ORGANIC ELECTROLUMINESCENT MATERIALS AND DEVICES

Abstract
A compound having an ancillary ligand L1 having the formula:
Description
FIELD OF THE INVENTION

The present invention relates to compounds for use as emitters and devices, such as organic light emitting diodes, including the same. More particularly, the compounds disclosed herein are novel ancillary ligands for metal complexes.


BACKGROUND

Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.


OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.


One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Color may be measured using CIE coordinates, which are well known to the art.


One example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy)3, which has the following structure:




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In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line.


As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.


As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.


As used herein, “solution processible” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.


A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.


As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.


As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.


More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.


SUMMARY OF THE INVENTION

According to an embodiment, a compound is provided that comprises a first ligand L1 having the formula:




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Formula I; wherein R1, R2, R3, and R4 are independently selected from group consisting of alkyl, cycloalkyl, aryl, and heteroaryl; wherein at least one of R1, R2, R3, and R4 has at least two C; wherein R5 is selected from 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 the first ligand L1 is coordinated to a metal M having an atomic number greater than 40; and wherein two adjacent substituents are optionally joined to form into a ring.


According to another aspect of the present disclosure, a first device comprising a first organic light emitting device is provided. The first organic light emitting device can comprise an anode, a cathode, and an organic layer, disposed between the anode and the cathode. The organic layer can include a compound comprising the first ligand L1 having Formula I. The first device can be a consumer product, an organic light-emitting device, and/or a lighting panel.


The compounds disclosed herein are novel ancillary ligands for metal complexes. The incorporation of these ligands can narrow the emission spectrum, decrease evaporation temperature, and improve device efficiency. The inventors have discovered that incorporating these novel ancillary ligands in iridium complexes improved sublimation of the resulting iridium complexes, color spectrum of phosphorescence by these iridium complexes, and their EQE.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 shows an organic light emitting device.



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



FIG. 3 shows Formula I as disclosed herein.





DETAILED DESCRIPTION

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.


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.


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.



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.


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 F4-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.



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.


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.


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.


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 OVID. 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.


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.


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.


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.


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.


As used herein, “substituted” indicates that a substituent other than H is bonded to the relevant carbon. Thus, where R2 is monosubstituted, then one R2 must be other than H. Similarly, where R3 is disubstituted, then two of R3 must be other than H. Similarly, where R2 is unsubstituted R2 is hydrogen for all available positions.


According to an embodiment, novel ancillary ligands for metal complexes are disclosed. The inventors have discovered that incorporation of these ligands unexpectedly narrow the emission spectrum, decrease evaporation temperature, and improve device efficiency.


According to an embodiment, a compound is provided that comprises a first ligand LI having the formula:




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Formula I; wherein R1, R2, R3, and R4 are independently selected from group consisting of alkyl, cycloalkyl, aryl, and heteroaryl; wherein at least one of R1, R2, R3, and R4 has at least two C; wherein R5 is selected from 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 the first ligand L1 is coordinated to a metal M having an atomic number greater than 40; and wherein two adjacent substituents are optionally joined to form into a ring. The dash lines in Formula I show the connection points to the metal.


In one embodiment the metal M is Ir. In one embodiment R5 is selected from group consisting of hydrogen, deuterium, alkyl, cycloalkyl, and combinations thereof. In one embodiment, R5 is hydrogen.


In another embodiment, R1, R2, R3, and R4 are alkyl or cycloalkyl. In one embodiment, R1, R2, R3, and R4 are 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.


In one embodiment, the compound has the formula of M(L1)x(L2)y(L3)z; wherein L2 is a second ligand and L3 is a third ligand and L2 and L3 can be the same or different; x is 1, 2, or 3; y is 0, 1, or 2; z is 0, 1, or 2; and x+y+z is the oxidation state of the metal M.


In one embodiment, L2 and L3 are independently selected from the group consisting of:




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wherein Ra, Rb, Rc, and Rd can represent mono, di, tri, or tetra substitution, or no substitution; and Ra, Rb, Rc, and Rd 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; and wherein two adjacent substituents of Ra, Rb, Rc, and Rd are optionally joined to form a fused ring or form a multidentate ligand. In another embodiment, L3 is same as L2 and the compound has the formula of M(L1)(L2)2.


In another embodiment where the compound has the formula of M(L1)x(L2)y(L3)z, the first ligand L1 is selected from group consisting of:




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In one embodiment, the second ligand L2 is selected from group consisting of:




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In one embodiment, the compound having the formula of M(L1)(L2)2 can be selected from the group consisting of Compound 1 to Compound 1729 defined in Table 1 below:

















TABLE 1





Compound number
L1
L2
Compound number
L1
L2
Compound number
L1
L2







[0001]
LA1
LQ1
[0001]
LA5
LQ46
[0001]
LA9
LQ91


[0002]
LA1
LQ2
[0002]
LA5
LQ47
[0002]
LA9
LQ92


[0003]
LA1
LQ3
[0003]
LA5
LQ48
[0003]
LA9
LQ93


[0004]
LA1
LQ4
[0004]
LA5
LQ49
[0004]
LA9
LQ94


[0005]
LA1
LQ5
[0005]
LA5
LQ50
[0005]
LA9
LQ95


[0006]
LA1
LQ6
[0006]
LA5
LQ51
[0006]
LA9
LQ96


[0007]
LA1
LQ7
[0007]
LA5
LQ52
[0007]
LA9
LQ97


[0008]
LA1
LQ8
[0008]
LA5
LQ53
[0008]
LA9
LQ98


[0009]
LA1
LQ9
[0009]
LA5
LQ54
[0009]
LA9
LQ99


[0010]
LA1
LQ10
[0010]
LA5
LQ55
[0010]
LA9
LQ100


[0011]
LA1
LQ11
[0011]
LA5
LQ56
[0011]
LA9
LQ101


[0012]
LA1
LQ12
[0012]
LA5
LQ57
[0012]
LA9
LQ102


[0013]
LA1
LQ13
[0013]
LA5
LQ58
[0013]
LA9
LQ103


[0014]
LA1
LQ14
[0014]
LA5
LQ59
[0014]
LA9
LQ104


[0015]
LA1
LQ15
[0015]
LA5
LQ60
[0015]
LA9
LQ105


[0016]
LA1
LQ16
[0016]
LA5
LQ61
[0016]
LA9
LQ106


[0017]
LA1
LQ17
[0017]
LA5
LQ62
[0017]
LA9
LQ107


[0018]
LA1
LQ18
[0018]
LA5
LQ63
[0018]
LA9
LQ108


[0019]
LA1
LQ19
[0019]
LA5
LQ64
[0019]
LA9
LQ109


[0020]
LA1
LQ20
[0020]
LA5
LQ65
[0020]
LA9
LQ110


[0021]
LA1
LQ21
[0021]
LA5
LQ66
[0021]
LA9
LQ111


[0022]
LA1
LQ22
[0022]
LA5
LQ67
[0022]
LA9
LQ112


[0023]
LA1
LQ23
[0023]
LA5
LQ68
[0023]
LA9
LQ113


[0024]
LA1
LQ24
[0024]
LA5
LQ69
[0024]
LA9
LQ114


[0025]
LA1
LQ25
[0025]
LA5
LQ70
[0025]
LA9
LQ115


[0026]
LA1
LQ26
[0026]
LA5
LQ71
[0026]
LA9
LQ116


[0027]
LA1
LQ27
[0027]
LA5
LQ72
[0027]
LA9
LQ117


[0028]
LA1
LQ28
[0028]
LA5
LQ73
[0028]
LA9
LQ118


[0029]
LA1
LQ29
[0029]
LA5
LQ74
[0029]
LA9
LQ119


[0030]
LA1
LQ30
[0030]
LA5
LQ75
[0030]
LA9
LQ120


[0031]
LA1
LQ31
[0031]
LA5
LQ76
[0031]
LA9
LQ121


[0032]
LA1
LQ32
[0032]
LA5
LQ77
[0032]
LA9
LQ122


[0033]
LA1
LQ33
[0033]
LA5
LQ78
[0033]
LA9
LQ123


[0034]
LA1
LQ34
[0034]
LA5
LQ79
[0034]
LA9
LQ124


[0035]
LA1
LQ35
[0035]
LA5
LQ80
[0035]
LA9
LQ125


[0036]
LA1
LQ36
[0036]
LA5
LQ81
[0036]
LA9
LQ126


[0037]
LA1
LQ37
[0037]
LA5
LQ82
[0037]
LA9
LQ127


[0038]
LA1
LQ38
[0038]
LA5
LQ83
[0038]
LA9
LQ128


[0039]
LA1
LQ39
[0039]
LA5
LQ84
[0039]
LA9
LQ129


[0040]
LA1
LQ40
[0040]
LA5
LQ85
[0040]
LA9
LQ130


[0041]
LA1
LQ41
[0041]
LA5
LQ86
[0041]
LA9
LQ131


[0042]
LA1
LQ42
[0042]
LA5
LQ87
[0042]
LA9
LQ132


[0043]
LA1
LQ43
[0043]
LA5
LQ88
[0043]
LA9
LQ133


[0044]
LA1
LQ44
[0044]
LA5
LQ89
[0044]
LA10
LQ1


[0045]
LA1
LQ45
[0045]
LA5
LQ90
[0045]
LA10
LQ2


[0046]
LA1
LQ46
[0046]
LA5
LQ91
[0046]
LA10
LQ3


[0047]
LA1
LQ47
[0047]
LA5
LQ92
[0047]
LA10
LQ4


[0048]
LA1
LQ48
[0048]
LA5
LQ93
[0048]
LA10
LQ5


[0049]
LA1
LQ49
[0049]
LA5
LQ94
[0049]
LA10
LQ6


[0050]
LA1
LQ50
[0050]
LA5
LQ95
[0050]
LA10
LQ7


[0051]
LA1
LQ51
[0051]
LA5
LQ96
[0051]
LA10
LQ8


[0052]
LA1
LQ52
[0052]
LA5
LQ97
[0052]
LA10
LQ9


[0053]
LA1
LQ53
[0053]
LA5
LQ98
[0053]
LA10
LQ10


[0054]
LA1
LQ54
[0054]
LA5
LQ99
[0054]
LA10
LQ11


[0055]
LA1
LQ55
[0055]
LA5
LQ100
[0055]
LA10
LQ12


[0056]
LA1
LQ56
[0056]
LA5
LQ101
[0056]
LA10
LQ13


[0057]
LA1
LQ57
[0057]
LA5
LQ102
[0057]
LA10
LQ14


[0058]
LA1
LQ58
[0058]
LA5
LQ103
[0058]
LA10
LQ15


[0059]
LA1
LQ56
[0059]
LA5
LQ104
[0059]
LA10
LQ16


[0060]
LA1
LQ60
[0060]
LA5
LQ105
[0060]
LA10
LQ17


[0061]
LA1
LQ61
[0061]
LA5
LQ106
[0061]
LA10
LQ18


[0062]
LA1
LQ62
[0062]
LA5
LQ107
[0062]
LA10
LQ19


[0063]
LA1
LQ63
[0063]
LA5
LQ108
[0063]
LA10
LQ20


[0064]
LA1
LQ64
[0064]
LA5
LQ109
[0064]
LA10
LQ21


[0065]
LA1
LQ65
[0065]
LA5
LQ110
[0065]
LA10
LQ22


[0066]
LA1
LQ66
[0066]
LA5
LQ111
[0066]
LA10
LQ23


[0067]
LA1
LQ67
[0067]
LA5
LQ112
[0067]
LA10
LQ24


[0068]
LA1
LQ68
[0068]
LA5
LQ113
[0068]
LA10
LQ25


[0069]
LA1
LQ69
[0069]
LA5
LQ114
[0069]
LA10
LQ26


[0070]
LA1
LQ70
[0070]
LA5
LQ115
[0070]
LA10
LQ27


[0071]
LA1
LQ71
[0071]
LA5
LQ116
[0071]
LA10
LQ28


[0072]
LA1
LQ72
[0072]
LA5
LQ117
[0072]
LA10
LQ29


[0073]
LA1
LQ73
[0073]
LA5
LQ118
[0073]
LA10
LQ30


[0074]
LA1
LQ74
[0074]
LA5
LQ119
[0074]
LA10
LQ31


[0075]
LA1
LQ75
[0075]
LA5
LQ120
[0075]
LA10
LQ32


[0076]
LA1
LQ76
[0076]
LA5
LQ121
[0076]
LA10
LQ33


[0077]
LA1
LQ77
[0077]
LA5
LQ122
[0077]
LA10
LQ34


[0078]
LA1
LQ78
[0078]
LA5
LQ123
[0078]
LA10
LQ35


[0079]
LA1
LQ79
[0079]
LA5
LQ124
[0079]
LA10
LQ36


[0080]
LA1
LQ80
[0080]
LA5
LQ125
[0080]
LA10
LQ37


[0081]
LA1
LQ81
[0081]
LA5
LQ126
[0081]
LA10
LQ38


[0082]
LA1
LQ82
[0082]
LA5
LQ127
[0082]
LA10
LQ39


[0083]
LA1
LQ83
[0083]
LA5
LQ128
[0083]
LA10
LQ40


[0084]
LA1
LQ84
[0084]
LA5
LQ129
[0084]
LA10
LQ41


[0085]
LA1
LQ85
[0085]
LA5
LQ130
[0085]
LA10
LQ42


[0086]
LA1
LQ86
[0086]
LA5
LQ131
[0086]
LA10
LQ43


[0087]
LA1
LQ87
[0087]
LA5
LQ132
[0087]
LA10
LQ44


[0088]
LA1
LQ88
[0088]
LA5
LQ133
[0088]
LA10
LQ45


[0089]
LA1
LQ89
[0089]
LA6
LQ1
[0089]
LA10
LQ46


[0090]
LA1
LQ90
[0090]
LA6
LQ2
[0090]
LA10
LQ47


[0091]
LA1
LQ91
[0091]
LA6
LQ3
[0091]
LA10
LQ48


[0092]
LA1
LQ92
[0092]
LA6
LQ4
[0092]
LA10
LQ49


[0093]
LA1
LQ93
[0093]
LA6
LQ5
[0093]
LA10
LQ50


[0094]
LA1
LQ94
[0094]
LA6
LQ6
[0094]
LA10
LQ51


[0095]
LA1
LQ95
[0095]
LA6
LQ7
[0095]
LA10
LQ52


[0096]
LA1
LQ96
[0096]
LA6
LQ8
[0096]
LA10
LQ53


[0097]
LA1
LQ97
[0097]
LA6
LQ9
[0097]
LA10
LQ54


[0098]
LA1
LQ98
[0098]
LA6
LQ10
[0098]
LA10
LQ55


[0099]
LA1
LQ99
[0099]
LA6
LQ11
[0099]
LA10
LQ56


[00100]
LA1
LQ100
[00100]
LA6
LQ12
[00100]
LA10
LQ57


[00101]
LA1
LQ101
[00101]
LA6
LQ13
[00101]
LA10
LQ58


[00102]
LA1
LQ102
[00102]
LA6
LQ14
[00102]
LA10
LQ59


[00103]
LA1
LQ103
[00103]
LA6
LQ15
[00103]
LA10
LQ60


[00104]
LA1
LQ104
[00104]
LA6
LQ16
[00104]
LA10
LQ61


[00105]
LA1
LQ105
[00105]
LA6
LQ17
[00105]
LA10
LQ62


[00106]
LA1
LQ106
[00106]
LA6
LQ18
[00106]
LA10
LQ63


[00107]
LA1
LQ107
[00107]
LA6
LQ19
[00107]
LA10
LQ64


[00108]
LA1
LQ108
[00108]
LA6
LQ20
[00108]
LA10
LQ65


[00109]
LA1
LQ109
[00109]
LA6
LQ21
[00109]
LA10
LQ66


[00110]
LA1
LQ110
[00110]
LA6
LQ22
[00110]
LA10
LQ67


[00111]
LA1
LQ111
[00111]
LA6
LQ23
[00111]
LA10
LQ68


[00112]
LA1
LQ112
[00112]
LA6
LQ24
[00112]
LA10
LQ69


[00113]
LA1
LQ113
[00113]
LA6
LQ25
[00113]
LA10
LQ70


[00114]
LA1
LQ114
[00114]
LA6
LQ26
[00114]
LA10
LQ71


[00115]
LA1
LQ115
[00115]
LA6
LQ27
[00115]
LA10
LQ72


[00116]
LA1
LQ116
[00116]
LA6
LQ28
[00116]
LA10
LQ73


[00117]
LA1
LQ117
[00117]
LA6
LQ29
[00117]
LA10
LQ74


[00118]
LA1
LQ118
[00118]
LA6
LQ30
[00118]
LA10
LQ75


[00119]
LA1
LQ119
[00119]
LA6
LQ31
[00119]
LA10
LQ76


[00120]
LA1
LQ120
[00120]
LA6
LQ32
[00120]
LA10
LQ77


[00121]
LA1
LQ121
[00121]
LA6
LQ33
[00121]
LA10
LQ78


[00122]
LA1
LQ122
[00122]
LA6
LQ34
[00122]
LA10
LQ79


[00123]
LA1
LQ123
[00123]
LA6
LQ35
[00123]
LA10
LQ80


[00124]
LA1
LQ124
[00124]
LA6
LQ36
[00124]
LA10
LQ81


[00125]
LA1
LQ125
[00125]
LA6
LQ37
[00125]
LA10
LQ82


[00126]
LA1
LQ126
[00126]
LA6
LQ38
[00126]
LA10
LQ83


[00127]
LA1
LQ127
[00127]
LA6
LQ39
[00127]
LA10
LQ84


[00128]
LA1
LQ128
[00128]
LA6
LQ40
[00128]
LA10
LQ85


[00129]
LA1
LQ129
[00129]
LA6
LQ41
[00129]
LA10
LQ86


[00130]
LA1
LQ130
[00130]
LA6
LQ42
[00130]
LA10
LQ87


[00131]
LA1
LQ131
[00131]
LA6
LQ43
[00131]
LA10
LQ88


[00132]
LA1
LQ132
[00132]
LA6
LQ44
[00132]
LA10
LQ89


[00133]
LA1
LQ133
[00133]
LA6
LQ45
[00133]
LA10
LQ90


[00134]
LA2
LQ1
[00134]
LA6
LQ46
[00134]
LA10
LQ91


[00135]
LA2
LQ2
[00135]
LA6
LQ47
[00135]
LA10
LQ92


[00136]
LA2
LQ3
[00136]
LA6
LQ48
[00136]
LA10
LQ93


[00137]
LA2
LQ4
[00137]
LA6
LQ49
[00137]
LA10
LQ94


[00138]
LA2
LQ5
[00138]
LA6
LQ50
[00138]
LA10
LQ95


[00139]
LA2
LQ6
[00139]
LA6
LQ51
[00139]
LA10
LQ96


[00140]
LA2
LQ7
[00140]
LA6
LQ52
[00140]
LA10
LQ97


[00141]
LA2
LQ8
[00141]
LA6
LQ53
[00141]
LA10
LQ98


[00142]
LA2
LQ9
[00142]
LA6
LQ54
[00142]
LA10
LQ99


[00143]
LA2
LQ10
[00143]
LA6
LQ55
[00143]
LA10
LQ100


[00144]
LA2
LQ11
[00144]
LA6
LQ56
[00144]
LA10
LQ101


[00145]
LA2
LQ12
[00145]
LA6
LQ57
[00145]
LA10
LQ102


[00146]
LA2
LQ13
[00146]
LA6
LQ58
[00146]
LA10
LQ103


[00147]
LA2
LQ14
[00147]
LA6
LQ59
[00147]
LA10
LQ104


[00148]
LA2
LQ15
[00148]
LA6
LQ60
[00148]
LA10
LQ105


[00149]
LA2
LQ16
[00149]
LA6
LQ61
[00149]
LA10
LQ106


[00150]
LA2
LQ17
[00150]
LA6
LQ62
[00150]
LA10
LQ107


[00151]
LA2
LQ18
[00151]
LA6
LQ63
[00151]
LA10
LQ108


[00152]
LA2
LQ19
[00152]
LA6
LQ64
[00152]
LA10
LQ109


[00153]
LA2
LQ20
[00153]
LA6
LQ65
[00153]
LA10
LQ110


[00154]
LA2
LQ21
[00154]
LA6
LQ66
[00154]
LA10
LQ111


[00155]
LA2
LQ22
[00155]
LA6
LQ67
[00155]
LA10
LQ112


[00156]
LA2
LQ23
[00156]
LA6
LQ68
[00156]
LA10
LQ113


[00157]
LA2
LQ24
[00157]
LA6
LQ69
[00157]
LA10
LQ114


[00158]
LA2
LQ25
[00158]
LA6
LQ70
[00158]
LA10
LQ115


[00159]
LA2
LQ26
[00159]
LA6
LQ71
[00159]
LA10
LQ116


[00160]
LA2
LQ27
[00160]
LA6
LQ72
[00160]
LA10
LQ117


[00161]
LA2
LQ28
[00161]
LA6
LQ73
[00161]
LA10
LQ118


[00162]
LA2
LQ29
[00162]
LA6
LQ74
[00162]
LA10
LQ119


[00163]
LA2
LQ30
[00163]
LA6
LQ75
[00163]
LA10
LQ120


[00164]
LA2
LQ31
[00164]
LA6
LQ76
[00164]
LA10
LQ121


[00165]
LA2
LQ32
[00165]
LA6
LQ77
[00165]
LA10
LQ122


[00166]
LA2
LQ33
[00166]
LA6
LQ78
[00166]
LA10
LQ123


[00167]
LA2
LQ34
[00167]
LA6
LQ79
[00167]
LA10
LQ124


[00168]
LA2
LQ35
[00168]
LA6
LQ80
[00168]
LA10
LQ125


[00169]
LA2
LQ36
[00169]
LA6
LQ81
[00169]
LA10
LQ126


[00170]
LA2
LQ37
[00170]
LA6
LQ82
[00170]
LA10
LQ127


[00171]
LA2
LQ38
[00171]
LA6
LQ83
[00171]
LA10
LQ128


[00172]
LA2
LQ39
[00172]
LA6
LQ84
[00172]
LA10
LQ129


[00173]
LA2
LQ40
[00173]
LA6
LQ85
[00173]
LA10
LQ130


[00174]
LA2
LQ41
[00174]
LA6
LQ86
[00174]
LA10
LQ131


[00175]
LA2
LQ42
[00175]
LA6
LQ87
[00175]
LA10
LQ132


[00176]
LA2
LQ43
[00176]
LA6
LQ88
[00176]
LA10
LQ133


[00177]
LA2
LQ44
[00177]
LA6
LQ89
[00177]
LA11
LQ1


[00178]
LA2
LQ45
[00178]
LA6
LQ90
[00178]
LA11
LQ2


[00179]
LA2
LQ46
[00179]
LA6
LQ91
[00179]
LA11
LQ3


[00180]
LA2
LQ47
[00180]
LA6
LQ92
[00180]
LA11
LQ4


[00181]
LA2
LQ48
[00181]
LA6
LQ93
[00181]
LA11
LQ5


[00182]
LA2
LQ49
[00182]
LA6
LQ94
[00182]
LA11
LQ6


[00183]
LA2
LQ50
[00183]
LA6
LQ95
[00183]
LA11
LQ7


[00184]
LA2
LQ51
[00184]
LA6
LQ96
[00184]
LA11
LQ8


[00185]
LA2
LQ52
[00185]
LA6
LQ97
[00185]
LA11
LQ9


[00186]
LA2
LQ53
[00186]
LA6
LQ98
[00186]
LA11
LQ10


[00187]
LA2
LQ54
[00187]
LA6
LQ99
[00187]
LA11
LQ11


[00188]
LA2
LQ55
[00188]
LA6
LQ100
[00188]
LA11
LQ12


[00189]
LA2
LQ56
[00189]
LA6
LQ101
[00189]
LA11
LQ13


[00190]
LA2
LQ57
[00190]
LA6
LQ102
[00190]
LA11
LQ14


[00191]
LA2
LQ58
[00191]
LA6
LQ103
[00191]
LA11
LQ15


[00192]
LA2
LQ59
[00192]
LA6
LQ104
[00192]
LA11
LQ16


[00193]
LA2
LQ60
[00193]
LA6
LQ105
[00193]
LA11
LQ17


[00194]
LA2
LQ61
[00194]
LA6
LQ106
[00194]
LA11
LQ18


[00195]
LA2
LQ62
[00195]
LA6
LQ107
[00195]
LA11
LQ19


[00196]
LA2
LQ63
[00196]
LA6
LQ108
[00196]
LA11
LQ20


[00197]
LA2
LQ64
[00197]
LA6
LQ109
[00197]
LA11
LQ21


[00198]
LA2
LQ65
[00198]
LA6
LQ110
[00198]
LA11
LQ22


[00199]
LA2
LQ66
[00199]
LA6
LQ111
[00199]
LA11
LQ23


[00200]
LA2
LQ67
[00200]
LA6
LQ112
[00200]
LA11
LQ24


[00201]
LA2
LQ68
[00201]
LA6
LQ113
[00201]
LA11
LQ25


[00202]
LA2
LQ69
[00202]
LA6
LQ114
[00202]
LA11
LQ26


[00203]
LA2
LQ70
[00203]
LA6
LQ115
[00203]
LA11
LQ27


[00204]
LA2
LQ71
[00204]
LA6
LQ116
[00204]
LA11
LQ28


[00205]
LA2
LQ72
[00205]
LA6
LQ117
[00205]
LA11
LQ29


[00206]
LA2
LQ73
[00206]
LA6
LQ118
[00206]
LA11
LQ30


[00207]
LA2
LQ74
[00207]
LA6
LQ119
[00207]
LA11
LQ31


[00208]
LA2
LQ75
[00208]
LA6
LQ120
[00208]
LA11
LQ32


[00209]
LA2
LQ76
[00209]
LA6
LQ121
[00209]
LA11
LQ33


[00210]
LA2
LQ77
[00210]
LA6
LQ122
[00210]
LA11
LQ34


[00211]
LA2
LQ78
[00211]
LA6
LQ123
[00211]
LA11
LQ35


[00212]
LA2
LQ79
[00212]
LA6
LQ124
[00212]
LA11
LQ36


[00213]
LA2
LQ80
[00213]
LA6
LQ125
[00213]
LA11
LQ37


[00214]
LA2
LQ81
[00214]
LA6
LQ126
[00214]
LA11
LQ38


[00215]
LA2
LQ82
[00215]
LA6
LQ127
[00215]
LA11
LQ39


[00216]
LA2
LQ83
[00216]
LA6
LQ128
[00216]
LA11
LQ40


[00217]
LA2
LQ84
[00217]
LA6
LQ129
[00217]
LA11
LQ41


[00218]
LA2
LQ85
[00218]
LA6
LQ130
[00218]
LA11
LQ42


[00219]
LA2
LQ86
[00219]
LA6
LQ131
[00219]
LA11
LQ43


[00220]
LA2
LQ87
[00220]
LA6
LQ132
[00220]
LA11
LQ44


[00221]
LA2
LQ88
[00221]
LA6
LQ133
[00221]
LA11
LQ45


[00222]
LA2
LQ89
[00222]
LA7
LQ1
[00222]
LA11
LQ46


[00223]
LA2
LQ90
[00223]
LA7
LQ2
[00223]
LA11
LQ47


[00224]
LA2
LQ91
[00224]
LA7
LQ3
[00224]
LA11
LQ48


[00225]
LA2
LQ92
[00225]
LA7
LQ4
[00225]
LA11
LQ49


[00226]
LA2
LQ93
[00226]
LA7
LQ5
[00226]
LA11
LQ50


[00227]
LA2
LQ94
[00227]
LA7
LQ6
[00227]
LA11
LQ51


[00228]
LA2
LQ95
[00228]
LA7
LQ7
[00228]
LA11
LQ52


[00229]
LA2
LQ96
[00229]
LA7
LQ8
[00229]
LA11
LQ53


[00230]
LA2
LQ97
[00230]
LA7
LQ9
[00230]
LA11
LQ54


[00231]
LA2
LQ98
[00231]
LA7
LQ10
[00231]
LA11
LQ55


[00232]
LA2
LQ99
[00232]
LA7
LQ11
[00232]
LA11
LQ56


[00233]
LA2
LQ100
[00233]
LA7
LQ12
[00233]
LA11
LQ57


[00234]
LA2
LQ101
[00234]
LA7
LQ13
[00234]
LA11
LQ58


[00235]
LA2
LQ102
[00235]
LA7
LQ14
[00235]
LA11
LQ59


[00236]
LA2
LQ103
[00236]
LA7
LQ15
[00236]
LA11
LQ60


[00237]
LA2
LQ104
[00237]
LA7
LQ16
[00237]
LA11
LQ61


[00238]
LA2
LQ105
[00238]
LA7
LQ17
[00238]
LA11
LQ62


[00239]
LA2
LQ106
[00239]
LA7
LQ18
[00239]
LA11
LQ63


[00240]
LA2
LQ107
[00240]
LA7
LQ19
[00240]
LA11
LQ64


[00241]
LA2
LQ108
[00241]
LA7
LQ20
[00241]
LA11
LQ65


[00242]
LA2
LQ109
[00242]
LA7
LQ21
[00242]
LA11
LQ66


[00243]
LA2
LQ110
[00243]
LA7
LQ22
[00243]
LA11
LQ67


[00244]
LA2
LQ111
[00244]
LA7
LQ23
[00244]
LA11
LQ68


[00245]
LA2
LQ112
[00245]
LA7
LQ24
[00245]
LA11
LQ69


[00246]
LA2
LQ113
[00246]
LA7
LQ25
[00246]
LA11
LQ70


[00247]
LA2
LQ114
[00247]
LA7
LQ26
[00247]
LA11
LQ71


[00248]
LA2
LQ115
[00248]
LA7
LQ27
[00248]
LA11
LQ72


[00249]
LA2
LQ116
[00249]
LA7
LQ28
[00249]
LA11
LQ73


[00250]
LA2
LQ117
[00250]
LA7
LQ29
[00250]
LA11
LQ74


[00251]
LA2
LQ118
[00251]
LA7
LQ30
[00251]
LA11
LQ75


[00252]
LA2
LQ119
[00252]
LA7
LQ31
[00252]
LA11
LQ76


[00253]
LA2
LQ120
[00253]
LA7
LQ32
[00253]
LA11
LQ77


[00254]
LA2
LQ121
[00254]
LA7
LQ33
[00254]
LA11
LQ78


[00255]
LA2
LQ122
[00255]
LA7
LQ34
[00255]
LA11
LQ79


[00256]
LA2
LQ123
[00256]
LA7
LQ35
[00256]
LA11
LQ80


[00257]
LA2
LQ124
[00257]
LA7
LQ36
[00257]
LA11
LQ81


[00258]
LA2
LQ125
[00258]
LA7
LQ37
[00258]
LA11
LQ82


[00259]
LA2
LQ126
[00259]
LA7
LQ38
[00259]
LA11
LQ83


[00260]
LA2
LQ127
[00260]
LA7
LQ39
[00260]
LA11
LQ84


[00261]
LA2
LQ128
[00261]
LA7
LQ40
[00261]
LA11
LQ85


[00262]
LA2
LQ129
[00262]
LA7
LQ41
[00262]
LA11
LQ86


[00263]
LA2
LQ130
[00263]
LA7
LQ42
[00263]
LA11
LQ87


[00264]
LA2
LQ131
[00264]
LA7
LQ43
[00264]
LA11
LQ88


[00265]
LA2
LQ132
[00265]
LA7
LQ44
[00265]
LA11
LQ89


[00266]
LA2
LQ133
[00266]
LA7
LQ45
[00266]
LA11
LQ90


[00267]
LA3
LQ1
[00267]
LA7
LQ46
[00267]
LA11
LQ91


[00268]
LA3
LQ2
[00268]
LA7
LQ47
[00268]
LA11
LQ92


[00269]
LA3
LQ3
[00269]
LA7
LQ48
[00269]
LA11
LQ93


[00270]
LA3
LQ4
[00270]
LA7
LQ49
[00270]
LA11
LQ94


[00271]
LA3
LQ5
[00271]
LA7
LQ50
[00271]
LA11
LQ95


[00272]
LA3
LQ6
[00272]
LA7
LQ51
[00272]
LA11
LQ96


[00273]
LA3
LQ7
[00273]
LA7
LQ52
[00273]
LA11
LQ97


[00274]
LA3
LQ8
[00274]
LA7
LQ53
[00274]
LA11
LQ98


[00275]
LA3
LQ9
[00275]
LA7
LQ54
[00275]
LA11
LQ99


[00276]
LA3
LQ10
[00276]
LA7
LQ55
[00276]
LA11
LQ100


[00277]
LA3
LQ11
[00277]
LA7
LQ56
[00277]
LA11
LQ101


[00278]
LA3
LQ12
[00278]
LA7
LQ57
[00278]
LA11
LQ102


[00279]
LA3
LQ13
[00279]
LA7
LQ58
[00279]
LA11
LQ103


[00280]
LA3
LQ14
[00280]
LA7
LQ59
[00280]
LA11
LQ104


[00281]
LA3
LQ15
[00281]
LA7
LQ60
[00281]
LA11
LQ105


[00282]
LA3
LQ16
[00282]
LA7
LQ61
[00282]
LA11
LQ106


[00283]
LA3
LQ17
[00283]
LA7
LQ62
[00283]
LA11
LQ107


[00284]
LA3
LQ18
[00284]
LA7
LQ63
[00284]
LA11
LQ108


[00285]
LA3
LQ19
[00285]
LA7
LQ64
[00285]
LA11
LQ109


[00286]
LA3
LQ20
[00286]
LA7
LQ65
[00286]
LA11
LQ110


[00287]
LA3
LQ21
[00287]
LA7
LQ66
[00287]
LA11
LQ111


[00288]
LA3
LQ22
[00288]
LA7
LQ67
[00288]
LA11
LQ112


[00289]
LA3
LQ23
[00289]
LA7
LQ68
[00289]
LA11
LQ113


[00290]
LA3
LQ24
[00290]
LA7
LQ69
[00290]
LA11
LQ114


[00291]
LA3
LQ25
[00291]
LA7
LQ70
[00291]
LA11
LQ115


[00292]
LA3
LQ26
[00292]
LA7
LQ71
[00292]
LA11
LQ116


[00293]
LA3
LQ27
[00293]
LA7
LQ72
[00293]
LA11
LQ117


[00294]
LA3
LQ28
[00294]
LA7
LQ73
[00294]
LA11
LQ118


[00295]
LA3
LQ29
[00295]
LA7
LQ74
[00295]
LA11
LQ119


[00296]
LA3
LQ30
[00296]
LA7
LQ75
[00296]
LA11
LQ120


[00297]
LA3
LQ31
[00297]
LA7
LQ76
[00297]
LA11
LQ121


[00298]
LA3
LQ32
[00298]
LA7
LQ77
[00298]
LA11
LQ122


[00299]
LA3
LQ33
[00299]
LA7
LQ78
[00299]
LA11
LQ123


[00300]
LA3
LQ34
[00300]
LA7
LQ79
[00300]
LA11
LQ124


[00301]
LA3
LQ35
[00301]
LA7
LQ80
[00301]
LA11
LQ125


[00302]
LA3
LQ36
[00302]
LA7
LQ81
[00302]
LA11
LQ126


[00303]
LA3
LQ37
[00303]
LA7
LQ82
[00303]
LA11
LQ127


[00304]
LA3
LQ38
[00304]
LA7
LQ83
[00304]
LA11
LQ128


[00305]
LA3
LQ39
[00305]
LA7
LQ84
[00305]
LA11
LQ129


[00306]
LA3
LQ40
[00306]
LA7
LQ85
[00306]
LA11
LQ130


[00307]
LA3
LQ41
[00307]
LA7
LQ86
[00307]
LA11
LQ131


[00308]
LA3
LQ42
[00308]
LA7
LQ87
[00308]
LA11
LQ132


[00309]
LA3
LQ43
[00309]
LA7
LQ88
[00309]
LA11
LQ133


[00310]
LA3
LQ44
[00310]
LA7
LQ89
[00310]
LA12
LQ1


[00311]
LA3
LQ45
[00311]
LA7
LQ90
[00311]
LA12
LQ2


[00312]
LA3
LQ46
[00312]
LA7
LQ91
[00312]
LA12
LQ3


[00313]
LA3
LQ47
[00313]
LA7
LQ92
[00313]
LA12
LQ4


[00314]
LA3
LQ48
[00314]
LA7
LQ93
[00314]
LA12
LQ5


[00315]
LA3
LQ49
[00315]
LA7
LQ94
[00315]
LA12
LQ6


[00316]
LA3
LQ50
[00316]
LA7
LQ95
[00316]
LA12
LQ7


[00317]
LA3
LQ51
[00317]
LA7
LQ96
[00317]
LA12
LQ8


[00318]
LA3
LQ52
[00318]
LA7
LQ97
[00318]
LA12
LQ9


[00319]
LA3
LQ53
[00319]
LA7
LQ98
[00319]
LA12
LQ10


[00320]
LA3
LQ54
[00320]
LA7
LQ99
[00320]
LA12
LQ11


[00321]
LA3
LQ55
[00321]
LA7
LQ100
[00321]
LA12
LQ12


[00322]
LA3
LQ56
[00322]
LA7
LQ101
[00322]
LA12
LQ13


[00323]
LA3
LQ57
[00323]
LA7
LQ102
[00323]
LA12
LQ14


[00324]
LA3
LQ58
[00324]
LA7
LQ103
[00324]
LA12
LQ15


[00325]
LA3
LQ59
[00325]
LA7
LQ104
[00325]
LA12
LQ16


[00326]
LA3
LQ60
[00326]
LA7
LQ105
[00326]
LA12
LQ17


[00327]
LA3
LQ61
[00327]
LA7
LQ106
[00327]
LA12
LQ18


[00328]
LA3
LQ62
[00328]
LA7
LQ107
[00328]
LA12
LQ19


[00329]
LA3
LQ63
[00329]
LA7
LQ108
[00329]
LA12
LQ20


[00330]
LA3
LQ64
[00330]
LA7
LQ109
[00330]
LA12
LQ21


[00331]
LA3
LQ65
[00331]
LA7
LQ110
[00331]
LA12
LQ22


[00332]
LA3
LQ66
[00332]
LA7
LQ111
[00332]
LA12
LQ23


[00333]
LA3
LQ67
[00333]
LA7
LQ112
[00333]
LA12
LQ24


[00334]
LA3
LQ68
[00334]
LA7
LQ113
[00334]
LA12
LQ25


[00335]
LA3
LQ69
[00335]
LA7
LQ114
[00335]
LA12
LQ26


[00336]
LA3
LQ70
[00336]
LA7
LQ115
[00336]
LA12
LQ27


[00337]
LA3
LQ71
[00337]
LA7
LQ116
[00337]
LA12
LQ28


[00338]
LA3
LQ72
[00338]
LA7
LQ117
[00338]
LA12
LQ29


[00339]
LA3
LQ73
[00339]
LA7
LQ118
[00339]
LA12
LQ30


[00340]
LA3
LQ74
[00340]
LA7
LQ119
[00340]
LA12
LQ31


[00341]
LA3
LQ75
[00341]
LA7
LQ120
[00341]
LA12
LQ32


[00342]
LA3
LQ76
[00342]
LA7
LQ121
[00342]
LA12
LQ33


[00343]
LA3
LQ77
[00343]
LA7
LQ122
[00343]
LA12
LQ34


[00344]
LA3
LQ78
[00344]
LA7
LQ123
[00344]
LA12
LQ35


[00345]
LA3
LQ79
[00345]
LA7
LQ124
[00345]
LA12
LQ36


[00346]
LA3
LQ80
[00346]
LA7
LQ125
[00346]
LA12
LQ37


[00347]
LA3
LQ81
[00347]
LA7
LQ126
[00347]
LA12
LQ38


[00348]
LA3
LQ82
[00348]
LA7
LQ127
[00348]
LA12
LQ39


[00349]
LA3
LQ83
[00349]
LA7
LQ128
[00349]
LA12
LQ40


[00350]
LA3
LQ84
[00350]
LA7
LQ129
[00350]
LA12
LQ41


[00351]
LA3
LQ85
[00351]
LA7
LQ130
[00351]
LA12
LQ42


[00352]
LA3
LQ86
[00352]
LA7
LQ131
[00352]
LA12
LQ43


[00353]
LA3
LQ87
[00353]
LA7
LQ132
[00353]
LA12
LQ44


[00354]
LA3
LQ88
[00354]
LA7
LQ133
[00354]
LA12
LQ45


[00355]
LA3
LQ89
[00355]
LA8
LQ1
[00355]
LA12
LQ46


[00356]
LA3
LQ90
[00356]
LA8
LQ2
[00356]
LA12
LQ47


[00357]
LA3
LQ91
[00357]
LA8
LQ3
[00357]
LA12
LQ48


[00358]
LA3
LQ92
[00358]
LA8
LQ4
[00358]
LA12
LQ49


[00359]
LA3
LQ93
[00359]
LA8
LQ5
[00359]
LA12
LQ50


[00360]
LA3
LQ94
[00360]
LA8
LQ6
[00360]
LA12
LQ51


[00361]
LA3
LQ95
[00361]
LA8
LQ7
[00361]
LA12
LQ52


[00362]
LA3
LQ96
[00362]
LA8
LQ8
[00362]
LA12
LQ53


[00363]
LA3
LQ97
[00363]
LA8
LQ9
[00363]
LA12
LQ54


[00364]
LA3
LQ98
[00364]
LA8
LQ10
[00364]
LA12
LQ55


[00365]
LA3
LQ99
[00365]
LA8
LQ11
[00365]
LA12
LQ56


[00366]
LA3
LQ100
[00366]
LA8
LQ12
[00366]
LA12
LQ57


[00367]
LA3
LQ101
[00367]
LA8
LQ13
[00367]
LA12
LQ58


[00368]
LA3
LQ102
[00368]
LA8
LQ14
[00368]
LA12
LQ59


[00369]
LA3
LQ103
[00369]
LA8
LQ15
[00369]
LA12
LQ60


[00370]
LA3
LQ104
[00370]
LA8
LQ16
[00370]
LA12
LQ61


[00371]
LA3
LQ105
[00371]
LA8
LQ17
[00371]
LA12
LQ62


[00372]
LA3
LQ106
[00372]
LA8
LQ18
[00372]
LA12
LQ63


[00373]
LA3
LQ107
[00373]
LA8
LQ19
[00373]
LA12
LQ64


[00374]
LA3
LQ108
[00374]
LA8
LQ20
[00374]
LA12
LQ65


[00375]
LA3
LQ109
[00375]
LA8
LQ21
[00375]
LA12
LQ66


[00376]
LA3
LQ110
[00376]
LA8
LQ22
[00376]
LA12
LQ67


[00377]
LA3
LQ111
[00377]
LA8
LQ23
[00377]
LA12
LQ68


[00378]
LA3
LQ112
[00378]
LA8
LQ24
[00378]
LA12
LQ69


[00379]
LA3
LQ113
[00379]
LA8
LQ25
[00379]
LA12
LQ70


[00380]
LA3
LQ114
[00380]
LA8
LQ26
[00380]
LA12
LQ71


[00381]
LA3
LQ115
[00381]
LA8
LQ27
[00381]
LA12
LQ72


[00382]
LA3
LQ116
[00382]
LA8
LQ28
[00382]
LA12
LQ73


[00383]
LA3
LQ117
[00383]
LA8
LQ29
[00383]
LA12
LQ74


[00384]
LA3
LQ118
[00384]
LA8
LQ30
[00384]
LA12
LQ75


[00385]
LA3
LQ119
[00385]
LA8
LQ31
[00385]
LA12
LQ76


[00386]
LA3
LQ120
[00386]
LA8
LQ32
[00386]
LA12
LQ77


[00387]
LA3
LQ121
[00387]
LA8
LQ33
[00387]
LA12
LQ78


[00388]
LA3
LQ122
[00388]
LA8
LQ34
[00388]
LA12
LQ79


[00389]
LA3
LQ123
[00389]
LA8
LQ35
[00389]
LA12
LQ80


[00390]
LA3
LQ124
[00390]
LA8
LQ36
[00390]
LA12
LQ81


[00391]
LA3
LQ125
[00391]
LA8
LQ37
[00391]
LA12
LQ82


[00392]
LA3
LQ126
[00392]
LA8
LQ38
[00392]
LA12
LQ83


[00393]
LA3
LQ127
[00393]
LA8
LQ39
[00393]
LA12
LQ84


[00394]
LA3
LQ128
[00394]
LA8
LQ40
[00394]
LA12
LQ85


[00395]
LA3
LQ129
[00395]
LA8
LQ41
[00395]
LA12
LQ86


[00396]
LA3
LQ130
[00396]
LA8
LQ42
[00396]
LA12
LQ87


[00397]
LA3
LQ131
[00397]
LA8
LQ43
[00397]
LA12
LQ88


[00398]
LA3
LQ132
[00398]
LA8
LQ44
[00398]
LA12
LQ89


[00399]
LA3
LQ133
[00399]
LA8
LQ45
[00399]
LA12
LQ90


[00400]
LA4
LQ1
[00400]
LA8
LQ46
[00400]
LA12
LQ91


[00401]
LA4
LQ2
[00401]
LA8
LQ47
[00401]
LA12
LQ92


[00402]
LA4
LQ3
[00402]
LA8
LQ48
[00402]
LA12
LQ93


[00403]
LA4
LQ4
[00403]
LA8
LQ49
[00403]
LA12
LQ94


[00404]
LA4
LQ5
[00404]
LA8
LQ50
[00404]
LA12
LQ95


[00405]
LA4
LQ6
[00405]
LA8
LQ51
[00405]
LA12
LQ96


[00406]
LA4
LQ7
[00406]
LA8
LQ52
[00406]
LA12
LQ97


[00407]
LA4
LQ8
[00407]
LA8
LQ53
[00407]
LA12
LQ98


[00408]
LA4
LQ9
[00408]
LA8
LQ54
[00408]
LA12
LQ99


[00409]
LA4
LQ10
[00409]
LA8
LQ55
[00409]
LA12
LQ100


[00410]
LA4
LQ11
[00410]
LA8
LQ56
[00410]
LA12
LQ101


[00411]
LA4
LQ12
[00411]
LA8
LQ57
[00411]
LA12
LQ102


[00412]
LA4
LQ13
[00412]
LA8
LQ58
[00412]
LA12
LQ103


[00413]
LA4
LQ14
[00413]
LA8
LQ59
[00413]
LA12
LQ104


[00414]
LA4
LQ15
[00414]
LA8
LQ60
[00414]
LA12
LQ105


[00415]
LA4
LQ16
[00415]
LA8
LQ61
[00415]
LA12
LQ106


[00416]
LA4
LQ17
[00416]
LA8
LQ62
[00416]
LA12
LQ107


[00417]
LA4
LQ18
[00417]
LA8
LQ63
[00417]
LA12
LQ108


[00418]
LA4
LQ19
[00418]
LA8
LQ64
[00418]
LA12
LQ109


[00419]
LA4
LQ20
[00419]
LA8
LQ65
[00419]
LA12
LQ110


[00420]
LA4
LQ21
[00420]
LA8
LQ66
[00420]
LA12
LQ111


[00421]
LA4
LQ22
[00421]
LA8
LQ67
[00421]
LA12
LQ112


[00422]
LA4
LQ23
[00422]
LA8
LQ68
[00422]
LA12
LQ113


[00423]
LA4
LQ24
[00423]
LA8
LQ69
[00423]
LA12
LQ114


[00424]
LA4
LQ25
[00424]
LA8
LQ70
[00424]
LA12
LQ115


[00425]
LA4
LQ26
[00425]
LA8
LQ71
[00425]
LA12
LQ116


[00426]
LA4
LQ27
[00426]
LA8
LQ72
[00426]
LA12
LQ117


[00427]
LA4
LQ28
[00427]
LA8
LQ73
[00427]
LA12
LQ118


[00428]
LA4
LQ29
[00428]
LA8
LQ74
[00428]
LA12
LQ119


[00429]
LA4
LQ30
[00429]
LA8
LQ75
[00429]
LA12
LQ120


[00430]
LA4
LQ31
[00430]
LA8
LQ76
[00430]
LA12
LQ121


[00431]
LA4
LQ32
[00431]
LA8
LQ77
[00431]
LA12
LQ122


[00432]
LA4
LQ33
[00432]
LA8
LQ78
[00432]
LA12
LQ123


[00433]
LA4
LQ34
[00433]
LA8
LQ79
[00433]
LA12
LQ124


[00434]
LA4
LQ35
[00434]
LA8
LQ80
[00434]
LA12
LQ125


[00435]
LA4
LQ36
[00435]
LA8
LQ81
[00435]
LA12
LQ126


[00436]
LA4
LQ37
[00436]
LA8
LQ82
[00436]
LA12
LQ127


[00437]
LA4
LQ38
[00437]
LA8
LQ83
[00437]
LA12
LQ128


[00438]
LA4
LQ39
[00438]
LA8
LQ84
[00438]
LA12
LQ129


[00439]
LA4
LQ40
[00439]
LA8
LQ85
[00439]
LA12
LQ130


[00440]
LA4
LQ41
[00440]
LA8
LQ86
[00440]
LA12
LQ131


[00441]
LA4
LQ42
[00441]
LA8
LQ87
[00441]
LA12
LQ132


[00442]
LA4
LQ43
[00442]
LA8
LQ88
[00442]
LA12
LQ133


[00443]
LA4
LQ44
[00443]
LA8
LQ89
[00443]
LA13
LQ1


[00444]
LA4
LQ45
[00444]
LA8
LQ90
[00444]
LA13
LQ2


[00445]
LA4
LQ46
[00445]
LA8
LQ91
[00445]
LA13
LQ3


[00446]
LA4
LQ47
[00446]
LA8
LQ92
[00446]
LA13
LQ4


[00447]
LA4
LQ48
[00447]
LA8
LQ93
[00447]
LA13
LQ5


[00448]
LA4
LQ49
[00448]
LA8
LQ94
[00448]
LA13
LQ6


[00449]
LA4
LQ50
[00449]
LA8
LQ95
[00449]
LA13
LQ7


[00450]
LA4
LQ51
[00450]
LA8
LQ96
[00450]
LA13
LQ8


[00451]
LA4
LQ52
[00451]
LA8
LQ97
[00451]
LA13
LQ9


[00452]
LA4
LQ53
[00452]
LA8
LQ98
[00452]
LA13
LQ10


[00453]
LA4
LQ54
[00453]
LA8
LQ99
[00453]
LA13
LQ11


[00454]
LA4
LQ55
[00454]
LA8
LQ100
[00454]
LA13
LQ12


[00455]
LA4
LQ56
[00455]
LA8
LQ101
[00455]
LA13
LQ13


[00456]
LA4
LQ57
[00456]
LA8
LQ102
[00456]
LA13
LQ14


[00457]
LA4
LQ58
[00457]
LA8
LQ103
[00457]
LA13
LQ15


[00458]
LA4
LQ59
[00458]
LA8
LQ104
[00458]
LA13
LQ16


[00459]
LA4
LQ60
[00459]
LA8
LQ105
[00459]
LA13
LQ17


[00460]
LA4
LQ61
[00460]
LA8
LQ106
[00460]
LA13
LQ18


[00461]
LA4
LQ62
[00461]
LA8
LQ107
[00461]
LA13
LQ19


[00462]
LA4
LQ63
[00462]
LA8
LQ108
[00462]
LA13
LQ20


[00463]
LA4
LQ64
[00463]
LA8
LQ109
[00463]
LA13
LQ21


[00464]
LA4
LQ65
[00464]
LA8
LQ110
[00464]
LA13
LQ22


[00465]
LA4
LQ66
[00465]
LA8
LQ111
[00465]
LA13
LQ23


[00466]
LA4
LQ67
[00466]
LA8
LQ112
[00466]
LA13
LQ24


[00467]
LA4
LQ68
[00467]
LA8
LQ113
[00467]
LA13
LQ25


[00468]
LA4
LQ69
[00468]
LA8
LQ114
[00468]
LA13
LQ26


[00469]
LA4
LQ70
[00469]
LA8
LQ115
[00469]
LA13
LQ27


[00470]
LA4
LQ71
[00470]
LA8
LQ116
[00470]
LA13
LQ28


[00471]
LA4
LQ72
[00471]
LA8
LQ117
[00471]
LA13
LQ29


[00472]
LA4
LQ73
[00472]
LA8
LQ118
[00472]
LA13
LQ30


[00473]
LA4
LQ74
[00473]
LA8
LQ119
[00473]
LA13
LQ31


[00474]
LA4
LQ75
[00474]
LA8
LQ120
[00474]
LA13
LQ32


[00475]
LA4
LQ76
[00475]
LA8
LQ121
[00475]
LA13
LQ33


[00476]
LA4
LQ77
[00476]
LA8
LQ122
[00476]
LA13
LQ34


[00477]
LA4
LQ78
[00477]
LA8
LQ123
[00477]
LA13
LQ35


[00478]
LA4
LQ79
[00478]
LA8
LQ124
[00478]
LA13
LQ36


[00479]
LA4
LQ80
[00479]
LA8
LQ125
[00479]
LA13
LQ37


[00480]
LA4
LQ81
[00480]
LA8
LQ126
[00480]
LA13
LQ38


[00481]
LA4
LQ82
[00481]
LA8
LQ127
[00481]
LA13
LQ39


[00482]
LA4
LQ83
[00482]
LA8
LQ128
[00482]
LA13
LQ40


[00483]
LA4
LQ84
[00483]
LA8
LQ129
[00483]
LA13
LQ41


[00484]
LA4
LQ85
[00484]
LA8
LQ130
[00484]
LA13
LQ42


[00485]
LA4
LQ86
[00485]
LA8
LQ131
[00485]
LA13
LQ43


[00486]
LA4
LQ87
[00486]
LA8
LQ132
[00486]
LA13
LQ44


[00487]
LA4
LQ88
[00487]
LA8
LQ133
[00487]
LA13
LQ45


[00488]
LA4
LQ89
[00488]
LA9
LQ1
[00488]
LA13
LQ46


[00489]
LA4
LQ90
[00489]
LA9
LQ2
[00489]
LA13
LQ47


[00490]
LA4
LQ91
[00490]
LA9
LQ3
[00490]
LA13
LQ48


[00491]
LA4
LQ92
[00491]
LA9
LQ4
[00491]
LA13
LQ49


[00492]
LA4
LQ93
[00492]
LA9
LQ5
[00492]
LA13
LQ50


[00493]
LA4
LQ94
[00493]
LA9
LQ6
[00493]
LA13
LQ51


[00494]
LA4
LQ95
[00494]
LA9
LQ7
[00494]
LA13
LQ52


[00495]
LA4
LQ96
[00495]
LA9
LQ8
[00495]
LA13
LQ53


[00496]
LA4
LQ97
[00496]
LA9
LQ9
[00496]
LA13
LQ54


[00497]
LA4
LQ98
[00497]
LA9
LQ10
[00497]
LA13
LQ55


[00498]
LA4
LQ99
[00498]
LA9
LQ11
[00498]
LA13
LQ56


[00499]
LA4
LQ100
[00499]
LA9
LQ12
[00499]
LA13
LQ57


[00500]
LA4
LQ101
[00500]
LA9
LQ13
[00500]
LA13
LQ58


[00501]
LA4
LQ102
[00501]
LA9
LQ14
[00501]
LA13
LQ59


[00502]
LA4
LQ103
[00502]
LA9
LQ15
[00502]
LA13
LQ60


[00503]
LA4
LQ104
[00503]
LA9
LQ16
[00503]
LA13
LQ61


[00504]
LA4
LQ105
[00504]
LA9
LQ17
[00504]
LA13
LQ62


[00505]
LA4
LQ106
[00505]
LA9
LQ18
[00505]
LA13
LQ63


[00506]
LA4
LQ107
[00506]
LA9
LQ19
[00506]
LA13
LQ64


[00507]
LA4
LQ108
[00507]
LA9
LQ20
[00507]
LA13
LQ65


[00508]
LA4
LQ109
[00508]
LA9
LQ21
[00508]
LA13
LQ66


[00509]
LA4
LQ110
[00509]
LA9
LQ22
[00509]
LA13
LQ67


[00510]
LA4
LQ111
[00510]
LA9
LQ23
[00510]
LA13
LQ68


[00511]
LA4
LQ112
[00511]
LA9
LQ24
[00511]
LA13
LQ69


[00512]
LA4
LQ113
[00512]
LA9
LQ25
[00512]
LA13
LQ70


[00513]
LA4
LQ114
[00513]
LA9
LQ26
[00513]
LA13
LQ71


[00514]
LA4
LQ115
[00514]
LA9
LQ27
[00514]
LA13
LQ72


[00515]
LA4
LQ116
[00515]
LA9
LQ28
[00515]
LA13
LQ73


[00516]
LA4
LQ117
[00516]
LA9
LQ29
[00516]
LA13
LQ74


[00517]
LA4
LQ118
[00517]
LA9
LQ30
[00517]
LA13
LQ75


[00518]
LA4
LQ119
[00518]
LA9
LQ31
[00518]
LA13
LQ76


[00519]
LA4
LQ120
[00519]
LA9
LQ32
[00519]
LA13
LQ77


[00520]
LA4
LQ121
[00520]
LA9
LQ33
[00520]
LA13
LQ78


[00521]
LA4
LQ122
[00521]
LA9
LQ34
[00521]
LA13
LQ79


[00522]
LA4
LQ123
[00522]
LA9
LQ35
[00522]
LA13
LQ80


[00523]
LA4
LQ124
[00523]
LA9
LQ36
[00523]
LA13
LQ81


[00524]
LA4
LQ125
[00524]
LA9
LQ37
[00524]
LA13
LQ82


[00525]
LA4
LQ126
[00525]
LA9
LQ38
[00525]
LA13
LQ83


[00526]
LA4
LQ127
[00526]
LA9
LQ39
[00526]
LA13
LQ84


[00527]
LA4
LQ128
[00527]
LA9
LQ40
[00527]
LA13
LQ85


[00528]
LA4
LQ129
[00528]
LA9
LQ41
[00528]
LA13
LQ86


[00529]
LA4
LQ130
[00529]
LA9
LQ42
[00529]
LA13
LQ87


[00530]
LA4
LQ131
[00530]
LA9
LQ43
[00530]
LA13
LQ88


[00531]
LA4
LQ132
[00531]
LA9
LQ44
[00531]
LA13
LQ89


[00532]
LA4
LQ133
[00532]
LA9
LQ45
[00532]
LA13
LQ90


[00533]
LA5
LQ1
[00533]
LA9
LQ46
[00533]
LA13
LQ91


[00534]
LA5
LQ2
[00534]
LA9
LQ47
[00534]
LA13
LQ92


[00535]
LA5
LQ3
[00535]
LA9
LQ48
[00535]
LA13
LQ93


[00536]
LA5
LQ4
[00536]
LA9
LQ49
[00536]
LA13
LQ94


[00537]
LA5
LQ5
[00537]
LA9
LQ50
[00537]
LA13
LQ95


[00538]
LA5
LQ6
[00538]
LA9
LQ51
[00538]
LA13
LQ96


[00539]
LA5
LQ7
[00539]
LA9
LQ52
[00539]
LA13
LQ97


[00540]
LA5
LQ8
[00540]
LA9
LQ53
[00540]
LA13
LQ98


[00541]
LA5
LQ9
[00541]
LA9
LQ54
[00541]
LA13
LQ99


[00542]
LA5
LQ10
[00542]
LA9
LQ55
[00542]
LA13
LQ100


[00543]
LA5
LQ11
[00543]
LA9
LQ56
[00543]
LA13
LQ101


[00544]
LA5
LQ12
[00544]
LA9
LQ57
[00544]
LA13
LQ102


[00545]
LA5
LQ13
[00545]
LA9
LQ58
[00545]
LA13
LQ103


[00546]
LA5
LQ14
[00546]
LA9
LQ59
[00546]
LA13
LQ104


[00547]
LA5
LQ15
[00547]
LA9
LQ60
[00547]
LA13
LQ105


[00548]
LA5
LQ16
[00548]
LA9
LQ61
[00548]
LA13
LQ106


[00549]
LA5
LQ17
[00549]
LA9
LQ62
[00549]
LA13
LQ107


[00550]
LA5
LQ18
[00550]
LA9
LQ63
[00550]
LA13
LQ108


[00551]
LA5
LQ19
[00551]
LA9
LQ64
[00551]
LA13
LQ109


[00552]
LA5
LQ20
[00552]
LA9
LQ65
[00552]
LA13
LQ110


[00553]
LA5
LQ21
[00553]
LA9
LQ66
[00553]
LA13
LQ111


[00554]
LA5
LQ22
[00554]
LA9
LQ67
[00554]
LA13
LQ112


[00555]
LA5
LQ23
[00555]
LA9
LQ68
[00555]
LA13
LQ113


[00556]
LA5
LQ24
[00556]
LA9
LQ69
[00556]
LA13
LQ114


[00557]
LA5
LQ25
[00557]
LA9
LQ70
[00557]
LA13
LQ115


[00558]
LA5
LQ26
[00558]
LA9
LQ71
[00558]
LA13
LQ116


[00559]
LA5
LQ27
[00559]
LA9
LQ72
[00559]
LA13
LQ117


[00560]
LA5
LQ28
[00560]
LA9
LQ73
[00560]
LA13
LQ118


[00561]
LA5
LQ29
[00561]
LA9
LQ74
[00561]
LA13
LQ119


[00562]
LA5
LQ30
[00562]
LA9
LQ75
[00562]
LA13
LQ120


[00563]
LA5
LQ31
[00563]
LA9
LQ76
[00563]
LA13
LQ121


[00564]
LA5
LQ32
[00564]
LA9
LQ77
[00564]
LA13
LQ122


[00565]
LA5
LQ33
[00565]
LA9
LQ78
[00565]
LA13
LQ123


[00566]
LA5
LQ34
[00566]
LA9
LQ79
[00566]
LA13
LQ124


[00567]
LA5
LQ35
[00567]
LA9
LQ80
[00567]
LA13
LQ125


[00568]
LA5
LQ36
[00568]
LA9
LQ81
[00568]
LA13
LQ126


[00569]
LA5
LQ37
[00569]
LA9
LQ82
[00569]
LA13
LQ127


[00570]
LA5
LQ38
[00570]
LA9
LQ83
[00570]
LA13
LQ128


[00571]
LA5
LQ39
[00571]
LA9
LQ84
[00571]
LA13
LQ129


[00572]
LA5
LQ40
[00572]
LA9
LQ85
[00572]
LA13
LQ130


[00573]
LA5
LQ41
[00573]
LA9
LQ86
[00573]
LA13
LQ131


[00574]
LA5
LQ42
[00574]
LA9
LQ87
[00574]
LA13
LQ132


[00575]
LA5
LQ43
[00575]
LA9
LQ88
[00575]
LA13
LQ133


[00576]
LA5
LQ44
[00576]
LA9
LQ89





[00577]
LA5
LQ45
[00577]
LA9
LQ90









In one embodiment, the compound comprising the first ligand L1 having Formula I as defined herein can be selected from the group consisting of:




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According to another aspect of the present disclosure, a first device comprising a first organic light emitting device is provided. The first organic light emitting device can comprise an anode, a cathode, and an organic layer, disposed between the anode and the cathode. The organic layer can include a compound comprising the first ligand L1 having Formula I, as defined herein.


In one embodiment, the compound can be selected from the group consisting of Compound 8, Compound 9, Compound 12, Compound 32, Compound 43, Compound 54, Compound 55, Compound 62, Compound 83, Compound 93, Compound 118, Compound 141, Compound 142, Compound 176, Compound 278, and Compound 320.


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


The organic layer 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.


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 CnH2n+1, OCnH2n+1, OAr1, N(CnH2n+1)2, N(Ar1)(Ar2), CH═CH—CnH2n+1, C≡C—CnH2n+1, Ar1, Ar1-Ar2, CnH2n-Ar1, or no substitution. In the preceding substituents n can range from 1 to 10; and Ari and Ar2 can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.


The host can be a compound selected from the group consisting of carbazole, dibenzothiphene, 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:




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and combinations thereof.


In yet another aspect of the present disclosure, a formulation comprising the first ligand L1 having Formula I, as defined herein, is also within the scope of the invention disclosed herein. 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


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:

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 porphryin 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 MoOx; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.


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




embedded image


Each of Ar1 to Ar9 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.


In one aspect, Ar1 to Ar9 is independently selected from the group consisting of:




embedded image


wherein k is an integer from 1 to 20; X101 to X108 is C (including CH) or N; Z101 is NAr1, O, or S; Ar1 has the same group defined above.


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




embedded image


wherein Met is a metal, which can have an atomic weight greater than 40; (Y101-Y102) is a bidentate ligand, Y101 and Y102 are independently selected from C, N, O, P, and S; L101 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.


In one aspect, (Y101-Y102) is a 2-phenylpyridine derivative. In another aspect, (Y101-Y102) 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+/Fc couple less than about 0.6 V.


Host:

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.


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




embedded image


wherein Met is a metal; (Y103-Y104) is a bidentate ligand, Y103 and Y104 are independently selected from C, N, O, P, and S; L101 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.


In one aspect, the metal complexes are:




embedded image


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


In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y103-Y104) is a carbene ligand.


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.


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




embedded image


embedded image


wherein R101 to R107 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. X101 to X108 is selected from C (including CH) or N. Z101 and Z102 is selected from NR101, O, or S.


HBL:

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.


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


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




embedded image


wherein k is an integer from 1 to 20; L101 is an another ligand, k′ is an integer from 1 to 3.


ETL:

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.


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




embedded image


wherein R101 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. Ar1 to Ar3 has the similar definition as Ar's mentioned above. k is an integer from 1 to 20. X101 to X108 is selected from C (including CH) or N.


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




embedded image


wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L101 is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.


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.


In addition to and/or in combination with the materials disclosed herein, many hole injection materials, hole transporting materials, host materials, dopant materials, exiton/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.











TABLE 2





MATERIAL
EXAMPLES OF MATERIAL
PUBLICATIONS















Hole injection materials









Phthalocyanine and porphryin compounds


embedded image


Appl. Phys. Lett. 69, 2160 (1996)





Starburst triarylamines


embedded image


J. Lumin. 72-74, 985 (1997)





CFx Fluorohydro- carbon polymer


embedded image


Appl. Phys. Lett. 78, 673 (2001)





Conducting polymers (e.g., PEDOT:PSS, polyaniline, polypthiophene)


embedded image


Synth. Met. 87, 171 (1997) WO2007002683





Phosphonic acid and sliane SAMs


embedded image


US20030162053





Triarylamine or polythiophene polymers with conductivity dopants


embedded image


EP1725079A1








embedded image











embedded image








Organic compounds with conductive inorganic compounds, such as molybdenum and tungsten oxides


embedded image


US20050123751 SID Symposium Digest, 37, 923 (2006) WO2009018009





n-type semiconducting organic complexes


embedded image


US20020158242





Metal organometallic complexes


embedded image


US20060240279





Cross-linkable compounds


embedded image


US20080220265





Polythiophene based polymers and copolymers


embedded image


WO 2011075644 EP2350216










Hole transporting materials









Triarylamines (e.g., TPD, α-NPD)


embedded image


Appl. Phys. Lett. 51, 913 (1987)








embedded image


US5061569








embedded image


EP650955








embedded image


J. Mater. Chem. 3, 319 (1993)








embedded image


Appl. Phys. Lett. 90, 183503 (2007)










Hole injection materials












embedded image


Appl. Phys. Lett. 90, 183503 (2007)





Triaylamine on spirofluorene core


embedded image


Synth. Met. 91, 209 (1997)





Arylamine carbazole compounds


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Adv. Mater. 6, 677 (1994), US20080124572





Triarylamine with (di)benzothiophene/ (di) benzofuran


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US20070278938, US20080106190 US20110163302





Indolocarbazoles


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Synth. Met. 111, 421 (2000)





Isoindole compounds


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Chem. Mater. 15, 3148 (2003)





Metal carbene complexes


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US20080018221










Phosphorescent OLED host materials


Red hosts









Arylcarbazoles


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Appl. Phys. Lett. 78, 1622 (2001)





Metal 8-hydroxyquinolates (e.g., Alq3, BAlq)


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Nature 395, 151 (1998)








embedded image


US20060202194








embedded image


WO2005014551








embedded image


WO2006072002





Metal phenoxy- benzothiazole compounds


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Appl. Phys. Lett. 90, 123509 (2007)





Conjugated oligomers and polymers (e.g., polyfluorene)


embedded image


Org. Electron. 1, 15 (2000)





Aromatic fused rings


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WO2009066779, WO2009066778, WO2009063833, US20090045731, US20090045730, WO2009008311, US20090008605, US20090009065










Hole injection materials









Zinc complexes


embedded image


WO2010056066





Chrysene based compounds


embedded image


WO2011086863










Green hosts









Arylcarbazoles


embedded image


Appl. Phys. Lett. 78, 1622 (2001)








embedded image


US20030175553








embedded image


WO2001039234





Aryltriphenylene compounds


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US20060280965








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US20060280965








embedded image


WO2009021126










Hole injection materials









Poly-fused heteroaryl compounds


embedded image


US20090309488 US20090302743 US20100012931





Donor acceptor type molecules


embedded image


WO2008056746








embedded image


WO2010107244





Aza-carbazole/ DBT/DBF


embedded image


JP2008074939








embedded image


US20100187984





Polymers (e.g., PVK)


embedded image


Appl. Phys. Lett. 77, 2280 (2000)





Spirofluorene compounds


embedded image


WO2004093207





Metal phenoxy- benzooxazole compounds


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WO2005089025








embedded image


WO2006132173








embedded image


JP200511610





Spirofluorene- carbazole compounds


embedded image


JP2007254297








embedded image


JP2007254297





Indolocabazoles


embedded image


WO2007063796








embedded image


WO2007063754





5-member ring electron deficient heterocycles (e.g., triazole, oxadiazole)


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J. Appl. Phys. 90, 5048 (2001)








embedded image


WO2004107822





Tetraphenylene complexes


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US20050112407





Metal phenoxypyridine compounds


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WO2005030900





Metal coordination complexes (e.g., Zn, Al with N{circumflex over ( )}N ligands)


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US20040137268, US20040137267










Blue hosts









Arylcarbazoles


embedded image


Appl. Phys. Lett, 82, 2422 (2003)








embedded image


US20070190359







Hole injection materials









Dibenzothiophene/ Dibenzofuran- carbazole compounds


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WO2006114966, US20090167162








embedded image


US20090167162








embedded image


WO2009086028








embedded image


US20090030202, US20090017330








embedded image


US20100084966





Silicon aryl compounds


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US20050238919








embedded image


WO2009003898





Silicon/Germanium aryl compounds


embedded image


EP2034538A





Aryl benzoyl ester


embedded image


WO2006100298





Carbazole linked by non- conjugated groups


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US20040115476





Aza-carbazoles


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US20060121308





High triplet metal organometallic complex


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US7154114










Phosphorescent dopants


Red dopants









Heavy metal porphyrins (e.g., PtOEP)


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Nature 395, 151 (1998)





Iridium(III) organometallic complexes


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Appl. Phys. Lett. 78, 1622 (2001)










Hole injection materials












embedded image


US2006835469








embedded image


US2006835469








embedded image


US20060202194








embedded image


US20060202194








embedded image


US20070087321








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US20080261076 US20100090591








embedded image


US20070087321








embedded image


Adv. Mater. 19, 739 (2007)








embedded image


WO2009100991








embedded image


WO2008101842








embedded image


US7232618





Platinum(II) organometallic complexes


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WO2003040257








embedded image


US20070103060





Osminum(III) complexes


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Chem. Mater. 17, 3532 (2005)





Ruthenium(II) complexes


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Adv. Mater. 17, 1059 (2005)





Rhenium (I), (II), and (III) complexes


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US20050244673










Green dopants









Iridium(III) organometallic complexes


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Inorg. Chem. 40, 1704 (2001)








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US20020034656








embedded image


US7332232








embedded image


US20090108737










Hole injection materials












embedded image


WO2010028151








embedded image


EP1841834B








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US20060127696








embedded image


US20090039776








embedded image


US6921915








embedded image


US20100244004








embedded image


US6687266








embedded image


Chem. Mater. 16, 2480 (2004)








embedded image


US20070190359








embedded image


US20060008670 JP2007123392








embedded image


WO2010086089, WO2011044988








embedded image


Adv. Mater. 16, 2003 (2004)








embedded image


Angew. Chem. Int. Ed. 2006, 45, 7800








embedded image


WO2009050290








embedded image


US20090165846








embedded image


US20080015355








embedded image


US20010015432








embedded image


US20100295032





Monomer for polymeric metal organometallic compounds


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US7250226, US7396598





Pt(II) organometallic complexes, including polydentated ligands


embedded image


Appl. Phys. Lett. 86, 153505 (2005)








embedded image


Appl. Phys. Lett. 86, 153505 (2005)








embedded image


Chem. Lett. 34, 592 (2005)








embedded image


WO2002015645








embedded image


US20060263635








embedded image


US20060182992 US20070103060





Cu complexes


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WO2009000673








embedded image


US20070111026





Gold complexes


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Chem. Commun. 2906 (2005)





Rhenium(III) complexes


embedded image


Inorg. Chem. 42, 1248 (2003)





Osmium(II) complexes


embedded image


US7279704





Deuterated organometallic complexes


embedded image


US20030138657





Organometallic complexes with two or more metal centers


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US20030152802








embedded image


US7090928










Blue dopants









Iridium(III) organometallic complexes


embedded image


WO2002002714








embedded image


WO2006009024








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US20060251923 US20110057559 US20110204333








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US7393599, WO2006056418, US20050260441, WO2005019373








embedded image


US7534505










Hole injection materials












embedded image


WO2011051404








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US7445855








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US20070190359, US20080297033 US20100148663








embedded image


US7338722








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US20020134984








embedded image


Angew. Chem. Int. Ed. 47, 4542 (2008)








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Chem. Mater. 18, 5119 (2006)








embedded image


Inorg. Chem. 46, 4308 (2007)








embedded image


WO2005123873








embedded image


WO2005123873








embedded image


WO2007004380








embedded image


WO2006082742





Osmium(II) complexes


embedded image


US7279704








embedded image


Organometallics 23, 3745 (2004)





Gold complexes


embedded image


Appl. Phys. Lett. 74, 1361 (1999)





Platinum(II) complexes


embedded image


WO2006098120, WO2006103874





Pt tetradentate complexes with at least one metal- carbene bond


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US7655323










Exciton/hole blocking layer materials









Bathocuprine compounds (e.g., BCP, BPhen)


embedded image


Appl. Phys. Lett. 75, 4 (1999)








embedded image


Appl. Phys. Lett. 79, 449 (2001)





Metal 8-hydroxyquinolates (e.g., BAlq)


embedded image


Appl. Phys. Lett. 81, 162 (2002)





5-member ring electron deficient heterocycles such as triazole, oxadiazole, imidazole, benzoimidazole


embedded image


Appl. Phys. Lett. 81, 162 (2002)





Triphenylene compounds


embedded image


US20050025993










Hole injection materials









Fluorinated aromatic compounds


embedded image


Appl. Phys. Lett. 79, 156 (2001)





Phenothiazine-S- oxide


embedded image


WO2008132085





Silylated five-membered nitrogen, oxygen, sulfur or phosphorus dibenzoheterocycles


embedded image


WO2010079051





Aza-carbazoles


embedded image


US20060121308










Electron transporting materials









Anthracene- benzoimidazole compounds


embedded image


WO2003060956








embedded image


US20090179554










Hole injection materials









Aza triphenylene derivatives


embedded image


US20090115316





Anthracene- benzothiazole compounds


embedded image


Appl. Phys. Lett. 89, 063504 (2006)





Metal 8-hydroxyquinolates (e.g., Alq3, Zrq4)


embedded image


Appl. Phys. Lett. 51, 913 (1987) US7230107





Metal hydroxy- benoquinolates


embedded image


Chem. Lett. 5, 905 (1993)





Bathocuprine compounds such as BCP, BPhen, etc


embedded image


Appl. Phys. Lett. 91, 263503 (2007)








embedded image


Appl. Phys. Lett. 79, 449 (2001)





5-member ring electron deficient heterocycles (e.g., triazole, oxadiazole, imidazole, benzoimidazole)


embedded image


Appl. Phys. Lett. 74, 865 (1999)








embedded image


Appl. Phys. Lett. 55, 1489 (1989)








embedded image


Jpn. J. Apply. Phys. 32, L917 (1993)





Silole compounds


embedded image


Org. Electron. 4, 113 (2003)





Arylborane compounds


embedded image


J. Am. Chem. Soc. 120, 9714 (1998)





Fluorinated aromatic compounds


embedded image


J. Am. Chem. Soc. 122, 1832 (2000)





Fullerene (e.g., C60)


embedded image


US20090101870





Triazine complexes


embedded image


US20040036077





Zn (N{circumflex over ( )}N) complexes


embedded image


US6528187









EXPERIMENTAL

Device Examples:


Materials Used in the Example Devices:


Comparative Compounds Used are:



embedded image


Other Material Used in the Devices:




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All example devices were fabricated by high vacuum (<10−7 Torr) thermal evaporation. The anode electrode is 1200 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of LiF followed by 1,000 Å of Al. All devices are encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H2O and O2) immediately after fabrication, and a moisture getter was incorporated inside the package.


The organic stack of the example devices consisted of sequentially from the ITO surface, 100 Å of HAT-CN as the hole injection layer (HIL), 400 Å of NPD as the hole transporting layer (HTL), 400 Å of the emissive layer (EML) which contains the compound of Formula 1, Compound SD, and Host (BAQ), 40 Å of BAlQ as the blocking layer (BL), 450 Å of AlQ3 as the electron transporting layer (ETL) and 10 Å of LiF as the electron injection layer (EIL). The comparative examples were fabricated similarly to the device examples except that the Comparative Compounds 1-4 were used as the emitter in the EML.









TABLE 3







Devices structures of inventive compounds and comparative compounds












Example
HIL
HTL
EML (400 Å, doping %)
BL
ETL

















Example 1
HAT-CN
NPD
BAlQ
Compound SD
Compound 8
BAlQ
AlQ3 450 Å



100 Å
400 Å
88%
9%
3%
40 Å



Comparative
HAT-CN
NPD
BAlQ
Compound SD
Comparative
BAlQ
AlQ3 450 Å


Example 1
100 Å
400 Å
88%
9%
Compound 1
40 Å








3%




Comparative
HAT-CN
NPD
BAlQ
Compound SD
Comparative
BAlQ
AlQ3 450 Å


Example 2
100 Å
400 Å
88%
9%
Compound 2
40 Å








3%




Comparative
HAT-CN
NPD
BAlQ
Compound SD
Comparative
BAlQ
AlQ3 450 Å


Example 3
100 Å
400 Å
88%
9%
Compound 3
40 Å








3%




Comparative
HAT-CN
NPD
BAlQ
Compound SD
Comparative
BAlQ
AlQ3 450 Å


Example 4
100 Å
400 Å
88%
9%
Compound 4
40 Å








3%
















TABLE 4







Device results1











1931 CIE

At 1,000 nits















CIE
CIE
FWHM
Voltage
LE
EQE
PE


Example
x
y
[a.u.]
[a.u.]
[a.u.]
[a.u.]
[a.u.]

















Compound 8
0.66
0.34
1.00
1.00
1.00
1.00
1.00


Comparative
0.67
0.33
1.11
1.09
0.78
0.90
0.71


Compound 1









Comparative
0.66
0.34
1.07
1.05
0.84
0.91
0.82


Compound 2









Comparative
0.66
0.34
1.04
1.06
0.86
0.94
0.81


Compound 3









Comparative
0.66
0.34
1.04
1.03
0.89
0.93
0.86


Compound 4






1All values in Table 4 are relative numbers (arbitrary units—au.) except for the CIE coordinates.







Table 4 is a summary of the device data. The luminous efficiency (LE), external quantum efficiency (EQE) and power efficiency (PE) were measured at 1000 nits. The inventive Compound 8 shows similar CIE to the comparative compounds since the emission color of these compounds are dominated by the Phenylquinoline ligand. However, the emission spectrum of Compound 8 is narrower than that of the comparative compounds as can be seen from the full width at the half maximum (FWHM) values in table 2. A smaller FWHM value means narrower emission spectrum. The device measurements show that all characteristics are better when a new ancillary ligand as disclosed here is used. For example, a relative driving voltage of 1.00 was obtained for Compound 8 whereas that voltage was between 1.03 and 1.09 for the comparative examples. As for the luminous efficacy (LE), it is much better than for the comparative example where it varies from 78 to 89% of the value for Compound 8. The same trend was found for the external quantum efficiency (EQE) and the power efficacy where the data for Compound 8 is higher compared to the comparative examples.


Table 5 below shows the unexpected performance improvement exhibited by an example of the inventive compounds, Compound 12, over Comparative Compounds 5 and 6 by way of each compounds' photoluminescence quantum yield (PLQY):










TABLE 5






PLQY in 5%


Compound Structure
PMMA film









embedded image


34%







embedded image


57%







embedded image


59%









Inventive Compound 12 showed higher PLQY than the comparative compounds. Higher PLQY is desirable for emitters in OLEDs for high EQE.


MATERIAL SYNTHESIS

All reactions were carried out under nitrogen protections unless specified otherwise. All solvents for reactions are anhydrous and used as received from commercial sources.


Synthesis of Compound 8



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To the Iridium (III) dimer (1.50 g, 1.083 mmol) was added 3,7-diethylnonane-4,6-dione (1.725 g, 8.13 mmol) and the mixture was solubilized in 2-ethoxyethanol (40 mL). The mixture was degassed by bubbling nitrogen for 30 minutes and potassium carbonate (1.123 g, 8.13 mmol) was then added. The mixture was stirred at room temperature for 48 h followed by addition of 200 mL of isopropanol. The mixture was filtered through a Celite® plug and washed with dichloromethane. The solvent was evaporated and the crude product was purified by column chromatography using 20% dichloromethane (DCM) in heptanes in a triethylamine pre-treated silica gel column. The solid product was washed with methanol (20 mL) and filtered to obtain 0.220 g (10% yield) of pure dopant (99.5% on HPLC).


Synthesis of Compound 9



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The Ir(III) Dimer (1.70 g, 1.18 mmol) and 3,7-diethylnonane-4,6-dione (2.51 g, 11.8 mmol) were dissolved in ethoxyethanol (50 mL), sodium carbonate (0.63 g, 5.90 mmol) was added followed with degassing by bubbling nitrogen through the mixture. The reaction mixture was stirred overnight at room temperature. The temperature was then increased to 45° C. for 2 hours. Upon cooling to room temperature, the precipitate was filtered through Celite, washed with MeOH and heptanes. The filtrate with Celite® was suspended in DCM (containing 5% of Et3N), filtered and evaporated. The red solid obtained (0.6 g) had a purity of 99.6% by HPLC.


Synthesis of Compound 12



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Iridium (III) dimer (1.75 g, 1.17 mmol) and 3,7-diethylnonane-4,6-dione (2.48 g, 11.7 mmol) were suspended in 2-ethoxyethanol (40 mL), degassed by bubbling nitrogen for 30 minutes and cesium carbonate (2.26 g, 11.7 mmol) was added to the solution. The mixture was then stirred at 90° C. overnight. Dichloromethane (100 mL) was added; the solution was filtered through a pad of Celite® and the pad was washed with dichloromethane. The solvents were evaporated and the red solid was coated on Celite® followed by purification by column chromatography on a triethylamine pre-treated silica gel column using 10% DCM in heptanes. Evaporation provided the red solid, which was washed with methanol to give a pure target compound (0.430 g, 40% yield) as a red solid.


Synthesis of Compound 32



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Ir(III) Dimer (1.32 g, 0.85 mmol) in 2-ethoxyethanol (40 mL) was degassed with nitrogen for 30 minutes and mixed with 3,7-diethylnonane-4,6-dione (1.81 g, 8.50 mmol) and potassium carbonate (1.18 g, 8.50 mmol). The reaction mixture was stirred at room temperature overnight. The mixture was then filtered through a plug of Celite® and washed with MeOH. The precipitate was extracted from Celite® with 5% Et3N/CH2Cl2 affording 0.2 g of 99.9% pure material (HPLC). The filtrate was concentrated in vacuo, dissolved in DCM and crystallized by layering methanol on top. Crystals obtained are 99.6% pure and they were combined with other product for a total of 0.42 g (26% yield) of the title compound.


Synthesis of Compound 43



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The Iridium (III) dimer (1.75 g, 1.09 mmol) and 3,7-diethylnonane-4,6-dione (2.31 g, 10.9 mmol) was diluted with 2-ethoxyethanol (40 mL), degassed by bubbling nitrogen for 30 minutes and potassium carbonate (1.50 g, 10.9 mmol) was added. The mixture was stirred at room temperature overnight. Dichloromethane (100 mL) was added; the reaction mixture was filtered through a pad of Celite® and the pad was washed with dichloromethane. The solvents were evaporated and the red solid was coated on Celite® followed by purification by column chromatography on a triethylamine pre-treated silica gel column using 10% DCM in heptanes as eluent. The red solid obtained was washed with methanol and re-purified by column chromatography by using 5% DCM in heptanes which affords the pure target compound (340 mg, 31% yield).


Synthesis of Compound 54
Synthesis of 5-cyclopentyl-2-(3,5-dimethylphenyl)quinoline



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5-chloro-2-(3,5-dimethylphenyl)quinoline (4.29 g, 16.0 mmol), 2′-(dicyclohexylphosphino)-N2,N2,N6,N6-tetramethyl-[1,1′-biphenyl]-2,6-diamine (CPhos) (0.28 g, 0.64 mmol) and diacetoxypalladium (0.072 g, 0.320 mmol) were dissolved in anhydrous THE (60 mL). A solution of cyclopentylzinc(II) bromide (44.9 ml, 22.4 mmol) in THF (0.5 M) was added dropwise via syringe, and stirred at room temperature for 3 hours. The mixture was diluted in EA, washed with brine, dried with sodium sulfate, and concentrated under reduced pressure. The crude material was purified by column chromatography on silica, eluted with heptanes/EA 4/1 (v/v). The yellow powder was then recrystallized from heptanes to afford the title compound as colorless crystals (3.5 g, 72% yield).


Synthesis of Ir(III) Dimer



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5-Cyclopentyl-2-(3,5-dimethylphenyl)quinoline (3.56 g, 11.8 mmol) and iridium(III) chloride trihydrate (1.30 g, 3.69 mmol) were dissolved in the mixture of ethoxyethanol (90 mL) and water (30 mL). Reaction mixture was degassed and heated to 105° C. for 24 h. The reaction mixture was then cooled down to room temperature and filtered through filter paper. The filtrate was washed with methanol and dried in vacuum, providing iridium complex dimer as dark solid 1.60 g (54% yield).


Synthesis of Compound 54



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Iridium complex dimer (1.60 g, 1.00 mmol), 3,7-diethylnonane-4,6-dione (2.12 g, 9.98 mmol) and sodium carbonate (0.53 g, 4.99 mmol) were suspended in 50 mL of ethoxyethanol, and stirred overnight under N2 at room temperature. The reaction mixture was then filtered through a pad of Celite®, washed with MeOH. Most of the red material was solubilized and passed through the Celite®. The Celite® was suspended in DCM, containing 10% of triethylamine and this suspension was combined with filtrate and evaporated. The residue was purified by column chromatography on silica gel, pre-treated with Et3N, eluted with hexane/ethyl acetate 9/1 (v/v) mixture, providing a dark red solid. Additional purification with reverse-phase C18 column, eluted with acetonitrile provided after evaporation target complex as dark red solid (0.75 mg, 37% yield).


Synthesis of Compound 55



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Ir(III) Dimer (2.40 g, 1.45 mmol), potassium carbonate (2.00 g, 14.5 mmol) and 3,7-diethylnonane-4,6-dione (3.08 g, 14.5 mmol) were suspended in 40 mL of ethoxyethanol, degassed and stirred overnight at 45° C. The reaction mixture was cooled down to room temperature and filtered through a pad of Celite, the pad was washed with cold MeOH. The precipitate combined with the pad of Celite® were suspended in 50 mL of DCM with 5% of Et3N, and filtered through silica plug. The solution was evaporated, providing red solid. Crystallization from DCM/Acetonitrile/MeOH mixture provided 1.4 g of target complex (48% yield).


Synthesis of Compound 62



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To a 500 mL round bottom flask was added the chloro-bridged dimer (6.08 g, 3.54 mmol), 3,7-diethylnonane-4,6-dione (4.26 g, 20.06 mmol), sodium carbonate (3.75 g, 35.4 mmol), and 120 mL 2-ethoxyethanol. The reaction mixture was stirred overnight under nitrogen. The reaction mixture was poured onto a plug containing Celite®, basic alumina, and silica gel. The plug was pretreated with 10% triethylamine/heptane, and then washed with heptane and dichloromethane. The plug was eluted with dichloromethane. The filtrate was evaporated in the presence of isopropanol and a solid was filtered from isopropanol. The solid was dissolved in tetrahydrofuran and isopropanol was added. The tetrahydrofuran was removed under reduced pressure and the solution condensed. A red solid was filtered off, washed with isopropanol and dried (4.39 g, 60% yield).


Synthesis of Compound 83



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Ir(III) dimer (2.50 g, 2.49 mmol), 3,7-diethylnonane-4,6-dione (3.70 g, 17.43 mmol) and potassium carbonate (2.41 g, 17.4 mmol) were suspended in 50 mL of ethoxyethanol, the reaction mixture was degassed and stirred for 24 h at ambient temperature. Then the reaction mixture was filtered through Celite® pad and the pad was washed with MeOH. The solid filtrate with Celite® was suspended in DCM, containing 10% of Et3N, filtered through silica plug and evaporated. The solid residue was crystallized from DCM/THF/MeOH mixture, providing target complex as red solid (3.1 g, 65% yield).


Synthesis of Compound 93
Synthesis of 4-fluoro-3,5-dimethylbenzoyl chloride



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Oxalyl chloride (6.93 ml, 79 mmol) was added dropwise to a solution of 4-fluoro-3,5-dimethylbenzoic acid (12.1 g, 72.0 mmol) in dichloromethane (360 mL) and DMF (0.06 mL, 0.720 mmol) under nitrogen at room temperature. The mixture was then stirred at room temperature and monitored by TLC. Complete solubilization of the mixture occurred within 3 hours. The reaction was complete after an additional hour. Solvent was removed under reduced pressure and the crude mixture was dried in high vacuum and used without further purification.


Synthesis of 4-fluoro-N-(4-isopropylphenethyl)-3,5-dimethylbenzamide



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Pyridine (12.12 ml, 150 mmol) and 2-(4-isopropylphenyl)ethanamine hydrochloride (10 g, 50.1 mmol) were added into a 3-necked flask and dissolved in DCM (50 mL). The solution was cooled with an ice-bath and 4-fluoro-3,5-dimethylbenzoyl chloride (10.28 g, 55.1 mmol) was added slowly (portions) and the mixture was stirred at room temperature for 12 hours. DCM was added and the organic layer was washed with 5% HCl and then 5% NaOH solution and dried with sodium sulfate. The solvent was evaporated and the crude compound was used without further purification.


Synthesis of 1-(4-fluoro-3,5-dimethylphenyl)-7-isopropyl-3,4-dihydroisoquinoline



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4-Fluoro-N-(4-isopropylphenethyl)-3,5-dimethylbenzamide (15 g, 47.9 mmol), phosphorus pentoxide (42.8 g, 302 mmol), and phosphoryl oxochloride (44.6 ml, 479 mmol) were diluted in xylene (100 mL) and then refluxed for 3 hours under nitrogen. By GCMS, reaction was complete after 2.5 h. The reaction mixture was cooled to RT and stir overnight, the solvent was decanted and ice was slowly added to the solid. The residue mixture in water was made weakly alkaline by adding 50% NaOH and the product was extracted with toluene. The organic layer was washed with water, dried over sodium sulfate, and the solvent was evaporated under reduced pressure. The crude product was used without further purification.


Synthesis of 1-(4-fluoro-3,5-dimethylphenyl)-7-isopropylisoquinoline



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The solution of 1-(4-fluoro-3,5-dimethylphenyl)-7-isopropyl-3,4-dihydroisoquinoline (14.4 g, 47.9 mmol) in xylene (240 mL) was degassed by bubbling nitrogen for 15 minutes. In the meantime, 5% palladium (2.55 g, 2.39 mmol) on carbon was added. The mixture was heated to reflux overnight. The reaction was monitored by TLC. The mixture was filtered through a pad of Celite® and the solvents were evaporated under reduced pressure. The product was coated on Celite® and purified by column chromatography using 10% EA in heptanes to let first impurities come out the EA volume was slowly increased to 15% to let the target come out. The product contains a 2% impurity which comes 10 minutes after the target on HPLC. A reverse phase chromatography on C18 column eluted with 95/5 MeCN/water (v/v) provided 4.5 g of pure material (32% yield over 4 steps).


Synthesis of Ir(III) Dimer



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Iridium(III) chloride trihydrate (1.64 g, 4.65 mmol) and 1-(4-fluoro-3,5-dimethylphenyl)-7-isopropylisoquinoline (4.09 g, 13.95 mmol) were suspended in ethoxyethanol (50 mL) and water (12 mL), degassed by bubbling nitrogen and immersed in the oil bath at 105° C. overnight. After cooling down to room temperature, the solid was filtered, washed with MeOH and dried under vacuum to afford 1.8 g (74% yield) of red solid.


Synthesis of Compound 93



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Ir(III) Dimer (1.00 g, 0.96 mmol) was combined with 3,7-diethylnonane-4,6-dione (1.53 g, 7.21 mmol) and the mixture was diluted with 2-ethoxyethanol (36 mL). The solution was degassed by bubbling nitrogen for 15 minute. Potassium carbonate (0.997 g, 7.21 mmol) was then added and the mixture was stirred at room temperature for 18 hours. Then the bright red precipitate was filtered on a Celite® pad and washed with MeOH. The filtrated was discarded and the solid on top of the Celite® was then washed with DCM. The crude product was coated on celite and purified by column chromatography using 5% DCM in heptanes on a triethylamine pre-treated silica gel column. The target compound was obtained as red solid (0.9 g).


Synthesis of Compound 118
Synthesis of 5-isobutylquinoline



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A mixture of 5-bromoquinoline (20 g, 93 mmol), isobutylboronic acid (19.4 g, 186 mmol) and potassium phosphate, H2O (64.4 g, 280 mmol) in toluene (600 mL) was purged with N2 for 20 minutes Pd2dba3 (1.71 g, 1.87 mmol) and dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine (3.06 g, 7.46 mmol) (SPhOS) were then added. The mixture was heated to reflux overnight. The reaction was worked up upon completion. The crude was purified by silica gel column chromatography using heptane/EA: 85/15 to 7/3 (v/v) gradient mixture as eluent to give an oil (11.5 g, 67% yield).


Synthesis of 5-isobutylquinoline 1-oxide



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3-Chloroperoxybenzoic acid (m-CPBA) (16.6 g, 74.2 mmol) was added by portions to a solution of 5-isobutylquinoline (12.5 g, 67.5 mmol) in DCM (150 mL) cooled at 0° C. under nitrogen. The mixture was then stirred at room temperature overnight and at 50° C. for 11 hours. More m-CPBA was added to complete the reaction. Upon completion, the reaction mixture was quenched with aqueous NaHCO3. Aqueous mixture was extracted with DCM, washed with water and brine, and dried over Na2SO4. The crude was purified by silica gel column chromatography using DCM/MeOH: 97/3 to 95/5 (v/v) gradient mixture as eluent to give an off-white solid (11.0 g, 80.0% yield).


Synthesis of 5-isobutylquinolin-2(1H)-one



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Trifluoroacetic anhydride (61.8 ml, 437 mmol) was added to a 0° C., stirred solution of 5-isobutylquinoline 1-oxide (11 g, 54.7 mmol) in DMF (70 mL) under N2. The mixture was then stirred at room temperature overnight. Upon completion, the trifluoroacetic anhydride was removed under reduced pressure. The residue was quenched with aqueous NaHCO3 and further diluted with water. The crude was recrystallized from aqueous DMF to give a white solid (8.2 g, 75% yield).


Synthesis of 2-chloro-5-isobutylquinoline



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Phosphorus oxychloride (7.60 ml, 81 mmol) was added dropwise to a solution of 5-isobutylquinolin-2(1H)-one (8.2 g, 40.7 mmol) in DMF (160 mL) over 30 minutes under N2. The reaction mixture was then heated at 80° C. After the reaction was complete, the remaining POCl3 was evaporated under reduced pressure and aqueous Na2CO3 was carefully added. The solid was isolated to give an off-white solid (8.1 g, 91% yield).


Synthesis of 2-(3,5-dichlorophenyl)-5-isobutylquinoline



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Nitrogen gas was bubbled into a mixture of (3,5-dichlorophenyl)boronic acid (10.6 g, 55.5 mmol), 2-chloro-5-isobutylquinoline (8.13 g, 37 mmol) and Na2CO3 (7.84 g, 74.0 mmol) in THE (250 mL) and water (50 mL) for 30 min. Tetrakis(triphenylphosphine)palladium (0) (1.71 g, 1.48 mmol) was added and the mixture was heated to reflux overnight. Upon completion (monitored by GCMS) the reaction was worked up by diluting in ethyl acetate and washing with brine and water. The organic layer was dried with sodium sulfate and solvent was evaporated under reduced pressure to give a crude material, which was purified by silica gel column chromatography using heptanes/EA: 98/2 to 96/(v/v) gradient mixture as eluent to yield a solid (8.0 g, 66% yield).


Synthesis of 2-(3,5-dimethyl(D6)phenyl)-5-isobutylquinoline



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CD3MgI (61 mL, 61 mmol) in diethyl ether (1.0 M) was added into a stirred mixture of 2-(3,5-dichlorophenyl)-5-isobutylquinoline (8.0 g, 24.2 mmol) and dichloro(1,3-bis(diphenylphosphino)propane)nickel (Ni(dppp)Cl2) (0.39 g, 0.73 mmol) in diethyl ether (120 mL) over a period of 30 min. The mixture was stirred at room temperature overnight. Upon completion, the reaction was cooled with an ice bath and quenched carefully with water. The mixture was extracted with EA, washed with water (3 times) and brine. The crude product was purified by silica gel column chromatography using heptanes/DCM/EA 89/10/1 to 84/15/1 (v/v/v) gradient mixture as eluent to yield an oil (6.5 g, 91% yield).


Synthesis of Ir(III) Dimer



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A mixture of 2-(3,5-dimethyl(D6)phenyl)-5-isobutylquinoline (5.17 g, 17.5 mmol) and iridium(III) chloride (1.80 g, 4.86 mmol) in ethoxyethanol (30 mL) and water (10 mL) was degassed by bubbling N2 for 30 minutes before heating at 100° C. for 19 h. The reaction mixture was cooled down and small amount of MeOH was added. The Ir(III) dimer was isolated by filtration to give a solid (2.40 g, 61% yield), which was used for next reaction without further purification.


Synthesis of Compound 118



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A mixture of Ir(III) dimer (1.30 g, 0.80 mmol), 3,7-diethylnonane-4,6-dione (1.69 g, 7.96 mmol), Na2CO3 (1.69 g, 15.9 mmol) in ethoxyethanol (25 mL) was degassed for 20 minutes and stirred at room temperature for 24 hours. The reaction mixture was filtered and washed with small amount of methanol and heptane. The solid was dissolved in 10% triethylamine (TEA) in DCM. The mixture was filtered and evaporated under reduced pressure. The red solid was recrystallized from DCM/IPA with 5% TEA to give a red solid (7.0 g, 44% yield).


Synthesis of Compound 141



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The Ir(III) dimer (0.80 g, 0.58 mmol) and 6-ethyl-2-methyloctane-3,5-dione (0.75 g, 4.06 mmol) were inserted in a round-bottom flask. The mixture was diluted in 2-ethoxyethanol (40 mL), degassed with nitrogen for 30 minutes and K2CO3 (0.60 g, 4.33 mmol) was inserted. The mixture was stirred at room temperature overnight. The precipitate was filtered through a pad of Celite®. The solvent was evaporated and the crude material was purified with column chromatography on silica gel by using a mixture of heptanes/DCM 95/5 (v/v). The pure material (0.65 g, 67% yield) was obtained.


Synthesis of Compound 142



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The Iridium (III) dimer (0.80 g, 0.56 mmol) and 6-ethyl-2-methyloctane-3,5-dione (0.77 g, 4.16 mmol) were diluted in ethoxyethanol (19 mL). The mixture was degassed by bubbling nitrogen for 15 minutes followed by the addition of K2CO3 (0.576 g, 4.16 mmol) and the mixture was stirred at room temperature overnight. Dichloromethane was added followed by filtration of the solution through a pad of Celite® and washed with dichloromethane until the filtrate is clear. The crude product was purified by column chromatography by using a triethylamine-treated silica gel column and eluting with a mixture of heptanes/dichloromethane 95/5 (v/v). The pure product was collected (0.35 g, 67% yield) as a red powder.


Synthesis of Compound 176



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The Ir(III) Dimer (0.75 g, 0.47 mmol) and 6-ethyl-2-methyloctane-3,5-dione (0.64 g, 3.50 mmol) were diluted with ethoxyethanol (16 mL), degassed with nitrogen for 30 minutes, K2CO3 (0.48 g, 3.50 mmol) was added and the mixture was stirred at room temperature overnight. DCM was added to the mixture to solubilize the product, the reaction mixture was filtered through a pad of Celite® and evaporated. The crude material was purified with column chromatography on silica gel, eluted with the mixture of heptanes/DCM 95/5 (v/v), provided the pure material (0.59 g, 66% yield)


Synthesis of Compound 278



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To a round bottom flask was added the chloro-bridged dimer (4.37 g, 2.91 mmol), 3,7-diethyl-5-methylnonane-4,6-dione (3.7 g, 16.4 mmol), sodium carbonate (3.08 g, 29.1 mmol), and 100 mL 2-ethoxyethanol. The reaction mixture was stirred at room temperature for 48 h under nitrogen. The reaction mixture was poured onto a plug containing Celite®, basic alumina, and silica gel. The plug was pretreated with 10% triethylamine/heptanes, and then washed with heptane and dichloromethane. The plug was eluted with dichloromethane. The filtrate was evaporated in the presence of isopropanol and a solid was filtered from isopropanol. The solid was dissolved in tetrahydrofuran and isopropanol was added. The tetrahydrofuran was removed on a rotovap and the solution condensed. A red solid was filtered off and washed with isopropanol (0.79 g, 16% yield).


Synthesis of Compound 320



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Ir(III) dimer (2.00 g, 1.25 mmol), 3,7-diethyl-5-methylnonane-4,6-dione (1.98 g, 8.73 mmol) and potassium carbonate (1.21 g, 8.73 mmol) were suspended in 50 mL of ethoxyethanol. The reaction mixture was degassed and stirred overnight at room temperature. It was then cooled in the ice bath, filtered through celite pad, and the pad was washed with cold MeOH. The precipitate with the Celite® was suspended in DCM, containing 5% of Et3N, and filtered through silica pad. The solution was evaporated, providing red solid. The solid was purified by crystallization from DCM/MeOH, providing target complex as red solid (1.5 g, 59%).


Synthesis of Comparative Compound 4



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The Iridium (III) Dimer (0.70 g, 0.51 mmol) and 3-ethyldecane-4,6-dione (0.75 g, 3.79 mmol) were suspended in ethoxyethanol (17 mL). The reaction was degassed by bubbling nitrogen for 15 minutes followed by addition K2CO3 (0.52 g, 3.79 mmol). The mixture was stirred at room temperature overnight. Thin layer chromatography was performed on the reaction mixture in the morning showing complete consumption of the dimer. Dichloromethane was added followed by filtration of the solution through a pad of Celite® and washed with dichloromethane until the filtrate is clear. The crude product was purified by column chromatography by using a triethylamine-treated column and eluting with a mixture of heptanes/dichloromethane (95/5, v/v). The pure product was collected (0.600 g, 70% yield) as a red powder.


It is understood that the various embodiments described herein are byway 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.

Claims
  • 1. A compound comprising a first ligand L1 having the formula:
  • 2. The compound of claim 1, wherein the metal M is Ir.
  • 3. The compound of claim 1, wherein R5 is selected from group consisting of hydrogen, deuterium, alkyl, cycloalkyl, and combinations thereof.
  • 4. The compound of claim 1, wherein R5 is hydrogen.
  • 5. The compound of claim 1, wherein R1, R2, R3, and R4 are alkyl or cycloalkyl.
  • 6. The compound of claim 1, wherein R1, R2, R3, and R4 are 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.
  • 7. The compound of claim 1, wherein the compound has the formula of M(L1)x(L2)y(L3)z;wherein L2 is a second ligand and L3 is a third ligand and L2 and L3 can be the same or different;wherein x is 1, 2, or 3;wherein y is 0, 1, or 2;wherein z is 0, 1, or 2;wherein x+y+z is the oxidation state of the metal M;wherein the second ligand L2 and the third ligand L3 are independently selected from the group consisting of:
  • 8. The compound of claim 7, wherein the compound has the formula of M(L1)(L2)2.
  • 9. The compound of claim 7, wherein L is selected from group consisting of:
  • 10. The compound of claim 9, wherein L2 is selected from group consisting of:
  • 11. The compound of claim 10, wherein the compound having the formula of M(L1)(L2)2 is selected from the group consisting of Compound 1 to Compound 1729 defined in the table below:
  • 12. The compound of claim 1, wherein the compound is selected from the group consisting of:
  • 13. The compound of claim 1, wherein at least two of R1, R2, R3, and R4 have at least two C atoms.
  • 14. The compound of claim 1, wherein at least three of R1, R2, R3, and R4 have at least two C atoms.
  • 15. The compound of claim 1, wherein each of R1, R2, R3, and R4 has at least two C atoms.
  • 16. A device comprising a first organic light emitting device, the first organic light emitting device comprising: an anode;a cathode; andan organic layer, disposed between the anode and the cathode, comprising a compound comprising a first ligand L1 having the formula:
  • 17. The device of claim 16, wherein the organic layer is an emissive layer and the compound is an emissive dopant.
  • 18. The first device of claim 16, wherein the organic layer further comprises a host material comprising at least one chemical group selected from the group consisting of carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
  • 19. The first device of claim 18, wherein the host material is selected from the group consisting of:
  • 20. A consumer product comprising a first organic light emitting device, the first organic light emitting device comprising: an anode;a cathode; andan organic layer, disposed between the anode and the cathode, comprising a compound comprising a first ligand L1 having the formula:
CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No. 16/129,152, filed Sep. 12, 2018, which is a continuation of U.S. application Ser. No. 13/932,508, filed Jul. 1, 2013, now U.S. Pat. No. 10,199,581, the disclosure of which is herein expressly incorporated by reference in its entirety.

Continuations (2)
Number Date Country
Parent 16129152 Sep 2018 US
Child 17210087 US
Parent 13932508 Jul 2013 US
Child 16129152 US