sup.117 L.sup.152 844. L.sup.117 L.sup.153 845. L.sup.117 L.sup.154 846. L.sup.117 L.sup.155 847. L.sup.117 L.sup.156 848. L.sup.117 L.sup.157 849. L.sup.117 L.sup.158 850. L.sup.117 L.sup.159 851. L.sup.118 L.sup.119 852. L.sup.118 L.sup.120 853. L.sup.118 L.sup.121 854. L.sup.118 L.sup.122 855. L.sup.118 L.sup.123 856. L.sup.118 L.sup.124 857. L.sup.118 L.sup.125 858. L.sup.118 L.sup.126 859. L.sup.118 L.sup.127 860. L.sup.118 L.sup.128 861. L.sup.118 L.sup.129 862. L.sup.118 L.sup.130 863. L.sup.118 L.sup.131 864. L.sup.118 L.sup.132 865. L.sup.118 L.sup.133 866. L.sup.118 L.sup.134 867. L.sup.118 L.sup.135 868. L.sup.118 L.sup.136 869. L.sup.118 L.sup.137 870. L.sup.118 L.sup.138 871. L.sup.118 L.sup.139 872. L.sup.118 L.sup.140 873. L.sup.118 L.sup.141 874. L.sup.118 L.sup.142 875. L.sup.118 L.sup.143 876. L.sup.118 L.sup.144 877. L.sup.118 L.sup.145 878. L.sup.118 L.sup.146 879. L.sup.118 L.sup.147 880. L.sup.118 L.sup.148 881. L.sup.118 L.sup.149 882. L.sup.118 L.sup.150 883. L.sup.118 L.sup.151 884. L.sup.118 L.sup.152 885. L.sup.118 L.sup.153 886. L.sup.118 L.sup.154 887. L.sup.118 L.sup.155 888. L.sup.118 L.sup.156 889. L.sup.118 L.sup.157 890. L.sup.118 L.sup.158 891. L.sup.118 L.sup.159 892. L.sup.119 L.sup.120 893. L.sup.119 L.sup.121 894. L.sup.119 L.sup.122 895. L.sup.119 L.sup.123 896. L.sup.119 L.sup.124 897. L.sup.119 L.sup.125 898. L.sup.119 L.sup.126 899. L.sup.119 L.sup.127 900. L.sup.119 L.sup.128 901. L.sup.119 L.sup.129 902. L.sup.119 L.sup.130 903. L.sup.119 L.sup.131 904. L.sup.119 L.sup.132 905. L.sup.119 L.sup.133 906. L.sup.119 L.sup.134 907. L.sup.119 L.sup.135 908. L.sup.119 L.sup.136 909. L.sup.119 L.sup.137 910. L.sup.119 L.sup.138 911. L.sup.119 L.sup.139 912. L.sup.119 L.sup.140 913. L.sup.119 L.sup.141 914. L.sup.119 L.sup.142 915. L.sup.119 L.sup.143 916. L.sup.119 L.sup.144 917. L.sup.119 L.sup.145 918. L.sup.119 L.sup.146 919. L.sup.119 L.sup.147 920. L.sup.119 L.sup.148 921. L.sup.119 L.sup.149 922. L.sup.119 L.sup.150 923. L.sup.119 L.sup.151 924. L.sup.119 L.sup.152 925. L.sup.119 L.sup.153 926. L.sup.119 L.sup.154 927. L.sup.119 L.sup.155 928. L.sup.119 L.sup.156 929. L.sup.119 L.sup.157 930. L.sup.119 L.sup.158 931. L.sup.119 L.sup.159 932. L.sup.120 L.sup.121 933. L.sup.120 L.sup.122 934. L.sup.120 L.sup.123 935. L.sup.120 L.sup.124 936. L.sup.120 L.sup.125 937. L.sup.120 L.sup.126 938. L.sup.120 L.sup.127 939. L.sup.120 L.sup.128 940. L.sup.120 L.sup.129 941. L.sup.120 L.sup.130 942. L.sup.120 L.sup.131 943. L.sup.120 L.sup.132 944. L.sup.120 L.sup.133 945. L.sup.120 L.sup.134 946. L.sup.120 L.sup.135 947. L.sup.120 L.sup.136 948. L.sup.120 L.sup.137 949. L.sup.120 L.sup.138 950. L.sup.120 L.sup.139 951. L.sup.120 L.sup.140 952. L.sup.120 L.sup.141 953. L.sup.120 L.sup.142 954. L.sup.120 L.sup.143 955. L.sup.120 L.sup.144 956. L.sup.120 L.sup.145 957. L.sup.120 L.sup.146 958. L.sup.120 L.sup.147 959. L.sup.120 L.sup.148 960. L.sup.120 L.sup.149 961. L.sup.120 L.sup.150 962. L.sup.120 L.sup.151 963. L.sup.120 L.sup.152 964. L.sup.120 L.sup.153 965. L.sup.120 L.sup.154 966. L.sup.120 L.sup.155 967. L.sup.120 L.sup.156 968. L.sup.120 L.sup.157 969. L.sup.120 L.sup.158 970. L.sup.120 L.sup.159 971. L.sup.121 L.sup.122 972. L.sup.121 L.sup.123 973. L.sup.121 L.sup.124 974. L.sup.121 L.sup.125 975. L.sup.121 L.sup.126 976. L.sup.121 L.sup.127 977. L.sup.121 L.sup.128 978. L.sup.121 L.sup.129 979. L.sup.121 L.sup.130 980. L.sup.121 L.sup.131 981. L.sup.121 L.sup.132 982. L.sup.121 L.sup.133 983. L.sup.121 L.sup.134 984. L.sup.121 L.sup.135 985. L.sup.121 L.sup.136 986. L.sup.121 L.sup.137 987. L.sup.121 L.sup.138 988. L.sup.121 L.sup.139 989. L.sup.121 L.sup.140 990. L.sup.121 L.sup.141 991. L.sup.121 L.sup.142 992. L.sup.121 L.sup.143 993. L.sup.121 L.sup.144 994. L.sup.121 L.sup.145 995. L.sup.121 L.sup.146 996. L.sup.121 L.sup.147 997. L.sup.121 L.sup.148 998. L.sup.121 L.sup.149 999. L.sup.121 L.sup.150 1000. L.sup.121 L.sup.151 1001. L.sup.121 L.sup.152 1002. L.sup.121 L.sup.153 1003. L.sup.121 L.sup.154 1004. L.sup.121 L.sup.155 1005. L.sup.121 L.sup.156 1006. L.sup.121 L.sup.157 1007. L.sup.121 L.sup.158 1008. L.sup.121 L.sup.159 1009. L.sup.122 L.sup.123 1010. L.sup.122 L.sup.124 1011. L.sup.122 L.sup.125 1012. L.sup.122 L.sup.126 1013. L.sup.122 L.sup.127 1014. L.sup.122 L.sup.128 1015. L.sup.122 L.sup.129 1016. L.sup.122 L.sup.130 1017. L.sup.122 L.sup.131 1018. L.sup.122 L.sup.132 1019. L.sup.122 L.sup.133 1020. L.sup.122 L.sup.134 1021. L.sup.122 L.sup.135 1022. L.sup.122 L.sup.136 1023. L.sup.122 L.sup.137 1024. L.sup.122 L.sup.138 1025. L.sup.122 L.sup.139 1026. L.sup.122 L.sup.140 1027. L.sup.122 L.sup.141 1028. L.sup.122 L.sup.142 1029. L.sup.122 L.sup.143 1030. L.sup.122 L.sup.144 1031. L.sup.122 L.sup.145 1032. L.sup.122 L.sup.146 1033. L.sup.122 L.sup.147 1034. L.sup.122 L.sup.148 1035. L.sup.122 L.sup.149 1036. L.sup.122 L.sup.150 1037. L.sup.122 L.sup.151 1038. L.sup.122 L.sup.152 1039. L.sup.122 L.sup.153 1040. L.sup.122 L.sup.154 1041. L.sup.122 L.sup.155 1042. L.sup.122 L.sup.156 1043. L.sup.122 L.sup.157 1044. L.sup.122 L.sup.158 1045. L.sup.122 L.sup.159 1046. L.sup.123 L.sup.124 1047. L.sup.123 L.sup.125 1048. L.sup.123 L.sup.126 1049. L.sup.123 L.sup.127 1050. L.sup.123 L.sup.128 1051. L.sup.123 L.sup.129 1052. L.sup.123 L.sup.130 1053. L.sup.123 L.sup.131 1054. L.sup.123 L.sup.132 1055. L.sup.123 L.sup.133 1056. L.sup.123 L.sup.134 1057. L.sup.123 L.sup.135 1058. L.sup.123 L.sup.136 1059. L.sup.123 L.sup.137 1060. L.sup.123 L.sup.138 1061. L.sup.123 L.sup.139 1062. L.sup.123 L.sup.140 1063. L.sup.123 L.sup.141 1064. L.sup.123 L.sup.142 1065. L.sup.123 L.sup.143 1066. L.sup.123 L.sup.144 1067. L.sup.123 L.sup.145 1068. L.sup.123 L.sup.146 1069. L.sup.123 L.sup.147 1070. L.sup.123 L.sup.148 1071. L.sup.123 L.sup.149 1072. L.sup.123 L.sup.150 1073. L.sup.123 L.sup.151 1074. L.sup.123 L.sup.152 1075. L.sup.123 L.sup.153 1076. L.sup.123 L.sup.154 1077. L.sup.123 L.sup.155 1078. L.sup.123 L.sup.156 1079. L.sup.123 L.sup.157 1080. L.sup.123 L.sup.158 1081. L.sup.123 L.sup.159 1082. L.sup.124 L.sup.125 1083. L.sup.124 L.sup.126 1084. L.sup.124 L.sup.127 1085. L.sup.124 L.sup.128 1086. L.sup.124 L.sup.129 1087. L.sup.124 L.sup.130 1088. L.sup.124 L.sup.131 1089. L.sup.124 L.sup.132 1090. L.sup.124 L.sup.133 1091. L.sup.124 L.sup.134 1092. L.sup.124 L.sup.135 1093. L.sup.124 L.sup.136 1094. L.sup.124 L.sup.137 1095. L.sup.124 L.sup.138 1096. L.sup.124 L.sup.139 1097. L.sup.124 L.sup.140 1098. L.sup.124 L.sup.141 1099. L.sup.124 L.sup.142 1100. L.sup.124 L.sup.143 1101. L.sup.124 L.sup.144 1102. L.sup.124 L.sup.145 1103. L.sup.124 L.sup.146 1104. L.sup.124 L.sup.147 1105. L.sup.124 L.sup.148 1106. L.sup.124 L.sup.149 1107. L.sup.124 L.sup.150 1108. L.sup.124 L.sup.151 1109. L.sup.124 L.sup.152 1110. L.sup.124 L.sup.153 1111. L.sup.124 L.sup.154 1112. L.sup.124 L.sup.155 1113. L.sup.124 L.sup.156 1114. L.sup.124 L.sup.157 1115. L.sup.124 L.sup.158 1116. L.sup.124 L.sup.159 1117. L.sup.125 L.sup.126 1118. L.sup.125 L.sup.127 1119. L.sup.125 L.sup.128 1120. L.sup.125 L.sup.129 1121. L.sup.125 L.sup.130 1122. L.sup.125 L.sup.131 1123. L.sup.125 L.sup.132 1124. L.sup.125 L.sup.133 1125. L.sup.125 L.sup.134 1126. L.sup.125 L.sup.135 1127. L.sup.125 L.sup.136 1128. L.sup.125 L.sup.137 1129. L.sup.125 L.sup.138 1130. L.sup.125 L.sup.139 1131. L.sup.125 L.sup.140 1132. L.sup.125 L.sup.141 1133. L.sup.125 L.sup.142 1134. L.sup.125 L.sup.143 1135. L.sup.125 L.sup.144 1136. L.sup.125 L.sup.145 1137. L.sup.125 L.sup.146 1138. L.sup.125 L.sup.147 1139. L.sup.125 L.sup.148 1140. L.sup.125 L.sup.149 1141. L.sup.125 L.sup.150 1142. L.sup.125 L.sup.151 1143. L.sup.125 L.sup.152 1144. L.sup.125 L.sup.153 1145. L.sup.125 L.sup.154 1146. L.sup.125 L.sup.155 1147. L.sup.125 L.sup.156 1148. L.sup.125 L.sup.157 1149. L.sup.125 L.sup.158 1150. L.sup.125 L.sup.159

[0063] In one embodiment, a first device comprising a first organic light emitting device is disclosed. The first organic light emitting device comprises an anode; a cathode; and an organic layer, disposed between the anode and the cathode, comprising a compound having the structure according Formula I, L.sup.1-Os-L.sup.2; wherein L.sup.1 and L.sup.2 are different; wherein L.sup.1 and L.sup.2 are independently selected from ligands having Formula II:

##STR00028##

wherein Y.sup.1, Y.sup.2 and Y.sup.3 comprise C or N; wherein R.sup.3 and R.sup.4 may represent mono-, or di-substitutions, or no substitution; wherein R.sup.5 may represent mono-, di-, or tri-substitutions, or no substitution; wherein R.sup.1 and R.sup.2 are independently selected from the group consisting of alkyl and cycloalkyl; wherein R.sup.3, R.sup.4 and R.sup.5 are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof; wherein any two adjacent substituents of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are optionally joined to condense into a fused ring; and wherein the dash lines show the connection points to osmium.

[0064] In one embodiment of the first device, Y.sup.1, Y.sup.2 and Y.sup.3 comprise C. In one embodiment, Y.sup.1, Y.sup.2 and Y.sup.3 are N. In one embodiment, R.sup.1 and R.sup.2 are independently selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, partially or fully deuterated variants thereof, and combinations thereof.

[0065] In some embodiments of the first device, L.sup.1 and L.sup.2 are independently selected from ligands having Formula III:

##STR00029##

[0066] wherein X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6, X.sup.7 and X.sup.8 comprise C or N. In some embodiments, X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6, X.sup.7 and X.sup.8 comprise C.

[0067] In some embodiments of the first device, the ligands having Formula II are selected from the group consisting of L.sup.101 to L.sup.159 defined herein.

[0068] In some embodiments of the first device, the first emitting compound is selected from the group consisting of Compounds 1 to 1159 defined in Table 1.

[0069] The first device can be one or more of a consumer product, an organic light-emitting device, and/or a lighting panel.

[0070] The organic layer in the organic light emitting device can be an emissive layer and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments.

[0071] The organic layer can also include a host. In some embodiments, the host can include a metal complex. In one embodiment, the host can be a metal 8-hydroxyquinolate. The host can be a triphenylene containing benzo-fused thiophene or benzo-fused furan. Any substituent in the host can be an unfused substituent independently selected from the group consisting of C.sub.nH.sub.2n+1, OC.sub.nH.sub.2n+1, OAr.sub.1, N(C.sub.nH.sub.2n+1).sub.2, N(Ar.sub.1)(Ar.sub.2), CH═CH—C.sub.nH.sub.2n+1, C≡C—C.sub.nH.sub.2n+1, Ar.sub.1, Ar.sub.1—Ar.sub.2, C.sub.nH.sub.2n—Ar.sub.1, or no substitution. In the preceding substituents n can range from 1 to 10; and Ar.sub.1 and Ar.sub.2 can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.

[0072] The host can be a compound selected from the group consisting of carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. The “aza” designation in the fragments described above, i.e., aza-dibenzofuran, aza-dibenzonethiophene, etc., means that one or more of the C—H groups in the respective fragment can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein. The host can include a metal complex. The host can be a specific compound selected from the group consisting of:

##STR00030## ##STR00031##

and combinations thereof.

[0073] In yet another aspect of the present disclosure, a formulation comprising the compound having a structure according to Formula I, L.sup.1-Os-L.sup.2, as defined herein, is disclosed. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, and an electron transport layer material, disclosed herein.

Combination with Other Materials

[0074] The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.

HIL/HTL:

[0075] A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but not limit to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoO.sub.x; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.

[0076] Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:

##STR00032##

[0077] Each of Ar.sup.1 to Ar.sup.9 is selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each Ar is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0078] In one aspect, Ar.sup.1 to Ar.sup.9 is independently selected from the group consisting of:

##STR00033##

wherein k is an integer from 1 to 20; X.sup.101 to X.sup.108 is C (including CH) or N; Z.sup.101 is NAr.sup.1, O, or S; Ar.sup.1 has the same group defined above.

[0079] Examples of metal complexes used in HIL or HTL include, but not limit to the following general formula:

##STR00034##

wherein Met is a metal, which can have an atomic weight greater than 40; (Y.sup.101-Y.sup.102) is a bidentate ligand, Y.sup.101 and Y.sup.102 are independently selected from C, N, O, P, and S; L.sup.101 is an ancillary ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.

[0080] In one aspect, (Y.sup.101-Y.sup.102) is a 2-phenylpyridine derivative. In another aspect, (Y.sup.101-Y.sup.102) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc.sup.+/Fc couple less than about 0.6 V.

Host:

[0081] The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. While the Table below categorizes host materials as preferred for devices that emit various colors, any host material may be used with any dopant so long as the triplet criteria is satisfied.

[0082] Examples of metal complexes used as host are preferred to have the following general formula:

##STR00035##

wherein Met is a metal; (Y.sup.103-Y.sup.104) is a bidentate ligand, Y.sup.103 and Y.sup.104 are independently selected from C, N, O, P, and S; L.sup.11 is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.

[0083] In one aspect, the metal complexes are:

##STR00036##

wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.

[0084] In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y.sup.103-Y.sup.104) is a carbene ligand.

[0085] Examples of organic compounds used as host are selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each group is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0086] In one aspect, host compound contains at least one of the following groups in the molecule:

##STR00037## ##STR00038##

wherein R.sup.101 to R.sup.107 is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above k is an integer from 0 to 20 or 1 to 20; k′″ is an integer from 0 to 20. X.sup.101 to X.sup.108 is selected from C (including CH) or N. Z.sup.101 and Z.sup.102 is selected from NR.sup.101, O, or S.

HBL:

[0087] A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED.

[0088] In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.

[0089] In another aspect, compound used in HBL contains at least one of the following groups in the molecule:

##STR00039##

wherein k is an integer from 1 to 20; L.sup.101 is an another ligand, k′ is an integer from 1 to 3.

ETL:

[0090] Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.

[0091] In one aspect, compound used in ETL contains at least one of the following groups in the molecule:

##STR00040##

wherein R.sup.101 is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. Ar.sup.1 to Ar.sup.3 has the similar definition as Ar's mentioned above. k is an integer from 1 to 20. X.sup.101 to X.sup.108 is selected from C (including CH) or N.

[0092] In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:

##STR00041##

wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L.sup.101 is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.

[0093] In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. encompasses undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also encompass undeuterated, partially deuterated, and fully deuterated versions thereof.

[0094] In addition to and/or in combination with the materials disclosed herein, many hole injection materials, hole transporting materials, host materials, dopant materials, exciton/hole blocking layer materials, electron transporting and electron injecting materials may be used in an OLED. Non-limiting examples of the materials that may be used in an OLED in combination with materials disclosed herein are listed in Table 2 below. Table 2 lists non-limiting classes of materials, non-limiting examples of compounds for each class, and references that disclose the materials.

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[0095] It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.