Attorney Docket No.: UDC-1693P2 (376.0041P)
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`ORGANIC ELECTROLUMINESCENT MATERIALS AND DEVICES
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`FIELD
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`[0001] The present disclosure generally relates to organometallic compounds and formulations and their
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`various uses including as hosts or emitters in devices such as organic light emitting diodes and related
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`electronic devices.
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`BACKGROUND
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`[0002] Opto-electronic devices that make use of organic materials are becomingincreasingly desirable
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`for various reasons. Many of the materials used to make such devicesare relatively inexpensive, so
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`organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition,
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`the inherent properties of organic materials, such as their flexibility, may make them well suited for
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`particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic
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`devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic
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`photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance
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`advantages over conventional materials.
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`[0003] OLEDs make use of thin organic films that emit light when voltage is applied across the device.
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`OLEDsare becomingan increasingly interesting technology for use in applications such as flat panel
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`displays, illumination, and backlighting.
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`[0004] Onc application for phosphorescent cmissive molccules is a full color display. Industry standards
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`for such a display call for pixels adapted to emit particular colors, referred to as "saturated" colors. In
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`particular, these standards call for saturated red, green, and blue pixels. Alternatively, the OLED canbe
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`designed to emit white light. In conventional liquid crystal displays emission from a white backlight is
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`filtered using absorptionfilters to produce red, green and blue emission. The same technique canalso be
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`used with OLEDs. The white OLED can be either a single emissive layer (EML) device or a stack
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`structure. Color may be measured using CIE coordinates, which are well knownto theart.
`
`SUMMARY
`
`[0005]
`
`In onc aspect, the present disclosure provides a compound of FormulaI:
`i"
`
`, FormulaI,
`
`iA
`
`re
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`Attorney Docket No.: UDC-1693P2 (376.004 1P)
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`wherein each Ar!-Ar? is a substituted or unsubstituted non-fused aromatic ring;
`
`Z is Si or Ge;
`
`A and B are each an aryl-amino group comprising 3 or morefused rings;
`
`L' is selected from the group consisting of a direct bond, phenyl, carbazole, azacarbazole,
`
`pyridine, azadibenzothiophene, azadibenzofuran, azadibenzoselenophene, pyrazine,
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`pyrimidine, and triazine, which may be further fused or substituted;
`
`L’ is selected from the group consisting of phenyl, carbazole, azacarbazole, pyridine,
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`azadibenzothiophene, azadibenzofuran, azadibenzoselenophene, pyrazine, pyrimidine, and
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`triazine, which maybefurther fused or substituted;
`L! and L’are not joined to form a ring;
`
`at least one of L! and L?is selected from the group consisting of pyridine, pyrazine,
`
`pyrimidine, and triazine, which may be further fused or substituted;
`with the proviso that when L! is a phenyl ring, the compound comprises only 1 Si atom:
`
`and wherein the following compound is excluded:
`
`
`
`See
`oN
`wh,
`sae aid$ ;
`
`PegVe
`
`ot
`
`
`
`[0006]
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`In another aspect, the present disclosure provides a formulation of the compoundas described
`
`herein.
`
`[0007]
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`In yet another aspect, the present disclosure provides an OLED having anorganic layer
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`comprising the compound as described herein.
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`

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`Attorney Docket No.: UDC-1693P2 (376.0041P)
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`[0008]
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`In yet another aspect, the present disclosure provides a consumer product comprising an OLED
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`with an organic layer comprising the compoundas described herein.
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`BRIEF DESCRIPTION OF THE DRAWINGS
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`[0009] FIG. | showsan organic light emitting device.
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`[0010] FIG. 2 showsan inverted organic light emitting device that does not have a separate electron
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`transport layer.
`
`A.
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`Terminology
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`DETAILED DESCRIPTION
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`[0011] Unless otherwise specified, the below terms used herein are defined as follows:
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`[0012] As used herein, the term "organic" includes polymeric materials as well as small molecule
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`organic materials that may be used to fabricate organic opto-electronic devices. "Small molecule" refers
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`to any organic material that is not a polymer, and "small molecules" may actually be quite large. Small
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`molecules may include repeat units in some circumstances. For example, using a long chain alkyl group
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`as a substituent does not remove a molecule from the "small molecule" class. Small molecules may also
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`be incorporated into polymers, for example as a pendent group on a polymer backboneoras a part of the
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`backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series
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`of chemical shells built on the core moiety. The core moiety of a dendrimer may bea fluorescent or
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`phosphorescent small molecule emitter. A dendrimer may be a “small molecule," and it is believed that
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`all dendrimers currently used in the field of OLEDsare small molecules.
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`[0013] As used herein, "top" means furthest away from the substrate, while "bottom" means closest to
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`the substrate. Wherea first layer is described as "disposed over" a second layer, the first layer 1s disposed
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`further away from substrate. There may be other layers between the first and second layer, unlessit is
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`specified that the first laycr is "in contact with" the second layer. For cxamplc, a cathode may be
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`described as "disposed over" an anode, even though there are various organic layers in between.
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`[0014] As used herein, “solution processable" means capable of being dissolved, dispersed, or
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`transported in and/or deposited from a liquid medium,either in solution or suspension form.
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`[0015] A ligand may be referred to as "photoactive" whenit is believed that the ligand directly
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`contributes to the photoactive properties of an emissive material. A ligand may be referred to as
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`"ancillary" when it is believed that the ligand does not contribute to the photoactive properties of an
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`emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.
`3
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`Attorney Docket No.: UDC-1693P2 (376.0041P)
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`[0016] As used herein, and as would be generally understood by one skilled in the art, a first "Highest
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`Occupied Molecular Orbital" (HOMO)or "Lowest Unoccupied Molecular Orbital” (LUMO)energy level
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`is "greater than" or "higher than" a second HOMO or LUMOcnergy levelif the first cnergy 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 HOMOenergy level corresponds to an IP having a smaller absolute value (an IP
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`that is less negative). Similarly, a higher LUMOenergy level correspondsto an electron affinity (EA)
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`having a smaller absolute value (an EA thatis less negative). On a conventional energy level diagram,
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`with the vacuum level at the top, the LUMOenergy level of a material is higher than the HOMOenergy
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`level of the same material. A "higher" HOMO or LUMOenergy level appears closer to the top of such a
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`diagram than a "lower" HOMO or LUMOencrgy level.
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`[0017] As used herein, and as would be generally understood by one skilled in the art, a first work
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`function is "greater than" or "higher than" a second work function if the first work function has a higher
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`absolute value. Because work functions are generally measured as negative numbersrelative to vacuum
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`level, this means that a "higher" work function is more negative. On a conventional energy level diagram,
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`with the vacuum level at the top, a "higher" work function is illustrated as further away from the vacuum
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`level in the downward direction. Thus, the definiuons of HOMO and LUMOenergy levels follow a
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`different convention than work functions.
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`[0018] The terms "halo," “halogen,” and "halide" are used interchangeably and refer to fluorine, chlorine,
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`bromine, and iodine.
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`[0019] The term "acyl" refers to a substituted carbonyl radical (C(O)-Rs).
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`[0020] The term "ester" refers to a substituted oxycarbonyl (-O—C(O)-Rs or —C(O)—O-Rs) radical.
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`[0021] The term "ether" refers to an —OR, radical.
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`[0022] The terms "sulfanyl" or "thio-ether" are used interchangeably and refer to a -SR, radical.
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`[0023] The term “selenyl’ refers to a —SeRgradical.
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`[0024] The term "sulfinyl” refers to a -S(O)-R;radical.
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`[0025] The term "sulfonyl" refers to a -SO2-R;radical.
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`[0026] The term "phosphino"refers to a —P(R;)3 radical, wherein each R; can be sameordifferent.
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`[0027] The term "silyl" refers to a —Si(Rg)3 radical, wherein each R; can be sameordifferent.
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`[0028] The term “germy]”refers to a -Ge(Rs)3 radical, wherein each Rs can be same or different.
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`[0029] The term "boryl" refers to a —B(Rs)2 radical or tts Lewis adduct —B(Rs)3 radical, wherein Rs can be
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`sameor different.
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`Attorney Docket No.: UDC-1693P2 (376.0041P)
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`[0030]
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`In each of the above, Rs can be hydrogen or a substituent selected from the group consisting of
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`deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino,
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`silyl, alkenyl, cycloalkenyl], hetcroalkenyl, alkynyl, aryl, hctcroaryl, and combination thereof. Preferred
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`R, is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinationthereof.
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`[0031] The term "alkyl" refers to and includes both straight and branched chain alkyl radicals. Preferred
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`alkyl groups are those containing from oneto fifteen carbon atoms and includes methyl, ethyl, propyl, 1-
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`methylethyl, butyl, 1-methylpropy]l, 2-methylpropy1, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methy lbuty1,
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`1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropy], and the like. Additionally, the alkyl group
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`may be optionally substituted.
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`[0032] The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spiro alkyl radicals.
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`Preferred cycloalkyl groupsare those containing 3 to 12 ring carbon atomsand includes cyclopropyl,
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`cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5 Jundecyl, adamanty], and the like.
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`Additionally, the cycloalkyl group may be optionally substituted.
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`[0033] The terms "heteroalkyl" or "heterocycloalkyl" refer to an alkyl or a cycloalkyl radical,
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`respectively, having at least one carbon atom replaced by a heteroatom. Optionally the at least one
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`heteroatom is selected from O, 8, N, P, B, Si and Se, preferably, O, S or N. Additionally, the heteroalky]
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`or heterocycloalkyl group may be optionally substituted.
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`[0034] The term "alkenyl" refers to and includes both straight and branched chain alkeneradicals.
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`Alkenyl groups arc essentially alkyl groups that include at least onc carbon-carbon double bond in the
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`alkyl chain. Cycloalkenyl groups are essentially cycloalkyl groups that include at least one carbon-carbon
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`double bond in the cycloalkyl ring. The term "heteroalkenyl" as used herein refers to an alkenyl radical
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`having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is
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`selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Preferred alkenyl, cycloalkenyl, or
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`heteroalkenyl groups are those containing twoto fifteen carbon atoms. Additionally, the alkenyl,
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`cycloalkenyl, or heteroalkenyl group may be optionally substituted.
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`[0035] The term "alkynyl" refers to and includes both straight and branched chain alkyneradicals.
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`Alkynyl groupsare essentially alkyl groups that include at least one carbon-carbontriple bond in the alkyl
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`chain. Preferred alkynyl groups are those containing twoto fifteen carbon atoms. Additionally, the
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`alkynyl group may be optionally substituted.
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`[0036] The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an alkyl group that is
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`substituted with an aryl group. Additionally, the aralkyl group may be optionally substituted.
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`Attorney Docket No.: UDC-1693P2 (376.0041P)
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`[0037] The term "heterocyclic group" refers to and includes aromatic and non-aromatic cyclic radicals
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`containing at least one heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B,
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`Si, and Sc, preferably, O, S, or N. Hetcro-aromatic cyclic radicals may be used interchangeably with
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`heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 to 7 ring atoms which
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`includes at least one hetero atom, and includes cyclic amines such as morpholino, piperidino, pyrrolidino,
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`and the like, and cyclic ethers/thio-ethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene,
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`and the like. Additionally, the heterocyclic group may be optionally substtuted.
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`[0038] The term "aryl" refers to and includes both single-ring aromatic hydrocarbyl groups and
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`polycyclic aromatic ring systems. The polycyclic rings may have two or more rings in which two carbons
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`arc commonto two adjoining rings (the rings are "fuscd") whercin at least one of the rings 1s an aromatic
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`hydrocarbyl group, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or
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`heteroaryls. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty
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`carbon atoms, more preferably six to twelve carbon atoms. Especially preferred is an aryl group having
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`six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, tripheny,
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`triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene,
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`chrysene, perylene, and azulene, preferably phenyl, biphenyl], tripheny1, triphenylene, Muorene, and
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`naphthalene. Additionally, the aryl group may be optionally substituted.
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`[0039] The term "heteroaryl" refers to and includes both single-ring aromatic groups and polycyclic
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`aromatic ring systemsthat include at Icast one hetcroatom. The hetcroatomsinclude, but are not limited
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`to O,S, N, P, B, Si, and Se.
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`In manyinstances, O, S, or N are the preferred heteroatoms. Hetero-single
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`ring aromatic systems are preferably single rings with 5 or 6 ring atoms, and the ring can have from one
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`to six heteroatoms. The hetero-polycyclic ring systems can have two or more rings in which two atoms
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`are commonto two adjoining rings (the rings are "fused") wherein at least one of the rings is a heteroaryl,
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`e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. The hetero-
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`polycyclic aromatic ring systems can have from oneto six heteroatomsper ring of the polycyclic aromatic
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`ring system. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably
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`three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups
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`include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran,
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`benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine,
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`pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine,
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`pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole,
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`indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline,
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`6
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`Attorney Docket No.: UDC-1693P2 (376.0041P)
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`quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine,
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`phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine,
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`benzosclenophenopyridinc, and sclenophcnodipyridine, preferably dibenzothiophence, dibenzofuran,
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`dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-
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`azaborine, |,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroary]
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`group may be optionally substituted.
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`[0040] Of the aryl and heteroaryl groupslisted above, the groups of triphenylene, naphthalene,
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`anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole,
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`pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, and the respective aza-analogs of each
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`thercof are of particular intcrest.
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`[0041] The terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl,
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`alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl, as used herein, are independently unsubstituted,
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`or independently substituted, with one or more general substituents.
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`[0042]
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`In many instances, the general substituents are selected from the group consisting of deuterium,
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`halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germy],
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`alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile,
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`isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinationsthereof.
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`[0043]
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`In some instances, the preferred general substituents are selected from the group consisting of
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`deuterium, fluorine, alkyl, cycloalkyl, hetcroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl,
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`cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, and combinationsthereof.
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`[0044]
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`In some instances, the more preferred general substituents are selected from the group consisting
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`of deuterium,fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino,silyl, bory], aryl, heteroaryl, sulfanyl,
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`and combinationsthereof.
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`[0045]
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`In yet other instances, the most preferred general substituents are selected from the group
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`consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinationsthereof.
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`[0046] The terms "substituted" and "substitution" refer to a substituent other than H that is bondedto the
`relevantposition, e.g., a carbon or nitrogen. For example, when R' represents mono-substitution, then
`one R! mustbe other than H (i.¢., a substitution). Similarly, when R' represents di-substitution, then two
`of R' must be other than H. Similarly, when R! represents zero or no substitution, R', for example, can be
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`a hydrogenfor available valencies of ring atoms, as in carbon atoms for benzene and the nitrogen atom in
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`pyrrole, or simply represents nothing for ring atomswith fully filled valencies, e.g., the nitrogen atom in
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`Attorney Docket No.: UDC-1693P2 (376.0041P)
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`pyridine. The maximum numberof substitutions possible in a ring structure will depend on the total
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`numberof available valencies in the ring atoms.
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`[0047] As used hercin, "combinations thercof" indicates that one or more membersofthe applicable list
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`are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can
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`envision from the applicable list. For example, an alkyl and deuterium can be combined to form a partial
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`or fully deuterated alkyl group; a halogen and alkyl can be combinedto form a halogenated alkyl
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`substituent; and a halogen, alkyl, and aryl can be combined to form a halogenated arylalkyl. In one
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`instance, the term substitution includes a combination of two to four of the listed groups.
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`In another
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`instance, the term substitution includes a combination of two to three groups. In yet another instance, the
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`term substitution includes a combination of two groups. Preferred combinations of substitucnt groups arc
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`those that contain up to fifty atoms that are not hydrogen or deuterium, or those which include up to forty
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`atoms that are not hydrogen or deuterium, or those that include up to thirty atoms that are not hydrogen or
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`deuterium. In many instances, a preferred combination of substituent groups will include up to twenty
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`atomsthat are not hydrogen or deuterium.
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`[0048] The "aza" designation in the fragments described herein, i.e. aza-dibenzofuran, aza-
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`dibenzothiophene, etc. means that one or more of the C-H groups im the respective aromatic ring can be
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`replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both
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`dibenzo[f/|quinoxaline and dibenzo[f‘A]quinoline. Oneof ordinary skill in the art can readily envision
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`other nitrogen analogs ofthe aza-dcrivatives described above, and all such analogs are intended to be
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`encompassedby the termsas set forth herein.
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`[0049] As used herein, "deutertum" refers to an isotope of hydrogen. Deuterated compounds can be
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`readily prepared using methods knownin the art. For example, U.S. Pat. No. 8,557,400, Patent Pub. No.
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`WO 2006/095951, and U.S. Pat. Application Pub. No. US 2011/0037057, whichare hereby incorporated
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`by reference in their entireties, describe the making of deutertum-substituted organometallic complexes.
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`Further reference is made to Ming Yan,ef al., Tetrahedron 2015, 71, 1425-30 and Atzrodtet al., Angew.
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`Chem. Int. Ed. (Reviews) 2007, 46, 7744-65, which are incorporated by reference in their entireties,
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`describe the deuteration of the methylene hydrogens in benzyl aminesand efficient pathways to replace
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`aromatic ring hydrogens with deuterium, respectively.
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`[0050]
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`It is to be understood that when a molecular fragment is described as being a substituent or
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`otherwise attached to another moiety, its name may be written as if it were a fragment(e.g. phenyl,
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`phenylene, naphthyl, dibenzofury]) or as if it were the whole molecule (e.g. benzene, naphthalene,
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`Attorney Docket No.: UDC-1693P2 (376.0041P)
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`dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are
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`considered to be equivalent.
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`[0051]
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`In someinstance, a pair of adjaccnt substitucnts can be optionally joined or fused into a ring. The
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`preferred ringis a five, six, or seven-membered carbocyclic or heterocyclic ring, includes both instances
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`where the portion of the ring formed by the pair of substituents 1s saturated and where the portion of the
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`ring formed by the pair of substituents is unsaturated. As used herein, "adjacent" meansthat the two
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`substituents involved can be on the same ring nextto each other, or on two neighboring rings having the
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`two closest available substitutable positions, such as 2, 2’ positions in a biphenyl, or 1, 8 position in a
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`naphthalene, as long as they can formastable fused ring system.
`
`B.
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`The Compoundsof the Present Disclosure
`
`[0052]
`
`In one aspect, the present disclosure provides a compound of Formula I:
`
`AP—ZLae
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`Ar'
`
`Ar
`
`, Formula I,
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`wherein each Ar!-Ar’?is a substituted or unsubstituted non-fused aromatic ring;
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`Z 1s Si or Ge;
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`A andBare each an aryl-amino group comprising 3 or more fused rings;
`L!is selected from the group consisting of a direct bond, phenyl, carbazole, azacarbazole,
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`pyridine, azadibenzothiophene, azadibenzofuran, azadibenzoselenophene, pyrazine,
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`pytimidine, and triazine, which may be further fused or substituted;
`L’is selected from the group consisting of phenyl, carbazole, azacarbazole, pyridine,
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`azadibenzothiophene, azadibenzofuran, azadibenzoselenophene, pyrazine, pyrimidine, and
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`triazine, which may be further fused or substituted;
`
`L' and L’ are not joined to form a ring;
`at least one of L' and L’is selected from the group consisting of pyridine, pyrazine,
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`pyrimidine, and triazine, which may be further fused or substituted;
`with the proviso that when L' is a phenyl ring, the compound comprises only 1 Si atom;
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`and wherein the following compound is excluded:
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`Attorney Docket No.: UDC-1693P2 (376.004 1P)
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`
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`[0053]
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`In some embodiments, L! is a direct bond.
`
`[0054]
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`In some embodiments, L! is selected from the group consisting of phenyl, carbazole, and
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`pyridyl.
`
`[0055]
`[0056]
`[0057]
`[0058]
`
`In some embodiments, L! is phenyl.
`In some embodiments, L! is phenyl whichis not further substituted.
`In some embodiments, L! or L” is further fused with one or more additionalrings.
`In some embodiments, L! or L” is further substituted with a group selected from the group
`
`consisting of: carbazole, 5A7-benzo[d]benzo[4,5 ]imidazo[3,2-a]imidazole (bimbim), nitrile, silyl,
`
`deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy,
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`aryloxy, amino, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl,
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`carboxylic acid, ether, ester, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and
`
`combinations thereof.
`
`[0059]
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`In some embodiments, L! or L” is further substituted with a group selected from the group
`
`consisting of: carbazole, 547-benzo|[d]benzo[4,5 |imidazo[3,2-a]imidazole (bimbim), nitrile, silyl.
`
`[0060]
`[0061]
`
`In some embodiments, L” is pyridine or pyrimidine.
`In some embodiments, L? is phenyl.
`
`[0062]
`
`In some embodiments, L” is carbazole.
`
`[0063]
`
`In somc embodiments, L” is azacarbazole.
`
`[0064]
`
`In some embodiments, L” is pyridine.
`
`10
`
`

`

`Attorney Docket No.: UDC-1693P2 (376.0041P)
`
`[0065]
`
`In some embodiments, L? is azadibenzofuran.
`
`[0066]
`
`[0067]
`
`[0068]
`
`[0069]
`
`In some embodiments, L” is azadibenzoselenophene.
`In some embodiments, L? is pyrazine.
`
`In some embodiments, L? is pyrimidine.
`In some embodiments, L? is triazine.
`
`[0070]
`
`In some embodiments, L” is azadibenzothiophene.
`
`[0071|
`
`In some cmbodiments, one of A and B 1s a carbazole.
`
`[0072|
`
`In some cmbodiments, both of A and B are a carbazole.
`
`[0073]
`
`In some embodiments, L” is in addition to A further substituted with at least one group
`
`different from hydrogen.
`
`[0074]
`
`[0075]
`
`[0076]
`
`[0077]
`
`[0078]
`
`[0079]
`
`[0080]
`
`[0081]
`
`In some embodiments, L? is in addition to A substituted with at least one carbazole group.
`In some embodiments, at least one of Ar'-Ar’ is unsubstituted phenyl.
`In some embodiments, at least two of Ar!-Ar’ are unsubstituted phenyl.
`
`In some embodiments, all of Ar'-Ar* are substituted or unsubstituted phenyl.
`In some embodiments, at least one of Ar'-Ar’?is a pyridinering.
`In some embodiments, all of Ar!-Ar* are unsubstituted phenyl.
`In some embodiments, one of Ar!-Ar? is substituted with at least one carbazole group.
`In some embodiments, one of Ar!-Ar’ is substituted with exactly one carbazole group.
`
`[0082]
`
`In some embodiments, the compound 1s selected from the group
`
`consisting of:
`
`11
`
`

`

`Attorney Docket No.: UDC-1693P2 (376.0041P)
`
`RD
`
`12
`
`

`

`Attorney Docket No.: UDC-1693P2 (376.0041P)
`
`R
`
`5
`
`X89X
`36
`
`38
`RE
`R*
`reLF”Kes
`x22, x26
`
`
` is
`
`13
`
`

`

`Attorney Docket No.: UDC-1693P2 (376.0041P)
`
`X28,29-R® RB
`
`
`aK
`27 a
`39
`RA—227* 26 X°7
`30
`
`x"X30es 31
`
`14
`
`

`

`Attorney Docket No.: UDC-1693P2 (376.0041P)
`
`15
`
`

`

`Attorney Docket No.: UDC-1693P2 (376.0041P)
`
`RA
`
`X39x38
`35
`RE
`2
`yeLe x29/,25
`- \ 36
`1
`MW
`k
`Xz
`X
`
`I
`
`B
`
`-R
`
`B
`
`-R
`
`22 x26
`
`
`2.571
`Z
`x27x28
`|si ~x2
`Z7-Z>
`L
`3130
`RD
`xt x?"
`x18 NeXx
`
`3Z
`
`Ro
`
`3038
`
`35 XX
`SK x37
`33/1
`S\x36
`
`E
`
`R
`
`RA
`x?
`X2R(25
`x22, 26
`
`2.51
`Z
`X2728
`|si ~%
`ZPZ°
`L
`3130
`RD
`xe x?
`x18 ye~x!
`
`3Z
`
`RC
`
`wherein X! to X*° are each independently C or N;
`
`R‘ to RS are each independently mono to the maximum allowable substitution or no substitution;
`R“ to R& are each independently selected from the group consisting of hydrogen, deuterium,
`
`halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino,silyl,
`
`germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester,
`
`nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof
`Z! to Z'° are each independently C or N;
`
`and at least one of Z! to Z'° is N.
`
`[0083]
`
`In some embodiments, R* to RS are each independently selected from the group consisting
`
`ofhydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl,
`
`cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino,silyl, boryl, alkenyl, cycloalkenyl,
`
`heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinationsthereof.
`
`[0084]
`
`In some embodiments, the compound is selected from the group
`
`16
`
`

`

`Attorney Docket No.: UDC-1693P2 (376.0041P)
`
`consisting of:
`
`
`Structure of compound
`Compound
`Structure of compound
`
`
`Rk SB
`| _N
`Ai
`
`Compound1-
`(A7)(B7)(RA), wherein
`Compound 1-
`(A1L(BI(RI to
`
`Compound 1-
`
`(A15)(B15)(R141),
`
`Compound 2-
`(Ad(By)(RA), wherein
`Compound 2-
`(A1)(B1I)\(RI) to
`
`Rk
`
`SBI
`| _N
`Ai
`
`Compound 2-
`
`(A15)(B15)\(R141),
`
`have the structure
`have the structure
`
`
`Bj
`
`SRK
`| _N
`Ai
`
`Compound3-
`(At)(Byj)(RA), wherein
`Compound 3-
`(ALDBIDRI to
`
`Compound 3-
`
`(A15)(B15)(R141),
`
`Compound 4-
`(Ad(Bys)(RA), wherein
`Compound 4-
`(AI(BDRI to
`
`a;
`
`f
`
`Rk
`| _N
`Ai
`
`Compound 4-
`
`(A15)(B15)\(R141),
`
`have the structure
`have the structure
`
`
` Compound have the structure
`
`Compound 6-
`(Ad)(Bs)(RA), wherein
`Compound 6-
`(AI(BDRI to
`
`Compound 6-
`
`Aj
`
`j
`
`SRK
`| ZN
`Bj
`
`Rk
`
`Aj
`i Ss
`NYN
`
`Bj
`
`
`
`
`
`
`
`(A15)(B15)(R141),
`
`have the structure
`
`Compound8-
`:
`.
`.
`(Ad(Bs)(RA), wherein
`Compound8-
`
`(AI(BDRI to
`
`Compound8-
`
`(A15)(B15)(R141),
`
`Ai
`
`SRK
`| _N
`Bj
`
`Rk
`
`Bj
`
`TST
`No N
`LT
`
`Compound5-
`(Af)(Bf)(RA), wherein
`Compound5-
`(ALDBIDRI to
`
`Compound5-
`
`(A15)(B15)(R141),
`
`have the structure
`
`Compound7-
`:
`.
`.
`(Ai)(Bs)(RA), wherein
`Compound 7-
`
`(A1)\(B1)\(R)) to
`
`Compound 7-
`
`(A15)(B15)(R141),
`
`have the structure
`
`

`

`
`
`Attorney Docket No.: UDC-1693P2 (376.0041P)
`
`Compound 9-
`
`Compound9-
`
`(A1)\(B1)(RI)) to
`
`Compound 9-
`
`(A15)(B15)(R141),
`
`N. =N
`
`L,
`
`NNNRk
`N. -N
`G
`
`Compound 10-
`
`(Aj)(B/)(RA), wherein
`
`Compound 10-
`
`(A1)(B1)(R1) to
`
`Compound 10-
`
`(AI5\BI5\(R141),
`
`havethe structure
`havethe structure
`
`
`(A7)(By/)(RE),wherein
`
`Compound | 1-
`Compound 1 1-
`(A1)\(B1\(R1)) to
`Compound11-
`
`(A15)(B15)(R141),
`
`RANNw Bj
`7
`
`N 2N
`
`(AD(B/(RAVR),
`
`Compound 12-
`wherein Compound 12-
`(A1)(B1)(R1\(R]1)to
`Compound 12-
`
`(A15)(B15)(R141)(R14
`
`RIAse
`
`Bj
`| 2
`
`RI
`
`(AD(B/(RAYR),
`
`wherein Compound 13-
`(A1)(B1I)(R1)\(RI)to
`Compound 13-
`
`RI
`
`
`
` (A‘)(Bs)(RA), wherein 1), have the structure
`
`
`have the structure
`1), have the structure
`
`Compound 13-
`Bj Rk
`Compound 14-
`Bj
`
`SN
`
`| Z
`
`(AD(B/(RAYR),
`
`wherein Compound 14-
`(A1)(B1)(R1)\(R]1)to
`Compound 14-
`
`Ai
`
`RIAnesAi
`
`| CN
`Ric
`
`(A15)\(B15)\(R141)(R14
`
`1), have the structure
`
`(A15)\(B15)(R141)(R14
`
`1), have the structure
`
`Ri Rk
`Compound 16-
`Ri
`Compound 15-
`(AD(B/(RAVR), NoUAI|(AD(B(RA(RD,Bj Bj SH
`
`
`
`
`wherein Compound 15-
`| Z
`wherein Compound 16-
`| Mk
`
`
`(A1)(B1\(R1)(RI)to Rk|(ADBILRIVRD)to Ai
`Compound 15-
`Compound 16-
`
`(A15)\(B15)\(R141)(R14
`
`1), have the structure
`
`(A15)\(B15)(R141)(R14
`
`18
`
`

`

`
`
`
`
`(A)(B/(RAVR), NW BF|(ADB/RORD. AahAi
`
`
`
`(A1(BIVYRI(RDto RK|(AL(BIVRIVRD)to By
`
`| Z
`wherein Compound 22-
`| 2
`wherein Compound 21-
`
`
`Compound21-
`Compound 22-
`
`
`
`
`
`Attorney Docket No.: UDC-1693P2 (376.0041P)
`
`Ri
`
`Bj
`
`(AD(B/(RAYR),
`
`wherein Compound 17-
`(A1)(B1\(R1)(RI)to
`Compound 17-
`
`(A15)\(B15)(R141\(R14
`
`| aN
`T
`
`Al
`
`Compound 18-
`
`wherein Compound 18-
`(A1\(B1\(RI)(RI)to
`Compound 18-
`
`(A15)(B15)(R141)\(R14
`
`(AD(B/(RAYR), AhBy
`
`Ai
`
`| Z
`
`Rk
`
`1), have the structure
`1), have the structure
`
`
`Compound 19-
`
`(A/)(B/(RAR),
`
`wherein Compound 19-
`(ADBI1I)(R1I\(RDto
`Compound 19-
`
`(A15)(B15)(R141\(R14
`
`RI
`
`Ai Rk
`
`SN
`
`| 2
`
`Compound 20-
`
`(Ai)(By\(RA(RD,
`
`wherein Compound 20-
`(ADBIRI\RIto
`Compound 20-
`
`(A15)(B15)(R141)\(R14
`
`By
`
`Ai
`
`ARewsBj
`
`| LN
`Bk
`
`1), have the structure
`1), have the structure
`
`
`Compound2 1-
`
`Ri
`
`Compound 22-
`
`Ri Rk
`
`
`
` Compound 17-
`
`(A15)\(B15\(R141\(R14
`
`1), have the structure
`
`Compound 23-
`
`(AD(B/(RAVR),
`wherein Compound 23-
`(ADBIRI\(RDto
`
`Compound 23-
`
`(A15)\(B15\(R141\(R14
`
`1), have the structure
`
`Ai
`
`Ri
`
`Bi
`| aN
`Rik
`
`19
`
`(A15)(B15)(R141)\(R14
`
`1), have the structure
`
`Compound 24-
`
`(AD(B/(RAVR),
`wherein Compound 24-
`(ADBI(RIRDto
`
`Compound 24-
`
`(A15)\(B15\(R141)\(R14
`
`1), have the structure
`
`Ai
`
`\AaNsrBy
`N LN
`Le
`
`

`

` Compound 27- 1), have the structure
`
`(A/)(B/(RAR), NAR|(AD(B)RARD. ALNw BjBj
`
`Compound3 1-
`
`wherein Compound 31-
`(A1)(B1)(R1)\(R]1)to
`Compound31-
`
`
`
`Rk
`
`| _N
`Ry
`
`Compound32-
`
`wherein Compound 32-
`(AD(BI\(R1I\(RDto
`Compound 32-
`
`
`
`Attorney Docket No.: UDC-1693P2 (376.0041P)
`
`
`
`Compound 25-
`
`(AD(B/(RAYR),
`
`wherein Compound 25-
`
`(ADBIRI\(RD to
`
`Compound 25-
`
`(A15)\(B15)(R141\(R14
`
`Compound 26-
`
`(AD)(B/)(RAV(RD,
`
`wherein Compound 26-
`
`(ADBIDRI\RI to
`
`Compound 26-
`
`(A15)\(B15)(R141)\(R14
`
`1), have the structure
`1), have the structure
`
`
`(AD(B/(RAVR), BjA,NoUAI|(AD(B)(RARD. RIaNw Rk
`
`
`whereinCompound27-
`Nn aN
`whereinCompound28-
`{J
`(A1)(B1)(R1)\(R]1)to
`Le
`(AD(B1I\(R1I\(RI)to
`Ai
`
`RI
`
`Compound 27-
`
`(A15)(B15)(R141)(R14
`
`Compound 28-
`
`Compound 28-
`
`(A15)(B15)(R141)(R14
`
`Bj
`
`1), have the structure
`1), have the structure
`
`
`-Bj
`
`No
`
`Ai
`
`R)
`
`Compound 29-
`
`(AD)(BARR,
`
`wherein Compound 29-
`(A1)(B1I)(R1)\(RI)to
`Compound 29-
`
`(A15)(B15)(R141)(R14
`
`1), have the structure
`
`| _N
`Rk
`
`Compound30-
`
`(Ad)(B/)(RA(RD,
`
`wherein Compound 30-
`(ADBI(RI\(RYto
`Compound 30-
`
`(A15)(B15)(R141)(R14
`
`1), have the structure
`
`Ri
`
`BjIoeNw _-Rk
`
`4 Z
`hi
`
`
`
`Rk
`
`x Z
`Ri
`
`
`
`
`
`(A15)(B15)(R141)(R14
`
`(A15)(B15)(R141)(R14
`
`1), have the structure
`
`20
`
`

`

` Compound33- 1), have the structure
`
`
`
`Com