Triphenylene-benzofuran / benzothiophene / benzoselenophene compounds with substituents that fuse together to form rings, and a device comprising these.

Abstract

Compound selected from the group consisting of: where XO, S or Se; where R1, R2 and R a are independently selected from hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, alkynyl, arylkyl, aryl and heteroaryl; where each of R1 and R2 can represent mono-, di-, tri- or tetrasubstitution; where at least two substituents of R1 or R2 are fused to form a ring; where R a represents mono- or di-substitutions that cannot fuse to form a benzo ring; where L represents a spacer or a direct bond with the benzofuran, benzothiophene, or benzoselenophene residue with additional fused rings; wherein R'1, R'2 and R'3 are independently selected from the group consisting of hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, alkynyl, arylcyl, aryl and heteroaryl; and where each of R'1, R'2 and R'3 can represent mono-, di-, tri- or tetrasubstitution.

Description

AREA OF INVENTION

[0001] The present invention relates to organic light-emitting devices (OLEDs). In particular, the present invention relates to phosphorescent materials comprising a triphenylene residue and a benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, benzoselenophene, or dibenzoselenophene residue. Specifically, the present invention relates to triphenylene-benzofuran / benzothiophene / benzoselenophene compounds with substituents that combine to form fused rings, and to a device comprising these. These materials can provide devices with improved performance. STATE OF THE ART

[0002] Optoelectronic devices utilizing organic materials are gaining popularity for a number of reasons. Many of the materials used to fabricate such devices are relatively inexpensive, giving organic optoelectronic devices the potential for cost advantages over inorganic devices. Additionally, the inherent properties of organic materials, such as their flexibility, make them well-suited for certain applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting diodes (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. In the case of OLEDs, organic materials can offer performance advantages over conventional materials. For example,The wavelength at which an organic emitter layer emits light can generally be easily adjusted using appropriate dopants.

[0003] OLEDs employ thin organic films that emit light when a voltage is applied across the device. OLEDs are currently considered an increasingly promising technology for applications such as flat panel displays, lighting, and backlighting. Several OLED materials and configurations are described in US patents 5,844,363 A, 6,303,238 B1, and 5,707,745 A. Further materials for use in an OLED are described, for example, in WO 2009 / 021126 A2.

[0004] One application for phosphorescent emitter molecules is a full-color display. Industry standards for such displays specify pixels designed to emit particular colors, also known as "saturated" colors. Specifically, these standards call for pixels with saturated red, green, and blue. Color can be measured using CIE coordinates, which are well-known according to the prior art.

[0005] An example of a green emitter molecule is Tris(2-phenylpyridine)iridium, designated Ir(ppy)3, which has the following structure:

[0006] In this and subsequent figures contained herein, we represent the coordinate bond between nitrogen and metal (here Ir) as a straight line.

[0007] As used herein, the term "organic" encompasses both polymeric materials and organic materials with small molecules used to fabricate organic optoelectronic devices. The term "small molecules" refers to any organic material that is not a polymer, and "small molecules" can indeed be quite large. Small molecules may contain repeating units. The use of a long-chain alkyl group as a substituent, for example, does not exclude a molecule from the class of "small molecules." Small molecules may also be incorporated into polymers, for example, as a side group on a polymer backbone or as part of the backbone itself. Small molecules may also serve as the core unit of a dendrimer, which consists of a series of chemical shells built upon the core unit.The core unit of a dendrimer can be a fluorescent or phosphorescent small molecule emitter. A dendrimer can be a "small molecule," and it is assumed that all dendrimers currently used in OLEDs are small molecules.

[0008] As used herein, "top" means furthest from the substrate, while "bottom" means closest to the substrate. When a first layer is described as "arranged above," the first layer is located farther away from the substrate. Other layers may also be located between the first and second layers unless it is explicitly stated that the first layer is "in contact with" the second layer. For example, a cathode may be described as "arranged above" an anode, even though various organic layers may be in between.

[0009] As used herein, “processable solution” means capable of being dissolved, dispersed or transported in and / or applied from a liquid medium, either in solution or suspension form.

[0010] A ligand can be described as "photoactive" if it is assumed that the ligand directly contributes to the photoactive properties of an emitter material. A ligand can be described as "ancillary" if it is assumed that the ligand does not contribute to the photoactive properties of an emitter material, although an ancillary ligand can modify the properties of a photoactive ligand.

[0011] As used herein and as generally understood by those skilled in the art, a "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 negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (an EA that is less than negative). On a conventional energy level diagram with the vacuum level on 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.

[0012] As used herein, and as generally understood by those skilled in the field, 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 the 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, the "higher" work function is represented as being farther away from the vacuum level in the downward direction. Therefore, the definitions of HOMO and LUMO energy levels follow a different convention than those of work functions.

[0013] More details about OLEDs and the definitions described above can be found in patent US 7 279 704 B2. SUMMARY OF THE INVENTION

[0014] Compounds comprising a triphenylene residue and a benzo- or dibenzofuran-, benzo- or dibenzothiophene-, or benzo- or dibenzoselenophene residue with fused substituents are provided. The compounds have the following formula:

[0015] R'1, R'2, and R'3 are independently selected from the group consisting of hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, alkynyl, aryl cyl, aryl, and heteroaryl. Each of R'1, R'2, and R'3 can represent a mono-, di-, tri-, or tetrasubstituent. The compound further comprises a benzofuran, benzothiophene, benzoselenophene, dibenzofuran, dibenzothiophene, or dibenzoselenophene residue, and additionally includes an aromatic or heteroaromatic ring fused to a benzo ring of the benzofuran, benzothiophene, benzoselenophene, dibenzofuran, dibenzothiophene, or dibenzselenophene residue.

[0016] According to one perspective, the aromatic or heteroaromatic ring is a 6-membered carbocyclic or heterocyclic ring. According to another perspective, the aromatic ring is a benzene ring.

[0017] According to the invention, the compound is selected from the group consisting of:

[0018] X is O, S, or Se. According to one aspect, X is S. According to another aspect, X is O. R1, R2, and R a are independently selected from hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, alkynyl, aryl, and heteroaryl. Each of R1 and R2 can represent a mono-, di-, tri-, or tetrasubstituent. At least two substituents of R1 and R2 are linked to form a fused ring. a Represents mono- or di-substituents that cannot be fused to form a benzo ring. L represents a spacer or a direct bond to the benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, benzoselenophene, or benzoselenophene residue with additional fused rings.

[0019] The compound preferably has the following formula:

[0020] According to one aspect, L is a direct bond. According to another aspect, L is a spacer with the formula:

[0021] A, B, C and D were each independently selected from the group consisting of:

[0022] A, B, C and D are optionally also available with R a Substituted. Each of p, q, r, and s is 0, 1, 2, 3, or 4. p+q+r+s is at least 1. L-phenyl is preferred.

[0023] According to one aspect, the benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, benzoselenophene or dibenzselenophene residue with the additional fused rings is selected from the group consisting of:

[0024] Examples of compounds are provided, including compounds selected from the group consisting of Formula 4 - 1 to Formula 4 - 28.

[0025] X is O, S, or Se. R1, R2, R3, R4, R5, R'1, R'2, and R'3 are each independently selected from the group consisting of hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, alkynyl, aryl, and heteroaryl. Each of R1, R2, R3, R4, R5, R'1, R'2, and R'3 can be a mono-, di-, tri-, or tetrasubstituent. L is a spacer or a direct bond.

[0026] Specific examples of the compounds are provided, including compounds selected from the group consisting of compound 3 - compound 69.

[0027] X is O, S or Se.

[0028] Additionally, a first device comprising an organic light-emitting device is provided. The organic light-emitting device further comprises an anode, a cathode, and an organic layer arranged between the anode and the cathode. The organic layer comprises a compound having the following formula:

[0029] R'1, R'2, and R'3 are independently selected from the group consisting of hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, alkynyl, aryl, and heteroaryl. Each of R'1, R'2, and R'3 can represent a mono-, di-, tri-, or tetrasubstituent. The compound further comprises a benzofuran, benzothiophene, benzoselenophene, dibenzofuran, dibenzothiophene, or dibenzselenophene residue, and additionally includes an aromatic or heteroaromatic ring fused to a benzoring of the benzofuran, benzothiophene, benzoselenophene, dibenzofuran, dibenzothiophene, or dibenzselenophene residue.

[0030] According to the invention, the compound is selected from the group consisting of:

[0031] X is O, S, or Se. R1, R2, and R aEach of the substituents R1 and R2 is independently selected from the group consisting of hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, alkynyl, aryl, and heteroaryl. Each of R1 and R2 can represent a mono-, di-, tri-, or tetrasubstituent. At least two substituents of R1 or R2 are linked to form a fused ring. a Represents mono- or disubstituents that cannot be fused to form a benzo ring. L represents a spacer or a direct bond to the benzofuran, benzothiophene, or benzoselenophene moiety with additional fused rings.

[0032] According to one aspect, the organic layer is an emitter layer and the compound of formula l is the host. According to another aspect, the organic layer further comprises an emitter compound. According to yet another aspect, the emitter compound is a transition metal complex with at least one ligand selected from the group consisting of:

[0033] Each of R' a , R' b , and R' c can represent mono-, di-, tri-, or tetrasubstituents. Each of R' a , R' b , and R' c Each substituent is independently selected from the group consisting of hydrogen, deuterium, alkyl, heteroalkyl, aryl, or heteroaryl. Two adjacent substituents can combine to form a ring.

[0034] According to another aspect, the device includes a second organic layer that is non-emitting and the compound comprising formula I is a non-emitting material in the second organic layer.

[0035] According to one aspect, the first device is an organic light-emitting device. According to another aspect, the first device is a consumer product. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] They show: Fig.1 an organic light-emitting device. Fig. 2 an inverted organic light-emitting device that does not have a separate electron transport layer. Fig. 3 compounds comprising a triphenylene residue and a benzo or dibenzo residue, which is further substituted with a fused substituent. DETAILED DESCRIPTION

[0037] In general, an OLED comprises at least one organic layer positioned between an anode and a cathode and electrically connected to them. When current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons migrate to the oppositely charged electrode. When an electron and a hole are located on the same molecule, an "exciton" is formed, which is a localized electron / hole pair in an excited energy state. Light is emitted when the exciton relaxes via a photoemitting mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, can also occur but are generally considered undesirable.

[0038] The original OLEDs used emitter molecules that emit light from the singlet state (“fluorescence”), as disclosed, for example, in US patent 4,769,292 A. Fluorescence emission generally occurs over a period of less than 10 nanoseconds.

[0039] Recently, OLEDs with emitter materials that emit light from the triplet state (“phosphorescence”) have been described. See Baldo et al., “High-efficiency phosphorescent emission from organic electroluminescent devices,” 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”). The phosphorescence is described in detail in US Patent 7,279,704 B2, columns 5–6.

[0040] Fig.Figure 1 shows an organic light-emitting device 100. The figures are not necessarily drawn to scale. The device 100 comprises a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emitter layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, and a cathode 160. The cathode 160 is a compound cathode with a first conductor layer 162 and a second conductor layer 164. The device 100 can be fabricated by applying the described layers in sequence. The properties and functions of these various layers, as well as exemplary materials, are described in detail in US Patent 7,279,704 B2, columns 6-10.

[0041] Further examples are available for each of these layers. For example, a flexible and transparent substrate / anode combination is disclosed in US patent application 5,844,363 A. An example of a p-doped hole transport layer is m-MTDATA doped with F.sub.4-TCNQ in a molar ratio of 50:1, as disclosed in US patent application 2003 / 0230980 A1. Examples of emitter and host materials are disclosed in US patent application 6,303,238 B1, granted to Thompson et al. An example of an n-doped electron transport layer is BPhen doped with Li in a molar ratio of 1:1, as disclosed in US patent application 2003 / 0230980 A. Patents US 5,703,436 A and US 5,707,745 A disclose examples of cathodes, including compound cathodes, with a thin layer of metal, such as Mg:Ag, with a superimposed, transparent, electrically conductive ITO layer applied by sputtering.The theory and use of blocking layers are described in detail in US patent specification 6,097,147 A and in US patent application 2003 / 0230980 A1. Examples of injection layers are provided in US patent application 2004 / 0174116 A. A description of protective layers can be found in US patent application 2004 / 0174116 A1.

[0042] Fig.Figure 2 shows an inverted OLED 200. The device comprises a substrate 210, a cathode 215, an emitter layer 220, a hole transport layer 225, and an anode 230. The device 200 can be fabricated by depositing the described layers sequentially. Since the most conventional OLED configuration has a cathode positioned above the anode, and the device 200 has a cathode 215 positioned below the anode 230, the device 200 can be described as an "inverted" OLED. Similar materials to those described with respect to the device 100 can be used in the corresponding layers of the device 200. Fig. Figure 2 shows an example of how some layers in the structure of device 100 can be omitted.

[0043] The in Fig. 1 and Fig.The simple layer structure shown in Figure 2 is provided as a non-limiting example, and it is understood that the embodiments of the invention can be used in conjunction with a wide variety of other structures. The specific materials and structures described are exemplary, and other materials and structures can also be used. Functional OLEDs can be achieved by combining the described layers in various ways, or layers can be omitted based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials not specifically described may be used. Although many of the examples provided herein describe different layers with a single material, it is understood that combinations of materials, such as...A mixture of host and dopant, or more generally any mixture, can be used. The layers can also have different sublayers. The various names given to the layers herein are not considered strictly restrictive. For example, in the device 200, the hole transport layer 225 transports holes and injects holes into the emitter layer 220 and can be described as a hole transport layer or a hole injection layer. According to one embodiment, an OLED as described may have an “organic layer” arranged between a cathode and an anode. This organic layer may comprise a single layer or may further comprise several layers of different organic materials as described, such as, for example, in relation to… Fig. 1 and Fig. 2.

[0044] Structures and materials not specifically described can also be used, such as polymer OLEDs (PLEDs), like those described in US Patent 5,247,190 A, granted to Friend et al. Another example is the use of OLEDs with a single organic layer. The OLEDs can also be stacked, as described in US Patent 5,707,745 A, granted to Forrest et al. The OLED structure can be derived from the one described in Fig. 1 and Fig. The substrate may differ from the simple layer structure shown in Figure 2. For example, it may contain an angled, reflective surface to improve extraction, such as a mesa structure as described in US Patent 6,091,195 A, granted to Forrest et al., and / or a pit structure as described in US Patent 5,834,893 A, granted to Bulovic et al.

[0045] Unless otherwise specified, any layers of the various embodiments described in US 6,087,196 A may be applied by any method. For the organic layers, preferred methods include thermal evaporation, inkjet printing (as described, for example, in US 6,013,982 A), organic vapor deposition (OVPD) (as described, for example, in US 6,337,102 B1, granted to Forrest et al.), and deposition by organic vapor jet printing (OVJP) (as described, for example, in US 2010 / 233470 A1). Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably carried out in a nitrogen or inert atmosphere. For the other layers, thermal evaporation is a preferred method. Preferred structuring methods include mask deposition and cold welding (as described, for example, in US 6,337,102 B1).The structuring process is described in US patents 6,294,398 B1 and 6,468,819 B1, and is associated with some of the deposition methods, such as inkjet and OVJD. Other methods may also be used. The materials to be deposited can be modified to make them compatible with a particular deposition method. Substituents, such as alkyl and aryl groups, branched or unbranched and preferably containing at least three carbons, can be used, for example, in small molecules to improve their ability to undergo solution processing. Substituents with 20 or more carbons can also be used, and a preferred range consists of 3 to 20 carbons.Materials with asymmetric structures may exhibit better solution processing capabilities than those with symmetric structures because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents can be used to improve the solution processing capabilities of small molecules.

[0046] Devices manufactured according to the embodiments of the invention can be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, televisions, billboards, indoor or outdoor lighting fixtures and / or displays, news displays, fully transparent displays, flexible displays, laser printers, telephones, mobile phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, microdisplays, vehicles, large-format walls, cinema or stadium screens, or in a sign. Various control mechanisms can be used to control the devices manufactured according to the present invention, including a passive matrix and an active matrix. Many of the devices are intended for use in a temperature range comfortable for humans, such as…18 degrees C to 30 degrees C and preferably at room temperature (20 - 25 degrees C).

[0047] The materials and structures described herein can also be used in devices other than OLEDs. Other optoelectronic devices, such as organic solar cells and organic photodetectors, can utilize these materials and structures. More generally, organic devices, such as organic transistors, can employ these materials and structures.

[0048] The terms halo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl cyl, heterocyclic group, aryl, aromatic group and heteroaryl are known according to the prior art and are defined in US 7 279 704 B2 in columns 31 - 32.

[0049] Compounds are provided, comprising triphenylene-containing benzofused furan, thiophene, or selenophene. Triphenylene is a polyaromatic hydrocarbon with high triplet energy, high π-conjugation, and a relatively small energy difference between the first singlet and first triplet levels. This suggests that triphenylene has relatively readily accessible HOMO and LUMO levels compared to other aromatic compounds with similar triplet energy (e.g., biphenyl). The advantage of using triphenylene and its derivatives as hosts is that they can accommodate red, green, and even blue phosphorescent dopants to provide higher efficiency without energy loss. Triphenylene hosts can be used to provide PHOLEDs with high efficiency and stability. See Kwong and Alleyene, Triphenylene Hosts in Phosphorescent Light Emitting Diodes, US 2006 / 0280965 A1.

[0050] Benzo-fused thiophenes can be used as organic hole transport conductors. Additionally, the triplet energies of benzothiophenes, namely dibenzo[b,d]thiophene (referred to herein as "dibenzothiophene"), benzo[b]thiophene, and benzo[c]thiophene, are relatively high.

[0051] Compounds with a combination of benzo-fused thiophenes and triphenyls can be advantageously used as hosts in PHOLEDs. Specifically, benzo-fused thiophenes are generally hole-transporting rather than electron-transporting, while triphenyls are more electron-transporting than hole-transporting. Therefore, combining these two groups in a single molecule can offer improved charge balance, which can enhance device performance in terms of lifetime, efficiency, and low voltage.

[0052] Different chemical linkages between the two residues can be used to adjust the properties of the resulting compound to make it most suitable for a particular phosphorescent emitter, device architecture, and / or manufacturing process. For example, an m-phenylene linkage is expected to result in a higher triplet energy and higher solubility, while a p-phenylene linkage is expected to result in a lower triplet energy and lower solubility.

[0053] Similar to the characterization of benzo-fused thiophenes, benzo-fused furans are also typically hole-transporting materials with a relatively high triplet energy. Examples of benzo-fused furans are benzofuran and dibenzofuran. Therefore, a material containing both a triphenylene and a benzofuran can be advantageously used as a host or hole-blocking material in a PHOLED. A compound containing both of these two groups can offer improved electron stabilization, which can enhance device stability and efficiency by lowering the voltage. The properties of triphenylene-containing benzofuran compounds can be tailored as needed by using various chemical linkages to connect the triphenylene and the benzofuran.

[0054] Organic light-emitting devices containing compounds with a triphenylene residue and a benzofuran, benzothiophene, or benzoselenophene residue are known to provide good performance and stability. See, for example, WO 2009 / 021126 A2 and WO 2010 / 036765 A1. Devices containing triphenylene-benzofuran / benzothiophene / benzoselenophene with additional fused rings can also exhibit good performance and stability, particularly if the fused rings are aromatic or heteroaromatic, since the aromatic fused rings increase the conjugation of the compound, leading to delocalization and stabilization of the charge in the oxidized or reduced state of the molecule.

[0055] Compounds are provided that comprise a triphenylene residue and a benzo- or dibenzofuran-, benzo- or dibenzothiophene-, or benzo- or dibenzselenophene residue with fused substituents (in Fig. 3 shown). The compounds comprise the formula:

[0056] R'1, R'2, and R'3 are each independently selected from the group consisting of hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, alkynyl, aryl cyl, aryl, and heteroaryl. Each of R'1, R'2, and R'3 can represent a mono-, di-, tri-, or tetrasubstituent. The compound further comprises a benzofuran, benzothiophene, benzoselenophene, dibenzofuran, dibenzothiophene, or dibenzselenophene residue, which further comprises an additional aromatic or heteroaromatic ring fused to a benzoring of the benzofuran, benzothiophene, benzoselenophene, dibenzofuran, dibenzothiophene, or dibenzselenophene residue.

[0057] According to one perspective, the aromatic or heteroaromatic ring is 6-membered and either carbocyclic or heterocyclic. According to another perspective, the aromatic ring is a benzene ring.

[0058] According to the invention, the compound is selected from the group consisting of:

[0059] X is O, S, or Se. According to one aspect, X is S. According to another aspect, X is O. R1, R2, and R a Each of the substituents R1 and R2 is independently selected from hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, alkynyl, aryl, and heteroaryl. Each can represent a mono-, di-, tri-, or tetrasubstituent. At least two substituents of R1 or R2 are linked to form a fused ring. a Represents mono- or di-substituents that cannot fuse to form a benzo ring. L represents a spacer or a direct bond to the benzofuran, benzothiophene, or benzoselenophene residue with additional fused rings.

[0060] The compound preferably has the following formula:

[0061] According to one aspect, L is a direct bond. According to another aspect, L is a spacer with the formula:

[0062] A, B, C and D were each independently selected from the group consisting of:

[0063] A, B, C and D are optionally still available with R a Substituted. Each of p, q, r, and s is 0, 1, 2, 3, or 4. p+q+r+s is at least 1. L-phenyl is preferred.

[0064] According to one aspect, the benzofuran, benzothiophene, or benzoselenophene moiety with additional fused rings is selected from the group consisting of:

[0065] Examples of connections are provided and include connections selected from the group consisting of:

[0066] X is O, S, or Se. R1, R2, R3, R4, R5, R'1, R'2, and R'3 are each independently selected from the group consisting of hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, alkynyl, aryl, and heteroaryl. Each of R1, R2, R3, R4, R5, R'1, R'2, and R'3 can be a mono-, di-, tri-, or tetrasubstituent. L is a spacer or a direct bond.

[0067] Specific examples of compounds are provided, including compounds selected from the group consisting of:

[0068] X is O, S or Se.

[0069] Additionally, a first device comprising an organic light-emitting device is provided. The organic light-emitting device further comprises an anode, a cathode, and an organic layer arranged between the anode and the cathode. The organic layer comprises a compound comprising the following formula:

[0070] R'1, R'2, and R'3 are each independently selected from the group consisting of hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, alkynyl, aryl cyl, aryl, and heteroaryl. Each of R'1, R'2, and R'3 can represent a mono-, di-, tri-, or tetrasubstituent. The compound further comprises a benzofuran, benzothiophene, benzoselenophene, dibenzofuran, dibenzothiophene, or dibenzselenophene residue, which further comprises an additional aromatic or heteroaromatic ring fused to a benzo ring of the benzofuran, benzothiophene, benzoselenophene, dibenzofuran, dibenzothiophene, or dibenzselenophene residue.

[0071] According to the invention, the compound is selected from the group consisting of:

[0072] X is O, S, or Se. R1, R2, and R aEach of the substituents R1 and R2 is independently selected from hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, alkynyl, aryl, and heteroaryl. Each of R1 and R2 can represent a mono-, di-, tri-, or tetrasubstituent. At least two substituents of R1 or R2 are linked to form a fused ring. a Represents mono- or di-substituents that cannot fuse to form a benzo ring. L represents a spacer or a direct bond to the benzofuran, benzothiophene, or benzoselenophene ring with additional fused rings.

[0073] According to one aspect, the organic layer is an emitter layer and the compound comprising formula 1 is the host. According to another aspect, the organic layer further comprises an emitting compound. According to yet another aspect, the emitting compound is a transition metal complex with at least one ligand selected from the group consisting of:

[0074] Each of R' a , R' b and R' c can represent mono-, di-, tri-, or tetrasubstituents. Each of R'2, R' b and R' c Each substituent is independently selected from the group consisting of hydrogen, deuterium, alkyl, heteroalkyl, aryl, or heteroaryl. Two adjacent substituents can form a ring.

[0075] According to another aspect, the device includes a second organic layer that is non-emitting and the compound comprising formula I is a non-emitting material in the second organic layer.

[0076] According to one aspect, the first device is an organic light-emitting device. According to another aspect, the first device is a consumer product. COMBINATION WITH OTHER MATERIALS / HTL:

[0077] The hole injection / transport material to be used in the present invention is not necessarily limited, and any compound may be used as long as it is typically used as a hole injection / transport material. Examples of the material include, but are not limited to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolecarbazole derivative; a fluorocarbon polymer; a polymer containing conductive dopants; a conductive polymer, such as PEDOT / PSS; a self-assembling monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoO₂. x ; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile; a metal complex; and a cross-linkable compound.

[0078] Examples of aromatic amine derivatives used in HIL or HTL include, but are not limited to, the following general structures:

[0079] Each of the Ar 1 to Ar 9is selected from the group consisting of aromatic, cyclic, hydrocarbon compounds, such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalen, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene;aus der Gruppe bestehend aus aromatischen heterozyklischen Verbindungen, wie z.B. Dibenzothiophen, Dibenzofuran, Dibenzselenophen, Furan, Thiophen, Benzofuran, Benzothiophen, Benzoselenophen, Carbazol, Indolcarbazol, Pyridylindol, Pyrrolodipyridin, Pyrazol, Imidazol, Triazol, Oxazol, Thiazol, Oxadiazol, Oxatriazol, Dioxazol, Thiadiazol, Pyridin, Pyridazin, Pyrimidin, Pyrazin, Triazin, Oxazin, Oxathiazin, Oxadiazin, Indol, Benzimidazol, Indazol, Indoxazin, Benzoxazol, Benzisoxazol, Benzthiazol, Quinolin, Isoquinolin, Cinnolin, Quinazolin, Quinoxalin, Naphthyridin, Phthalazin, Pteridin, Xanthen, Acridin, Phenazin, Phenothiazin, Phenoxazin, Benzfuropyridin, Furodipyridin, Benzothienopyridin, Thiendipyridin, Benzoselenphenopyridin und Selenphenodipyridin;and from the group consisting of 2 to 10 cyclic structural units, which are groups of the same type or of different types, selected from the aromatic cyclic hydrocarbon group and from the aromatic heterocyclic group, and which are linked directly or via at least one 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, alkyl, alkoxy, amino, alkenyl, alkynyl, arylalkyl, heteroalkyl, aryl and heteroaryl.

[0080] According to one aspect, Ar 1 to Ar 9 independently selected from the group consisting of: k is an integer from 1 to 20; X 1 up to X 8 is CH or N is; Ar 1 exhibits the same group as defined above.

[0081] Examples of metal complexes used in HIL or HTL include, but are not limited to, the following general formula:

[0082] M is a metal that has an atomic weight of more than 40; (Y 1 - Y 2 ) is a bidentate ligand, Y1 and are Y 2 independently selected from C, N, O, P and S; L is an ancillary ligand; m is an integer from 1 to the maximum number of ligands that can be attached to the metal; and m+n is the maximum number of ligands that can be attached to the metal.

[0083] According to one aspect, (Y 1 - Y 2 ) a 2-phenylpyridine derivative.

[0084] According to another aspect, (Y 1 - Y 2 ) a carbene ligand.

[0085] According to another aspect, M is selected from Ir, Pt, Os and Zn.

[0086] According to another aspect, the metal complex exhibits the lowest oxidation potential in solution towards Fc. + / Fc coupling of less than approximately 0.6 V. Host:

[0087] The light-emitting layer of the organic EL device of the present invention preferably contains at least one metal complex as a light-emitting material and can contain a host material that uses the metal complex as a dopant. Examples of the host material are not necessarily limiting, and any metal complexes or organic compounds can be used as long as the triplet energy of the host is greater than that of the dopant.

[0088] Examples of metal complexes used as hosts preferably have the following general formula:

[0089] M is a metal; (Y 3 - Y 4 ) is a bidentate ligand, Y 3 and Y 4are each independently selected from C, N, O, P and S; L is an additional ligand; m is an integer from 1 to the maximum number of ligands that can be attached to the metal; and m+n is the maximum number of ligands that can be attached to the metal.

[0090] According to one aspect, the metal complexes are:

[0091] (O - N) is a bidentate ligand with a metal coordinated to the atoms O and N.

[0092] According to another aspect, M is selected from Ir and Pt.

[0093] According to another aspect, (Y 3 - Y 4 ) a carbene ligand.

[0094] Examples of organic compounds used as hosts are selected from the group consisting of benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalen, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene;aus der Gruppe bestehend aus aromatischen heterozyklischen Verbindungen, wie z.B. Dibenzothiophen, Dibenzofuran, Dibenzselenophen, Furan, Thiophen, Benzofuran, Benzothiophen, Benzoselenophen, Carbazol, Indolcarbazol, Pyridylindol, Pyrrolodipyridin, Pyrazol, Imidazol, Triazol, Oxazol, Thiazol, Oxadiazol, Oxatriazol, Dioxazol, Thiadiazol, Pyridin, Pyridazin, Pyrimidin, Pyrazin, Triazin, Oxazin, Oxathiazin, Oxadiazin, Indol, Benzimidazol, Indazol, Indoxazin, Benzoxazol, Benzisoxazol, Benzthiazol, Quinolin, Isoquinolin, Cinnolin, Quinazolin, Quinoxalin, Naphthyridin, Phthalazin, Pteridin, Xanthen, Acridin, Phenazin, Phenothiazin, Phenoxazin, Benzofuropyridin, Furodipyridin, Benzothienopyridin, Thiendipyridin, Benzoselenphenopyridin und Selenphenodipyridin;and from the group consisting of 2 to 10 cyclic structural units, which are groups of the same or different types, selected from the aromatic cyclic hydrocarbon group and the aromatic heterocyclic group, and which are linked directly or via at least one oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, a chain structural unit, and the aliphatic cyclic group. Each group is further substituted by a substituent selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, arylalkyl, heteroalkyl, aryl, and heteroaryl.

[0095] According to one aspect, the host compound contains at least one of the following groups in the molecule:

[0096] R 1 to R 7are each independently selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, arylalkyl, heteroalkyl, aryl and heteroaryl; if it is aryl or heteroaryl, it has a similar definition to the Ars mentioned above.

[0097] k is an integer from 0 to 20.

[0098] X 1 up to X 8 is selected from CH or N. HBL:

[0099] A hole-blocking layer (HBL) can be used to reduce the number of holes and / or excitons that leave the emitter layer. The presence of such a blocking layer in a device can lead to significantly higher efficiency compared to a similar device without a blocking layer. A blocking layer can also be used to restrict emission to a desired region of an OLED.

[0100] According to one aspect, the compound used in HBL contains the same molecule that is used as a host, as described above.

[0101] According to another aspect, the compound used in HBL contains at least one of the following groups in the molecule:

[0102] k is an integer from 0 to 20; L is an ancillary ligand, m is an integer from 1 to 3. ETL:

[0103] The electron transport layer (ETL) can contain a material capable of transporting electrons. The ETL can be intrinsic (undoped) or doped. Doping can be used to improve conductivity. Examples of ETL materials are not necessarily limiting, and any metal complex or organic compound can be used, as long as it is typically used to transport electrons.

[0104] According to one aspect, the compound used in the ETL contains at least one of the following groups in the molecule:

[0105] R 1 is selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, arylalkyl, heteroalkyl, aryl and heteroaryl; if it is aryl or heteroaryl, it has a similar definition to the Ar's mentioned above.

[0106] Ar 1 to Ar 3 have a similar definition to the Ar's mentioned above.

[0107] k is an integer from 0 to 20.

[0108] X 1 up to X 8 is selected from CH or N.

[0109] According to another aspect, the metal complexes used in the ETL include, but are not limited to, the following general formula:

[0110] (O - N) or (N - N) is a bidentate ligand with a metal that coordinates with the atoms O, N or N, N; L is an ancillary ligand; m is an integer from 1 to the maximum number of ligands that can be attached to the metal.

[0111] In any of the above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or completely deuterated.

[0112] In addition to and / or in combination with the materials disclosed herein, many hole-injecting materials, hole-transporting materials, host materials, dopant materials, exciton / hole-blocking layer materials, electron-transporting and electron-injecting materials can be used in an OLED. Non-restrictive examples of materials that can be used in an OLED in combination with the materials disclosed herein are listed in Table 1 below. Table 1 lists non-restrictive classes of materials, non-restrictive examples of compounds for each class, and references that disclose the materials. TABLE 1 MATERIAL EXAMPLES OF MATERIAL PUBLICATIONS Hole injection materials Phthalocyanin and porphyrin compounds Appl. Phys. Lett. 69.2160 (1996) Star-shaped triarylamines J. Lumin. 72-74, 985(1997) CF x fluorocarbon polymer Appl. Phys. Lett. 78, 673 (2001) Conductive polymers (e.g. PEDOT:PSS, polyaniline, polythiophene) Synth. Met. 87, 171 (1997)WO 2007 / 002683 A2 Phosphonic acid and silane SAMs US 2003 / 0162053 A1 Triarylamine or polythiophene polymer with conductive dopants and EA 2001 725 079 A1 Arylamines complexed with metal oxides, such as molybdenum and tungsten oxides SID Symposium Digest,37, 923 (2006)WO 2009 / 018009 A1 p-type semiconducting organic complexes US 2002 / 0158242 A1 Metal-organic metal complexes US 2006 / 0240279 A1 Cross-connected links US 2008 / 0220265 A1 Hole transporting materials Triarylamine (e.g. TPD, α-NPD) Appl. Phys. Lett. 51, 913 (1987) US 5 061 569 A EP 650 955 A1 J. Mater. Chem. 3, 319(1993) Appl. Phys. Lett. 90.183503 (2007) Appl. Phys. Lett. 90.183503 (2007) Triacylamine at the spirofluorene core Synth. Met. 91, 209(1997) Arylamine carbazole compounds Adv. Mater. 6, 677 (1994), US 2008 / 0124572 A1 Triarylamine with (Di)benzothiophene / (Di)benzofuran US 2007 / 0278938 A1, US 2008 / 0106190 A1 Indolecarbazole Synth. Met. 111,421(2000) Isoindole compounds Chem. Mater. 15, 3148(2003) Metal carbene complexes US 2008 / 0018221 A1 Phosphorescent OLED host materials Red Hosts Arylcarbazole Appl. Phys. Lett. 78.1622 (2001) Metal 8-hydroxyquinolates (e.g. Alq3, BAlq) Nature 395, 151 (1998) US 2006 / 0202194 A1 WO 2005 / 014551 A1 WO 2006 / 072002 A2 Metal-phenoxybenzothiazole compounds Appl. Phys. Lett. 90.123509 (2007) Conjugated oligomers and polymers (e.g., polyfluorene) Org. Electron. 1, 15(2000) Aromatic fused rings WO 2009 / 066779 A1,WO 2009 / 066778 A1,WO 2009 / 063833 A1,US 2009 / 0045731 A1,US 2009 / 0045730 A1,WO 2009 / 008311 A1,US 2009 / 0008605 A1, US 2009 / 0009065 A1 Zinc complexes WO 2009 / 062578 A1 Green hosts Arylcarbazole Appl. Phys. Lett. 78.1622 (2001) US 2003 / 0175553 A1 WO 2001 / 039234 A2 Aryltriphenylene compounds US 2006 / 0280965 A1 US 2006 / 0280965 A1 WO 2009 / 021126 A2 Donor-acceptor molecules WO 2008 / 056746 A1 Azacarbazole / DBT / DBF JP 2008 - 074 939 A Polymers (e.g., PVK) Appl. Phys. Lett. 77.2280 (2000) Spirofluorene compounds WO 2004 / 093207 A2 Metal-phenoxybenzoxazole compounds WO 2005 / 089025 A1 WO 2006 / 132173 A1 JP 2005 - 11610 A Spirofluorencarbazole compounds JP 2007 - 254297 A JP 2007 - 254297 A Indolecabazole WO 2007 / 063796 A1 WO 2007 / 063754 A1 5-membered, electron-deficient ring heterocycles (e.g. triazole, oxadiazole) J. Appl. Phys. 90,5048(2001) WO 2004 / 107822 A1 Tetraphenylene complexes US 2005 / 0112407 A1 Metal-phenoxypyridine compounds WO 2005 / 030900 A1 Metal coordination complexes (e.g. Zn, Al with N^N ligands) US 2004 / 0137268 A1, US 2004 / 0137267 A1 Blue Hosts Arylcarbazole Appl. Phys. Lett, 82.2422 (2003) US 2007 / 0190359 A1 Dibenzothiophene / dibenzofuran-carbazole compounds WO 2006 / 114966 A1, US 2009 / 0167162 A1 US 2009 / 0167162 A1 WO 2009 / 086028 A2 US 2009 / 0030202 A1, US 2009 / 0017330 A1 Silicon aryl compounds US 2005 / 0238919 A1 WO 2009 / 003898 A1 Silicon / germanium aryl compounds EP 2 034 538 A Arylbenzoyl ester WO 2006 / 100298 A1 Metal-metal-organic complex with high triplet US 7 154 114 B2 Phosphorescent dopants Red dopants Heavy metal porphyrins (e.g. PtOEP) Nature 395, 151 (1998) Iridium(III) organometallic complexes Appl. Phys. Lett. 78.1622 (2001) US 2006 / 835469 A US 2006 / 835469 A US 2006 / 0202194 A1 US 2006 / 0202194 A1 US 2007 / 0087321 A1 US 2007 / 0087321 A1 Adv. Mater. 19, 739(2007) WO 2009 / 100991 A1 WO 2008 / 101842 A1 Platinum(II) organometallic complexes WO 2003 / 040257 A1 Osmium(III) complexes Chem. Mater. 17, 3532(2005) Ruthenium(II) complexes Adv. Mater. 17, 1059(2005) Rhenium (I), (II) and (III) complexes US 2005 / 0244673 A1 Green dopants Iridium(III) organometallic complexes and its derivatives Inorg. Chem. 40, 1704(2001) US 2002 / 0034656 A1 US 7 332 232 B2 US 2009 / 0108737 A1 US 2009 / 0039776 A1 US 6 921 915 B2 US 6 687 266 B1 Chem. Mater. 16, 2480(2004) US 2007 / 0190359 A1 US 2006 / 0008670 A1JP 2007 - 123 392 A Adv. Mater. 16, 2003(2004) Angew. Chem. Int. Ed.2006, 45, 7800 WO 2009 / 050290 A1 US 2009 / 0165846 A1 US 2008 / 0015355 A1 Monomer for polymer-metal-organic compounds US 7,250,226 B2, US 7,396,598 B2 Pt(II) organometallic complexes, including multidentate ligands Appl. Phys. Lett. 86.153505 (2005) Appl. Phys. Lett. 86.153505 (2005) Chem. Lett. 34, 592(2005) WO 2002 / 015645 A1 US 2006 / 0263635 A1 Cu complexes WO 2009 / 000673 A2 Gold complexes Chem. Commun. 2906(2005) Rhenium(III) complexes Inorg. Chem. 42, 1248(2003) Deuterated metal-organic complexes US 2003 / 0138657 A1 Organometallic complexes with two or more metal centers US 2003 / 0152802 A1 US 7 090 928 B2 Blue dopants Iridium(III) organometallic complexes WO 2002 / 002714 A2 WO 2006 / 009024 A1 US 2006 / 0251923 A1 US 7 393 599 B2,WO 2006 / 056418 A2,US 2005 / 0260441 A1,WO 2005 / 019373 A2 US 7 534 505 B2 US 7 445 855 B2 US 2007 / 0190359 A1,US 2008 / 0297033 A1 US 7 338 722 B2 US 2002 / 0134984 A1 Angew. Chem. Int. Ed.47, 1 (2008) Chem. Mater. 18, 5119(2006) Inorg. Chem. 46, 4308(2007) WO 2005 / 123873 A1 WO 2005 / 123873 A1 WO 2007 / 004380 A1 WO 2006 / 082742 A1 Osmium(II) Komplexe US 7 279 704 B2 Organometallics 23,3745 (2004) Gold-Komplexe Appl. Phys. Lett.74, 1361(1999) Platin(II) Komplexe WO 2006 / 098120 A1,WO 2006 / 103874 A1 Exciton- / lochblockierende Schichtmaterialien Bathocuprin-Verbindungen(z.B. BCP, BPhen) Appl. Phys. Lett. 75, 4(1999) Appl. Phys. Lett. 79, 449(2001) Metall-8-Hydroxyquinolate(z.B. BAlq) Appl. Phys. Lett. 81, 162(2002) 5-gliedrige elektronenarmeHeterozyklen, wie z.B.Triazol, Oxadiazol, Imidazol,Benzimidazol Appl. Phys. Lett. 81, 162(2002) Triphenylen-Verbindungen US 2005 / 0025993 A1 Fluorierte aromatischeVerbindungen Appl. Phys. Lett. 79, 156(2001) Phenothiazin-S-Oxid WO 2008 / 132085 A1 Electron-transporting materials Anthracene benzimidazole compounds WO 2003 / 060956 A2 US 2009 / 0179554 A1 Azatriphenylene derivatives US 2009 / 0115316 A1 Anthracene benzothiazole compounds Appl. Phys. Lett. 89.063504 (2006) Metal 8-Hydroxyquinolates(e.g. Alq3, Zrq4) Appl. Phys. Lett. 51, 913 (1987) US 7,230,107 B1 Metal hydroxybenoquinolates Chem. Lett. 5, 905 (1993) Bathocuprine compounds, such as BCP, BPhen, etc. Appl. Phys. Lett. 91.263503 (2007) Appl. Phys. Lett. 79, 449 (2001) 5-membered electron-deficient ring heterocycles (e.g. triazole, oxadiazole, imidazole, benzimidazole) Appl. Phys. Lett. 74, 865 (1999) Appl. Phys. Lett. 55.1489 (1989) Jpn. J.Apply. Phys. 32,L917 (1993) Silol compounds Org. Electron. 4, 113(2003) Arylborane compounds J.Am. Chem. Soc. 120.9714 (1998) Fluorinated aromatic compounds J.Am. Chem. Soc. 122.1832 (2000) Fullerene (e.g. C60) US 2009 / 0101870 A1 Triazine complexes US 2004 / 0036077 A1 Zn (N^N) complexes US 6 528 187 B1 EXAMPLES Compound examples Example 1. Synthesis of 5-(3-(Triphenylen-2-yl)phenyl)benzo[b]naphtho[2,1-d]thiophene (or compound 69S).

[0113] Synthesis of 3-styrylbenzo[b]thiophene. This is based on the article 18(5), 967-72, 1981 in the Journal of Heterocyclic Chemistry. NaH (1.3 g, 28 mmol) was reacted with a mixture of 3-carbaldehyde benzo[b]thiophene (4.27, 25 mmol) and diethylbenzylphosphonate (5.76 g, 25 mmol) in 50 ml of 1,2-dimethoxyethane at 0 °C under N 2 The mixture was added and stirred for 15 minutes at 0 °C and for 3 hours at room temperature. The reaction mixture was then poured into ice water and filtered. The solid from the filtration was recrystallized from ethanol to yield 4.5 g of the desired product, which was obtained as a yellow solid.

[0114] Synthesis of benzo[b]naphtha[2,1-d]thiophene. 3-Styrylbenzo[b]thiophene (13.8 g, 58 mmol), I₂ (0.13 g, 3 mmol), and 1.1 L toluene were added to a photoreaction flask. The mixture was irradiated with a medium-pressure mercury lamp for 6 hours with stirring. The mixture was then concentrated and purified by silica gel column chromatography (15% EtOAc in hexanes). The product was further recrystallized from 20% EtOAc in methanol to give 12.9 g of pure product.

[0115] Synthesis of 5-bromobenzo[b]naphtho[2,1-d]thiophene. Br₂ (1.53 g, 9.4 mmol) in ~50 mL of CHCl₃ was added dropwise to a solution of benzo[b]naphtha[2,1-d]thiophene (2.2 g, 9.4 mmol) in 300 mL of CHCl₃ at room temperature. The mixture was stirred for 22 hours. The reaction was slaked with aqueous Na₂SO₃. After preparation, silica gel column chromatography (50% CH₂Cl₂ in hexanes), and washing with minimal amounts of methanol and hexane, 2.8 g of the product were obtained.

[0116] Synthesis of compound 69S. A mixture of 5-bromobenzo[b]naphtho[2,1-d]thiophene (1.45 g, 4.6 mmol), 4,4,5,5-tetramethyl-2-(3-(triphenylen-2-yl)phenyl)-1,3,2-dioxaborolane (2.4 g, 5.58 mmol), K3PO4 (5.85 g, 27.6 mmol), 100 ml toluene and 10 ml water was reacted with N 2 Blow through for 15 minutes. Then Pd2(dba)3 (212 mg, 0.23 mmol) and 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (378 mg, 0.92 mmol) were added. The mixture was blown through with N for a further 20 minutes.2 The mixture was purged and then left to reflux overnight. After preparation by silica gel column chromatography (40% CH₂Cl₂ in hexanes), 2.2 g of the product was obtained as a white solid. Compound 4S exhibited a triplet energy of 491 nm at 77 K in 2-methylTHF. Example 2. Synthesis of 7-(3-(Triphenylen-2-yl)phenyl)triphenyleno[1,12-bed]thiophene (or compound 67S).

[0117] Synthesis of triphenyleno[1,12-bed]thiophene. To an oven-dried, 250 mL three-necked round-bottom flask equipped with a condenser and two rubber septa, 100 mL of dry hexanes were added via a cannula. The flask was cooled to -50 °C using an acetone / dry ice bath. TMEDA (3.3 mL, 21.0 mmol) was added via a syringe, followed by n-BuLi (1.6 M, 13.7 mL, 21.9 mmol) via a syringe. The solution was allowed to stand to warm to room temperature. After stirring for 30 minutes, triphenylene (1.0 g, 4.38 mmol) was added and subjected to reflux under N 2The mixture was heated. It turned dark red and was kept under reflux for 3 hours. S₂Cl₂ (0.9 ml, 10.95 mmol) was added to the cooled solution. A vigorous reaction took place, followed by the precipitation of a solid. Water was then added, and the mixture was extracted twice with CH₂Cl₂. The organic extracts were dried over MgSO₄, filtered, and evaporated, and the residue was purified by silica gel column chromatography (0–2.5% CH₂Cl₂ in hexanes). 0.5 g of triphenyleno[1,12-bed]thiophene was collected.

[0118] Synthesis of 7-bromotriphenyleno[1,12-bed]thiophene. Triphenyleno[1,12-bed]thiophene (1.5 g, 5.8 mmol) was dissolved in 100 ml of chloroform. Br₂ was slowly added to the reaction solution. After stirring the reaction at room temperature for 3 days, the mixture was filtered through a Celite stopper and washed with CH₂Cl₂. The combined filtrate was concentrated to obtain 2.2 g of 7-bromotriphenyleno[1,12-bed]thiophene, which was then used for the next step without further purification.

[0119] Synthesis of 4,4,5,5-tetramethyl-2-(triphenyleno[1,12-bed]thiophen-3-yl)-1,3,2-dioxaborolane. A mixture of 7-bromotriphenyleno[1,12-bed]thiophene (2.2 g, 6.5 mmol), KOAc (1.6 g, 20 mmol), and 300 ml of dioxane was reacted with N₂ for 25 minutes. 2 The mixture was blown through. Then Pd(dppf)Cl2 (0.16 g, 0.2 mmol) was added and the mixture was heated with N for a further 25 minutes. 2The mixture was purged by blowing through the filter. The reaction was heated to 90 °C overnight. The mixture was then cooled to temperature, filtered through a Celite stopper, and washed with CH₂Cl₂. The combined filtrate was concentrated. The crude product was purified as an eluate by silica gel column chromatography (3% EtOAc in hexanes) to yield 0.25 g of product.

[0120] Synthesis of compound 67S. A mixture of 4,4,5,5-tetramethyl-2-(triphenyleno[1,12-bed]thiophen-7-yl)-1,3,2-dioxaborolane (0.24 g, 0.62 mmol), 3-(triphenylen-2-yl)phenyltrifluoromethanesulfonate (0.26 g, 0.57 mmol), K3PO4 (0.36 g, 1.7 mmol), dioxane (30 ml) and water (3 ml) were reacted with N for 1 hour 2 The mixture was blown through. Then Pd2(dba)3 (5.2 mg, 0.0057 mmol) and (Biphenyl-2-yl)dicyclohexylphosphine (8 mg, 0.023 mmol) were added and the mixture was heated with N for a further 15 minutes. 2The mixture was purged by blowing through a filter. After stirring overnight at room temperature, additional PD2(dba)3 (5.2 mg, 0.0057 mmol) and (biphenyl-2-yl)dicyclohexylphosphine (8 mg, 0.023 mmol) were added. The reaction was stirred at room temperature for three days. The precipitate was collected by filtration and purified by silica gel column chromatography (0–40% CH2Cl2 in hexanes) to yield 50 mg of the product as a white solid exhibiting a triplet energy of 490 nm at 77 K in 2-methylTHF. Example 3. Synthesis of phenanthro[4,5-bed]thiophene

[0121] The synthesis is based on the article 5(2), 113-19, 1994 in Heteroatom Chemistry. Phenanthrene (5.7 g, 32 mmol) and 220 mL of dry hexanes were added to an oven-dried, 3-necked 1L round-bottom flask equipped with a condenser and a dropping funnel. Then, TMEDA (24 mL, 160 mmol) followed by n-BuLi (1.6 M, 100 mL, 160 mmol) was added dropwise via a dropping funnel. The solution was refluxed for 3 hours under N 2The reaction mixture was heated. It was cooled in an ice bath, and S₂Cl₂ (6.4 mL, 80.0 mmol) was slowly added. The mixture was left to stand overnight at room temperature with stirring. Water and CH₂Cl₂ were added, and the layers were separated. The aqueous layer was extracted with CH₂Cl₂. The organic extracts were dried over MgSO₄, filtered, and evaporated. The material was purified by silica gel column chromatography (0–10% CH₂Cl₂ in hexanes) to yield 2.3 g of a cream-colored solid contaminated with sulfur. Further column chromatography, eluted with hexanes, provided 0.42 g of pure material. Phenanthro[4,5-bed]thiophene exhibited a triplet energy of 508 nm at 77 K in 2-methylTHF. Example 4. Synthesis of Benzo[b]phenanthro[9,10-d]thiophene

[0122] The synthesis is based on Tetrahedron, 37(I), 75-81, 1981. To a 500 ml, 3-necked round-bottom flask, 2,3-dibromobenzo[b]thiophene (5.0 g, 17.12 mmol), phenylboronic acid (5.2 g, 42.81 mmol), 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (281 mg, 0.68 mmol), K3PO4 (11.8 g, 51.36 mmol), 150 ml toluene, and 5 ml water were added. 2The mixture was purged directly in the flask for 20 minutes. Pd₂(dba)₃ (157 mg, 0.171 mmol) was added to the reaction mixture, which was then heated to reflux for 5 hours. Water was added to the cooled reaction mixture, and the layers were separated. The aqueous layer was extracted twice with CH₂Cl₂, and the organic extracts were dried over MgSO₄, filtered, and evaporated to give a red oil, which was dried to yield 5.71 g of a red solid. The solid was purified by silica gel column chromatography (10–20% CH₂Cl₂ in hexanes) to give 4.81 g of the product as a white solid.

[0123] A photoreactor was loaded with 2,3-diphenylbenzo[b]thiophene (4.81 g, 16.8 mmol) and 800 mL of toluene. The solution was irradiated under a medium-pressure mercury lamp for 12 hours. The solvent was evaporated, and the residue was purified by silica gel column chromatography (0–20% EtOAc in hexanes). The product was collected and recrystallized from hexanes (with a small amount of EtOAc to initially dissolve the material) to yield 1.61 g of a cream-colored solid. Benz[b]phenanthro[9,10-d]thiophene exhibited a triplet energy of 488 nm at 77 K in 2-methylTHF. Example 5. Synthesis of benzo[b]triphenylene[2,1-d]thiophene

[0124] This synthesis is based on the Journal of Heterocyclic Chemistry, 21(6), 1775-9, 1984.

[0125] Synthesis of 9-methylphenanthrene. 9-Bromphenanthrene (27 g, 102 mmol) was dissolved in 400 mL of dry ether and cooled to -78 °C. 170 mL of BuLi (1.6 M in hexane) was slowly added to this solution over 45 minutes. The reaction mixture was warmed to room temperature. The mixture was then stirred at room temperature for 2 hours before being cooled again to -78 °C and Me₂SO₄ (17.6 g, 133 mmol) in ether was slowly added. The mixture was stirred at room temperature for 10 hours. The mixture was poured into 15% aqueous HCl solution and extracted with CH₂Cl₂ and dried over MgSO₄. The solvent was evaporated to give a residue, which was recrystallized from hexane to yield 14.2 g of the product as a white solid.

[0126] Synthesis of 9-(bromomethyl)phenanthrene. A mixture of 9-methylphenanthrene (14.2 g, 74 mmol), benzoyl peroxide (40 mg, 0.16 mmol), and NBS (13.3 g, 74.6 mmol) in 210 mL of benzene was refluxed for 5 hours. The reaction mixture was cooled to 0 °C, and the precipitated succinimide was removed by filtration. The filtrate was washed with 15% NaOH, dried over MgSO4, and concentrated to yield 18 g of product, which was used without further purification for the next step.

[0127] Synthesis of diethyl(phenynthren-9-ylmethyl)phosphonate. 9-(Bromomethyl)phenanthrene (18 g, 66.4 mmol) and triethyl phosphite (10.7 g) were mixed together and heated for 4 hours under N 2 The mixture was heated to 150 °C. The reaction mixture was concentrated, and the remainder was purified by silica gel column chromatography to obtain 12 g of the product.

[0128] Synthesis of 3-(2-(phenanthren-9-yl)vinyl)benzo[b]thiophene. Diethyl(phenanthren-9-ylmethyl)phosphonate (11 g, 33.5 mmol) and 3-carbaldehyde benzo[b]thiophene (5.5 g, 33.5 mmol) were dissolved in 250 ml of 1,2-dimethoxyethane. The mixture was cooled to 0 °C and NaH (6 g, 150 mmol) was added portionwise. The reaction mixture was heated to room temperature and then heated on reflux for 2.5 hours. The reaction mixture was concentrated, and the residue was purified by silica gel column chromatography (30% CH₂Cl₂ in hexane) to yield 6 g of the product.

[0129] Synthesis of benzo[b]triphenyleno[2,1-d]thiophene. 3-(2-Phenanthren-9-yl)vinyl)benzo[b]thiophene (0.5 g, 1.5 mmol), I₂ (38 mg, 0.15 mmol), and 250 mL of toluene were loaded into a photoreactor. The reaction mixture was irradiated with a medium-pressure mercury lamp for 3.5 hours. The reaction mixture was concentrated to yield a residue, which was purified by silica gel column chromatography (10% CH₂Cl₂ in hexanes) to give 0.3 g of the product. Benzo[b]triphenyleno[2,1-d]thiophene exhibited a triplet energy of 463 nm at 77 K in 2-methylTHF. Examples of devices

[0130] All device examples were tested by thermal evaporation in a high vacuum (<10 -7Torr). The anode electrode consists of 1200 Å of indium tin oxide (ITO). The cathode consists of 10 Å of LiF followed by 1000 Å of Al. All devices were encapsulated with a glass lid, which was sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H2O and O2) immediately after manufacture, and a moisture-retaining agent was incorporated into the packaging.

[0131] The organic stack of device examples 1 - 4 in Table 1 consisted successively, starting from the ITO surface, of 100 Å of compound A as a hole injection layer (HIL), 300 Å of 4,4'-bis[N-(1-Naphthyl)-N-phenylamino]biphenyl (α-NPD) as a hole transport layer (HTL), 300 Å of compound 4S doped with 10 or 15 wt% of compound A as an emitter layer (EML), 100 Å or 50 Å of compound 69S or compound B as ETL2 and 400 Å or 450 Å of Alq3 (Tris-8-hydroxyquinolinaluminium) as ETL1.

[0132] Comparison device examples were manufactured similarly to the device examples, except that CBP was used as the host.

[0133] The device data for the device examples and comparison device examples are shown in Table 2. Ex. is an abbreviation for example. Comp. is an abbreviation for comparable. Cmpd. is an abbreviation for connection. Table 2. Data of the device examples and the comparison device examples. Device Ex. Cmpd. A% ETL2 (Ä) ETL1(Å) at 1000 cd / m 2 40 mA / cm 2 x x v(V) LE(cd / A) EQE(%) PE(Im / W) L0(cd / m2) LT 80 (h) 1 10 695(100) Alq3(400) 0,371 0,595 7,2 31 8,6 13,5 8878 80 2 15 695(100) Alq3(400) 0,369 0,598 6,9 34,6 9,6 15,7 9816 141 3 10 B (50) Alq3(450) 0,369 0,598 6,5 35,5 9,8 17,1 9497 72 4 15 B (50) Alq3(450) 0,367 0,602 6,1 46,8 12,9 24,1 11974 95 Comp.-Ex. 1 10 B (50) Alq3(450) 0,345 0,615 5,8 61 16,7 33,0 16118 82

[0134] As used herein, the following compounds have the following structures:

[0135] The apparatus examples use compound 69S as the host. The external quantum efficiencies are 8.8–12.9%, which is lower than the efficiency of the comparison apparatus examples that use CBP as the host. This may be due to a certain degree of luminescence that quenches the phosphorescence of compound A by compound 69S because of the similar triplet energies (compound 69S T1 = 491 nm; compound A T1 = 525 nm). However, the operating lifetimes of the apparatus examples are compared to those of the comparison apparatus examples. Apparatus example 2 features an LT 80 (time required until the initial luminance L0 drops from 80%) from 141 hours, whereas comparison device example 1 is an LT 80of 82 hours. The result demonstrates the stability of triphenylene-benzo / dibenzo residue compounds with fused rings. Since the triplet energy of triphenylene-benzo / dibenzo residue compounds with fused benzo rings can be lower than 490 nm, they may be particularly suitable as host materials for yellow, orange, red, or IR-phosphorescent emitters.

Claims

[1] Compound selected from the group consisting of: where XO, S or Se; where R1, R2 and R a are independently selected from hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, alkynyl, arylkyl, aryl and heteroaryl; where each of R1 and R2 can represent mono-, di-, tri- or tetrasubstitution; where at least two substituents of R1 or R2 are fused to form a ring; where R a represents mono- or di-substitutions that cannot fuse to form a benzo ring; where L represents a spacer or a direct bond with the benzofuran, benzothiophene, or benzoselenophene residue with additional fused rings; wherein R'1, R'2 and R'3 are independently selected from the group consisting of hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, alkynyl, arylcyl, aryl and heteroaryl; and where each of R'1, R'2 and R'3 can represent mono-, di-, tri- or tetrasubstitution. [2] Compound according to claim 1, wherein at least two substituents of R1 or R2 are fused to form an aromatic or heteroaromatic ring which is 6-membered carbocyclic or heterocyclic. [3] Compound according to claim 2, wherein the aromatic ring is a benzene ring. [4] Compound according to claim 1, wherein the compound has the following formula: [5] Compound according to claim 1, wherein XS is. [6] Compound according to claim 1, wherein XO is. [7] Compound according to claim 1, wherein L is a direct bond. [8] Compound according to claim 1, wherein L has the following formula: where A, B, C and D are each independently selected from the group consisting of: where A, B, C and D are each optionally further equipped with R a are substituted; where each of p, q, r and s is 0, 1, 2, 3 or 4; where p+q+r+s is at least 1. [9] Compound according to claim 1, wherein L is phenyl. [10] Compound according to claim 1, wherein the compound is selected from the group consisting of: where XO, S or Se; wherein R1, R2, R3, R4, R5, R'1, R'2 and R'3 are each independently selected from the group consisting of hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, alkynyl, arylcyl, aryl and heteroaryl; where each of R1, R2, R3, R4, R5, R'1, R'2 and R'3 can represent mono-, di-, tri- or tetrasubstitution; and where L is a spacer or a direct link. [11] Compound according to claim 1, wherein the compound is selected from the group consisting of: where XO, S or Se. [12] First apparatus comprising an organic light-emitting apparatus, further comprising: an anode; a cathode; and an organic layer arranged between the anode and the cathode, wherein the organic layer comprises a compound according to claim 1. [13] First device according to claim 12, wherein the organic layer is an emitter layer and the compound according to claim 1 is the host. [14] First device according to claim 13, wherein the organic layer further comprises an emitting compound. [15] First apparatus according to claim 14, wherein the emitting compound is a transition metal complex with at least one ligand selected from the group consisting of: where each of R' a , R' b and R' c can represent mono-, di-, tri- or tetrasubstitution; where each of R' a , R' b and R' cEach is independently selected from the group consisting of hydrogen, deuterium, alkyl, heteroalkyl, aryl and heteroaryl; and where two adjacent substituents can form a ring. [16] First device according to claim 12, wherein the device comprises a second organic layer which is non-emitting and the compound according to claim 1 is a non-emitting material in the second organic layer. [17] First device according to claim 12, wherein the first device is an organic light-emitting device. [18] First device according to claim 12, wherein the first device is a consumer product.

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