JP2019501872A - Crosslinkable hole transport material - Google Patents

Abstract

The present invention relates to novel hole transport materials which can be represented as compounds of formula I or polymers derived therefrom. Also disclosed is an organic electronic device comprising an anode, a cathode, and at least one organic active layer therebetween, wherein the organic active layer comprises a hole transport material.

Description

  The present disclosure relates to novel hole transport compounds. The present disclosure further relates to an electronic device having at least one layer comprising such a hole transport compound.

  In organic electronic devices such as organic light emitting diodes (“OLEDs”) that make up OLED displays, one or more organic electroactive layers are sandwiched between two electrical contact layers. In an OLED, at least one organic electroactive layer emits light through the light transmissive electrical contact layer when a voltage is applied across the electrical contact layer.

  It is known to use organic electroluminescent compounds as light emitting components in light emitting diodes. Simple organic molecules, conjugated polymers, and organometallic complexes have been used.

  Devices that use electroluminescent materials often comprise one or more charge transport layers disposed between a photoactive (eg, light emitting) layer and a contact layer (hole injection contact layer). The device can comprise more than one contact layer. The hole transport layer may be disposed between the photoactive layer and the hole injection contact layer. The hole injection contact layer may also be called an anode. The electron transport layer can be disposed between the photoactive layer and the electron injection contact layer. The electron injection contact layer may be called a cathode.

  There is a continuing need for electroactive materials for use in electronic devices.

  Formula I

Wherein Q ¹ and Q ² are the same or different and are H, D, alkyl, deuterated alkyl, aryl, deuterated aryl, and formula II

Selected from the group consisting of: provided that at least one of Q ¹ and Q ² is a group having formula II;
Where
HT is the same or different for each occurrence, is a hole transport group,
L ¹ is the same or different at each occurrence and is selected from the group consisting of alkyl, aryl, their substituted derivatives, their deuterated analogs, and combinations thereof;
R ¹ and R ² are the same or different and are H or D;
The group consisting of D, CN, halogen, alkyl, alkoxy, silyl, germyl, deuterated alkyl, deuterated alkoxy, deuterated silyl, and deuterated germyl, wherein R ³ is the same or different for each occurrence Selected from
a is an integer of 0 to 4,
b is the same or different for each occurrence, is 0 or 1, and
A compound is provided having ^* indicates a point of attachment.

  Formula III

[Where:
L ¹ is the same or different at each occurrence and is selected from the group consisting of alkyl, aryl, their substituted derivatives, their deuterated analogs, and combinations thereof;
R ¹ and R ² are the same or different and are H or D;
The group consisting of D, CN, halogen, alkyl, alkoxy, silyl, germyl, deuterated alkyl, deuterated alkoxy, deuterated silyl, and deuterated germyl, wherein R ³ is the same or different for each occurrence Selected from
R ⁴ is selected from the group consisting of H, D, and L ¹ ;
a is an integer from 0 to 4, and
A polymer having at least one monomer unit of ^* indicates the point of attachment] is provided.

  Formula IV

[Where:
A is a monomer unit containing at least one hole transport group;
M1 is a monomer unit having at least three points of attachment in the copolymer;
M2 is an aromatic monomer unit having two points of attachment or a deuterated analog thereof,
E is of formula III-a

A monomer unit having the formula:
L ¹ is selected from the group consisting of alkyl, aryl, substituted derivatives thereof, deuterated analogs thereof, and combinations thereof;
R ¹ and R ² are the same or different and are H or D;
The group consisting of D, CN, halogen, alkyl, alkoxy, silyl, germyl, deuterated alkyl, deuterated alkoxy, deuterated silyl, and deuterated germyl, wherein R ³ is the same or different for each occurrence Selected from
R ^4a is H or D;
a is an integer of 0 to 4,
x, y, z and w are the same or different, are mole fractions, at least x and w are not 0, and
A copolymer is provided having ^* indicates the point of attachment.

  Further provided are electronic devices having at least one layer comprising a compound having formula I, a polymer having at least one monomer unit having formula III, or a copolymer having formula IV.

  The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims.

  Embodiments are described in the accompanying drawings to facilitate understanding of the concepts presented herein.

1 shows an illustration of one example of an organic electronic device. Fig. 4 shows an illustration of another example of an organic electronic device.

  It will be apparent to those skilled in the art that the objects in the drawings are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, some dimensions of the objects in the figures may be exaggerated relative to other objects to help deepen the understanding of the embodiments.

  Provided are compounds having Formula I, described in detail herein.

  There is provided a polymer having at least one monomer unit having the formula III, as described in detail herein.

  Copolymers having Formula IV, described in detail herein, are provided.

  There is provided an electronic device having at least one layer comprising a compound having formula I, a polymer having at least one monomer unit having formula III, or a copolymer having formula IV.

  Many aspects and embodiments have been described above and are merely exemplary and not limiting. After reading this specification, skilled artisans will appreciate that other aspects and embodiments are possible without departing from the scope of the invention.

  Other features and advantages of any one or more embodiments will be apparent from the following detailed description, and from the claims. The detailed description begins with a definition and explanation of terms, followed by compounds, copolymers, electronic devices, and finally examples.

1. Definitions and Explanations of Terms Before addressing details of embodiments described below, some terms are defined or clarified.

  The term “alkyl” includes branched and straight-chain aliphatic saturated hydrocarbon groups. Unless otherwise noted, terms are also intended to include cyclic groups. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, isobutyl, secbutyl, tertbutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, isohexyl and the like. The term “alkyl” further includes both substituted and unsubstituted hydrocarbon groups. In some embodiments, the alkyl group may be mono-, di-, and tri-substituted. An example of a substituted alkyl group is trifluoromethyl. Other substituted alkyl groups are formed from one or more of the substituents described herein. In certain embodiments, the alkyl group has 1-20 carbon atoms. In other embodiments, the group has 1-6 carbon atoms. This term is intended to include heteroalkyl groups. A heteroalkyl group may have 1 to 20 carbon atoms.

  The term “aromatic compound” is intended to mean an organic compound comprising at least one unsaturated cyclic group having delocalized π electrons. The term includes both aromatic compounds having only carbon and hydrogen atoms and heteroaromatic compounds in which one or more of the carbon atoms in the cyclic group is replaced by another atom such as nitrogen, oxygen, sulfur, etc. It is intended to include.

  The term “aryl” or “aryl group” means a moiety derived from an aromatic compound. A group “derived from” a compound refers to a radical formed by removal of one or more H or D. Aryl groups can be monocyclic (monocyclic) or multiple rings (bicyclic or higher) fused together or linked by covalent bonds. Examples of aryl moieties include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, dihydronaphthyl, tetrahydronaphthyl, biphenyl, anthryl, phenanthryl, fluorenyl, indanyl, biphenylenyl, acenaphthenyl, acenaphthylenyl, and the like. In some embodiments, aryl groups have 6-60 ring carbon atoms, in some embodiments, 6-30 ring carbon atoms. This term is intended to include heteroaryl groups. A heteroaryl group may have 3 to 50 ring carbon atoms, in some embodiments, 4 to 30 ring carbon atoms.

  “Alkoxy” is intended to mean the group —OR, wherein R is alkyl.

  The term “aryloxy” is intended to mean the group —OR, where R is aryl.

Unless otherwise stated, all groups can be substituted or unsubstituted. Although not limited, an optionally substituted group such as alkyl or aryl may be substituted with one or more substituents which may be the same or different. Suitable substituents include D, alkyl, aryl, nitro, cyano, —N (R ⁷ ) (R ⁸ ), halo, hydroxy, carboxy, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, hetero Aryloxy, alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy, arylalkyl, silyl, siloxane, thioalkoxy, —S (O) ₂ —N (R ′) (R ″), —C (═O) —N (R ') (R''),(R') (R '') N-alkyl, (R ') (R'') N-alkoxyalkyl, (R') (R '') N-alkylaryloxyalkyl , -S (O) _s -aryl (where s = 0-2) or -S (O) _s -heteroaryl (where s = 0-2). Each R ′ and R ″ is independently an optionally substituted alkyl, cycloalkyl, or aryl group. In certain embodiments, R ′ and R ″, together with the nitrogen atom to which they are attached, can form a ring system. Further, the substituent may be a crosslinking group.

  When the term “charge transport” refers to a layer, material, member or structure, such layer, material, member or structure is relatively efficient and with low charge loss, such layer, material, It is intended to mean facilitating such charge transfer through the thickness of the member or structure. The hole transport material facilitates a positive charge, and the electron transport material facilitates a negative charge. The luminescent material may also have some charge transport properties, but the term “charge transport layer, material, member or structure” is intended to encompass a layer, material, member or structure whose primary function is luminescence. Is not intended.

  The term “compound” is intended to mean an uncharged material composed of molecules further containing atoms that cannot be separated from their corresponding molecules by physical means without breaking chemical bonds. To do. The term is intended to encompass oligomers and polymers.

  The term “crosslinkable group” or “crosslinking group” refers to a compound or polymer that can be bonded to another compound or polymer chain by heat treatment, use of an initiator, or exposure to radiation, where the bond is a covalent bond. It is intended to mean a group on the chain. In some embodiments, the radiation is ultraviolet light or visible radiation. Examples of crosslinkable groups include, but are not limited to, vinyl, acrylate, perfluorovinyl ether, 1-benzo-3,4-cyclobutane, o-quinodimethane group, siloxane, cyanate group, cyclic ether (epoxide), cycloalkene, and acetylene. A group is included.

  The term “electroactive”, when it refers to a layer or material, is intended to indicate a layer or material that electronically facilitates the operation of the device. Examples of electroactive materials include, but are not limited to, materials that conduct, inject, transport, or block charges (charges can be either electrons or holes), or materials that emit radiation or electrons when they receive radiation. -Materials that show changes in the concentration of hole pairs are included. Examples of inert materials include, but are not limited to, planarization materials, insulating materials, and environmental barrier materials.

  The prefix “fluoro” is intended to indicate that one or more hydrogen atoms in a group are replaced by fluorine atoms.

  The prefix “hetero” indicates that one or more carbon atoms have been replaced with a different atom. In some embodiments, the heteroatom is O, N, S, or a combination thereof.

  The term “liquid composition” refers to a liquid medium in which the material is dissolved to form a solution, a liquid medium in which the material is dispersed to form a dispersion, or the material is suspended to form a suspension or emulsion. It is intended to mean a liquid medium.

  The term “photoactive” refers to light emission when activated by an applied voltage (such as in a light emitting diode or chemical cell), light emission after absorption of a photon (such as in a downconverting phosphor device), or Refers to a material or layer that responds to radiant energy (such as in a photodetector or photovoltaic cell) and generates a signal with or without an applied bias voltage.

The term “silyl” refers to the group R ₃ Si—, where R is H, D, C 1-20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons in the R alkyl group are substituted with Si. In some embodiments, the silyl group is (hexyl) ₂ Si (Me) CH ₂ CH ₂ Si (Me) ₂ — and [CF ₃ (CF ₂ ) ₆ CH ₂ CH ₂ ] ₂ SiMe—.

The term “siloxane” refers to the group (RO) ₃ Si—, where R is H, D, C 1-20 alkyl, or fluoroalkyl.

  The phrase “adjacent to” when used to refer to a layer in a device does not necessarily mean that one layer is immediately adjacent to another layer. On the other hand, the phrase “adjacent R groups” is used to refer to R groups that are next to each other in a chemical formula (ie, R groups that are on atoms joined by a bond).

  Unless specifically stated otherwise herein or indicated to the contrary in relation to use, embodiments of the subject matter herein include, include, include, certain features or elements One or more features or elements in addition to those explicitly stated or described are described or described as having, consisting of, or by or consisting of May be present. Alternative embodiments of the disclosed subject matter herein are described as consisting essentially of certain features or elements, which in this embodiment substantially alter the principles of operation or the distinguishing characteristics of the embodiments. Features and elements do not exist there. Additional alternative embodiments of the subject matter described herein are described as comprising certain features or elements, and are specifically described or described in this embodiment, or in its non-existent variations. Only the features or elements that exist are present.

  Further, unless stated to the contrary, “or” means inclusive “or” and not exclusive “or”. For example, condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or does not exist), and A is false (or does not exist) And B is true (or present), and both A and B are true (or present).

  Also, the use of “a” or “an” is used to describe the elements and components described herein. This is for convenience only and to give a general sense of the scope of the invention. This description should be interpreted to include one, or at least one, and the singular also includes the plural unless it is obvious that it has another meaning.

The “new notation” convention is used so that the group number corresponding to the column of the periodic table of elements can be found in CRC Handbook of Chemistry and Physics, 81 ^st Edition (2000-2001).

  Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are hereby incorporated by reference in their entirety, unless a particular section is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

  To the extent not described here, many details regarding specific materials, processing operations, and circuits are conventional and include texts on organic light emitting diode displays, photodetectors, photovoltaic cells, and semiconductor component technologies and It can be found in other sources.

2. Compounds described herein are compounds of formula I

Wherein Q ¹ and Q ² are the same or different and are H, D, alkyl, deuterated alkyl, aryl, deuterated aryl, and formula II

Selected from the group consisting of: provided that at least one of Q ¹ and Q ² is a group having formula II;
Where
HT is the same or different for each occurrence, is a hole transport group,
L ¹ is the same or different at each occurrence and is selected from the group consisting of alkyl, aryl, their substituted derivatives, their deuterated analogs, and combinations thereof;
R ¹ and R ² are the same or different and are H or D;
The group consisting of D, CN, halogen, alkyl, alkoxy, silyl, germyl, deuterated alkyl, deuterated alkoxy, deuterated silyl, and deuterated germyl, wherein R ³ is the same or different for each occurrence Selected from
a is an integer of 0 to 4,
b is the same or different for each occurrence, is 0 or 1, and
^{* Indicates a} bonding point].

  In some embodiments, the compound having Formula I is deuterated. The term “deuterated” is intended to mean that at least one hydrogen (“H”) is replaced with deuterium (“D”). The term “deuterated analog” refers to a structural analog of a compound or group in which one or more available hydrogens are replaced with deuterium. In the deuterated compound or deuterated analog, deuterium is present at least 100 times its natural abundance level. In some embodiments, the compound is at least 10% deuterated. “% Deuterated” or “% deuterated” intends the ratio of deuterons expressed as a percentage to the sum of protons + deuterons. In some embodiments, the compound is at least 10% deuterated, in some embodiments at least 20% deuterated, and in some embodiments at least 30% deuterated. And in some embodiments at least 40% deuterated, in some embodiments at least 50% deuterated, and in some embodiments at least 60% deuterated. And in some embodiments at least 70% deuterated, in some embodiments at least 80% deuterated, and in some embodiments at least 90% deuterated. And in some embodiments, 100% deuterated.

  Deuterated materials are less likely to decompose by holes, electrons, excitons, or combinations thereof. Deuteration can in some cases inhibit compound degradation during device operation, and can also result in improved device lifetime. In general, this improvement is achieved without sacrificing other device properties. Furthermore, deuterated compounds often have greater air resistance than non-deuterated analogs. This can increase the processing tolerance both for the preparation and purification of the material and when the material is used to form the electronic device.

In some embodiments of Formula I, Q ¹ = Q ² .

In some embodiments of Formula I, Q ¹ ≠ Q ² .

In some embodiments of Formula I, Q ¹ is H or D.

In some embodiments of Formula I, Q ¹ has 1 to 12 carbons, in some embodiments 1 to 8 carbons, and in some embodiments 3 to 8 carbons. An alkyl or deuterated alkyl group.

In some embodiments of Formula I, Q ¹ is 6-60 ring carbons, in some embodiments 6-30 ring carbons, in some embodiments 10-20 ring carbons. Is a hydrocarbon aryl or deuterated analog having

In some embodiments of Formula I, Q ¹ is a hydrocarbon aryl group having at least one fused ring or a deuterated analog thereof.

In some embodiments of Formula I, Q ¹ is selected from the group consisting of naphthyl, anthranyl, naphthylphenyl, phenylnaphthyl, fluorenyl, substituted derivatives thereof, and deuterated analogs thereof.

In some embodiments of Formula I, Q ¹ is a hydrocarbon aryl group having no fused rings.

In some embodiments of Formula I, Q ¹ is represented by the formula a

[Where:
R ²⁰ is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy, siloxane, silyl, germyl, and their deuterated analogs;
p is the same or different for each occurrence and is an integer from 0 to 4;
q is an integer of 0 to 5;
r is an integer from 1 to 5, and
^* Represents a bond point].

In some embodiments of Formula I, Q ¹ is of formula b

Wherein R ²⁰ , p, q, r and ^* are the same as in formula a.

In some embodiments of Formula I, Q ¹ is selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, substituted derivatives thereof, and deuterated analogs thereof. In some embodiments, the substituent is selected from the group consisting of D, F, CN, alkyl, silyl, germyl, deuterated alkyl, deuterated silyl, and deuterated germyl.

In some embodiments of Formula I, Q ¹ is heteroaryl having 3 to 60 ring carbons or a deuterated analog thereof. In some embodiments, the heteroaryl has 3-30 ring carbons, in some embodiments, 5-20 ring carbons.

In some embodiments of Formula I, Q ¹ is N-heteroaryl or a deuterated analog thereof.

  In some embodiments, the N-heteroaryl is pyrrole, pyridine, pyrimidine, carbazole, imidazole, benzimidazole, imidazolobenzimidazole, triazole, benzotriazole, triazolopyridine, indolocarbazole, phenanthroline, quinoline, isoquinoline, A group derived from a compound selected from the group consisting of quinoxaline, indole, indoloindole, substituted derivatives thereof, and deuterated analogs thereof.

In some embodiments of Formula I, Q ¹ is a group having the Formula II defined above.

  In some embodiments of Formula II, b = 0.

  In some embodiments of Formula II, b = 1.

In some embodiments of Formula II, b = 1 and L ¹ is 1-12 carbons, in some embodiments 1-8 carbons, in some embodiments 3- An alkyl or deuterated alkyl group having 8 carbons.

In some embodiments of Formula II, b = 1 and L ¹ is 6-60 ring carbons, in some embodiments 6-30 ring carbons, in some embodiments 10 A hydrocarbon aryl or deuterated analog having -20 ring carbons.

In some embodiments of Formula II, b = 1 and L ¹ is a hydrocarbon aryl group having at least one fused ring or a deuterated analog thereof.

In some embodiments of Formula II, b = 1 and L ¹ is selected from the group consisting of naphthyl, anthranyl, naphthylphenyl, phenylnaphthyl, fluorenyl, substituted derivatives thereof, and deuterated analogs thereof. Is done.

In some embodiments of Formula II, b = 1 and L ¹ is a hydrocarbon aryl group having no fused rings.

In some embodiments of Formula II, b = 1 and L ¹ is of the formula c

Wherein R ²⁰ , p, r and ^* are the same as in formula a.

In some embodiments of Formula II, b = 1 and L ¹ is of formula d

Wherein R ²⁰ , p, r and ^* are the same as in formula a.

In some embodiments of Formula II, b = 1 and L ¹ consists of phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, substituted derivatives thereof, and deuterated analogs thereof Selected from the group. In some embodiments, the substituent is selected from the group consisting of D, F, CN, alkyl, silyl, germyl, deuterated alkyl, deuterated silyl, and deuterated germyl.

In some embodiments of Formula II, b = 1 and L ¹ is heteroaryl having 3 to 60 ring carbons or a deuterated analog thereof. In some embodiments, the heteroaryl has 3-30 ring carbons, in some embodiments, 5-20 ring carbons.

In some embodiments of Formula II, b = 1 and L ¹ is N-heteroaryl or a deuterated analog thereof.

  In some embodiments of Formula II, HT is selected from the group consisting of arylamino, N-heterocyclic, fused hydrocarbon aromatic, substituted derivatives thereof, combinations thereof, and deuterated analogs thereof. Including parts.

  In some embodiments of Formula II, HT is selected from the group consisting of diarylamino, triarylamino, substituted derivatives thereof, and deuterated analogs thereof. In some embodiments, HT is a moiety that includes at least two arylamino groups.

  In some embodiments of Formula II, HT is an N heterocyclic group having one or more nitrogen heteroatoms and no other heteroatoms, or deuterated analogs thereof.

  In some embodiments, the N heterocyclic group having only nitrogen heteroatoms is carbazole, benzocarbazole, azacarbazole, acridan, indole, indoloindole, indolocarbazole, imidazole, benzimidazole, pyrrolopyrrole, diazine, Derived from a compound selected from the group consisting of pyridine, pyrimidine, pyridazine, pyrazine, triazine, triazolopyridine, quinoline, isoquinoline, substituted derivatives thereof, and deuterated analogs thereof.

  In some embodiments of Formula II, HT is an N heterocyclic group having at least one nitrogen heteroatom and at least one oxygen or sulfur heteroatom.

  In some embodiments, the N heterocyclic group is selected from the group consisting of oxazine, phenoxazine, oxazole, benzoxazole, phenothiazine, benzothiazole, benzothiadiazole, substituted derivatives thereof, and deuterated analogs thereof. Derived from the compound.

  In some embodiments of Formula II, HT is a hydrocarbon aryl group having a fused ring or a deuterated analog thereof.

  In some embodiments, the hydrocarbon aryl group is a compound selected from the group consisting of fluorene, anthracene, benzoanthracene, triphenylene, indane, indenofluorene, substituted derivatives thereof, and deuterated analogs thereof. Derived from.

  In some embodiments of Formula II, HT is selected from the group consisting of at least one arylamino group and carbazole, benzocarbazole, indolocarbazole, fluorene, substituted derivatives thereof, and deuterated analogs thereof. And a second group derived from the compound to be produced.

  In some embodiments, HT is of formula HT-1

[Where:
Ar ¹ is an aryl or deuterated aryl group,
Ar ² is the same or different at each occurrence and is an aryl or deuterated aryl group;
b1 is 0 or 1, and
^* Represents a bond point].
In Formula I, b = 1 if HT has Formula HT-1 and b1 = 0.

In some embodiments of Formula HT-1, Ar ¹ has formula c, or formula d, as defined above.

In some embodiments of Formula HT-1, Ar ¹ is selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, anthranyl, substituted analogs thereof, and deuterated analogs thereof.

In some embodiments of Formula HT-1, Ar ² has Formula a or Formula b as defined above.

In some embodiments of Formula HT-1, Ar ² is phenyl, biphenyl, terphenyl, naphthyl, anthranyl, carbazolyl, combinations of such groups joined together by covalent bonds, substituted derivatives thereof, and Selected from the group consisting of:

  In some embodiments, HT is of formula HT-1a

[Where:
Ar ^1a and Ar ^2a are the same or different at each occurrence and are derived from a compound selected from the group consisting of fluorene, arylenecarbazole, triarylamine, substituted derivatives thereof, and their deuterated analogs; and
^* Represents a bond point].

  In some embodiments, HT is of formula HT-2.

[Where:
Ar ¹ is an aryl or deuterated aryl group,
Ar ² is the same or different at each occurrence and is an aryl or deuterated aryl group;
Ar ³ is aryl, (CR ′ ₂ ) _r , adamantyl, bicyclic cyclohexyl, bicyclic groups in which an aliphatic ring is bonded by a single atom, substituted derivatives thereof, and deuterated analogs thereof Selected from the group consisting of
R ′ is the same or different at each occurrence and is H, D, alkyl, fluoroalkyl, aryl, deuterated alkyl, deuterated fluoroalkyl, and deuterated aryl, and
^* Represents a bond point].

In some embodiments of Formula HT-2, Ar ³ has Formula a or Formula b as defined above.

In some embodiments of Formula HT-2, Ar ³ is selected from the group consisting of phenyl, naphthyl, anthranyl, substituted derivatives thereof, and deuterated analogs thereof.

All of the above embodiments for Ar ¹ and Ar ² of formula HT- ¹ apply equally to Ar ¹ and Ar ² of formula HT-2.

  In some embodiments, HT is of formula HT-2a

[Where:
Ar ² is the same or different at each occurrence and is an aryl or deuterated aryl group;
R ^{5 to} R ⁹ are the same or different at each occurrence, and D, F, CN, alkyl, fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy, Deuterated alkyl, deuterated partially fluorinated alkyl, deuterated aryl, deuterated heteroaryl, deuterated amino, deuterated silyl, deuterated germyl, deuterated alkoxy, deuterated aryloxy, Selected from the group consisting of deuterated fluoroalkoxy, deuterated siloxane, deuterated siloxy, and bridging groups, adjacent R ⁵ or R ⁹ groups joined together to form a fused 5- or 6-membered aromatic ring Can form
a1 is the same or different for each occurrence and is an integer from 0 to 4;
b3 is 0 or 1,
f is the same or different for each occurrence and is 0 to the maximum number of available binding positions;
g is an integer of 0 to 3,
h is 1 or 2, and
^* Represents a bond point].

In some embodiments of Formula HT-2a, the two Ar ² groups are the same.

In some embodiments of Formula HT-2a, the two Ar ² groups are different.

In some embodiments of Formula HT-2a, at least one Ar ² is an aryl group having no fused rings.

In some embodiments of Formula HT-2a, at least one Ar ² has formula c or formula d, as defined above.

In some embodiments of Formula HT-2a, Ar ² is phenyl, biphenyl, terphenyl, as well as derivatives thereof having one or more substituents selected from the group consisting of alkyl, alkoxy, and silyl, As well as selected from the group consisting of their deuterated analogs.

In some embodiments of Formula HT-2a, R ⁵ -R ⁹ are D or C _1-10 alkyl. In some embodiments, the alkyl group is deuterated.

  In some embodiments of Formula HT-2a, all a1 = 0.

  In some embodiments of Formula HT-2a, at least one a1> 0.

  In some embodiments of Formula HT-2a, all f = 0.

  In some embodiments of Formula HT-2a, at least one f> 0.

  In some embodiments of Formula HT-2a, b3 = 1.

  In some embodiments of Formula HT-2a, h = 2.

  In some embodiments of Formula HT-2a, g = 1.

  In some embodiments of Formula HT-2a, g = 2.

  In some embodiments, HT is of formula HT-3.

[Where:
Ar ¹ is an aryl or deuterated aryl group,
Ar ² is the same or different at each occurrence and is an aryl or deuterated aryl group;
Ar ⁴ is an aryl or deuterated aryl group, and
^* Represents a bond point].

All of the above embodiments for Ar ¹ and Ar ² of the formula HT-1 apply equally to Ar ¹ and Ar ² of the formula HT-3.

In some embodiments of Formula HT-3, Ar ⁴ is a fused hydrocarbon aryl group having 10 to 36 ring carbons, substituted derivatives thereof, or deuterated analogs thereof.

In some embodiments of Formula HT-3, Ar ⁴ is selected from the group consisting of benzene, phenylbenzene, naphthalene, anthracene, pyrene, chrysene, substituted derivatives thereof, and deuterated analogs thereof Derived from.

  In some embodiments, HT is of formula HT-4

[Where:
Ar ¹ is the same or different at each occurrence and is an aryl group or a deuterated aryl group;
Ar ² is the same or different at each occurrence and is an aryl group or a deuterated aryl group;
Ar ⁵ is the same or different at each occurrence and is selected from the group consisting of phenylene, substituted phenylene, naphthylene, substituted naphthylene, and their deuterated analogs;
T ¹ and T ² are independently the same or different at each occurrence and are conjugated moieties bound in a non-planar configuration, or their deuterated analogs;
d is the same or different for each occurrence and is an integer from 1 to 6;
e is an integer from 1 to 6, and
^* Represents a bond point].

In some embodiments of Formula HT-4, at least one Ar ⁵ is substituted phenyl having a substituent selected from the group consisting of alkyl, alkoxy, silyl, and deuterated analogs thereof.

  In some embodiments of Formula HT-4, d is 1-4.

  In some embodiments of Formula HT-4, d is 1-3.

  In some embodiments of Formula HT-4, d = 1.

Any of the aromatic rings of formula HT-4 may be substituted at any position. Substituents may be present to improve one or more physical properties of the compound, such as solubility. In some embodiments, the substituent is selected from the group consisting of D, C _1-12 alkyl group, C _1-12 alkoxy group, silyl group, germyl group, and deuterated analogs thereof. In some embodiments, the alkyl group is a heteroalkyl group. In some embodiments, the alkyl group is a fluoroalkyl group.

All of the above embodiments for Ar ¹ and Ar ² of the formula HT-1 apply equally to Ar ¹ and Ar ² of the formula HT-4.

In some embodiments of Formula HT-4, at least one Ar ² has a substituent selected from the group consisting of alkyl, alkoxy, silyl, and deuterated analogs thereof.

In formula HT-4, T ¹ and T ² are conjugated moieties. In some embodiments, T ¹ and T ² are aromatic or deuterated aromatic moieties.

In some embodiments of Formula HT-4, T ¹ and T ² are selected from the group consisting of phenylene, naphthylene, anthranyl, and deuterated analogs thereof.

In some embodiments of Formula HT-4, [T ¹ -T ² ] is a substituted biphenylene group or a deuterated analog thereof. The term “biphenylene” is intended to mean a biphenyl group having two points of attachment to the main chain of the compound. The term “biphenyl” is intended to mean a group in which two phenyl units are joined by a single bond. A biphenylene group can be attached at one of 2, 3, 4 or 5 positions and at one of 2 ′, 3 ′, 4 ′ or 5 ′ positions. The substituted biphenylene group has at least one substituent at the 2-position. In some embodiments of Formula HT-4, the biphenylene group has substituents at least at the 2- and 2 ′ positions.

In some embodiments of Formula HT-4, [T ¹ -T ² ] is a binaphthylene group or a deuterated binaphthylene group. The term “binaphthylene” is intended to mean a binaphthyl group having two points of attachment to the backbone of the compound. The term “binaphthyl” is intended to mean a group in which two naphthalene units are joined by a single bond. In some embodiments, the binaphthylene group is 1,1′-binaphthylene, which is one of 3, 4, 5, 6, or 7 positions and 3 ′, 4 ′, 5 ′, 6 ′, or It is attached to the main chain of the compound at one of the 7 'positions.

In some embodiments of Formula HT-4, [T ¹ -T ² ] is a phenylene-naphthylene group or a deuterated phenylene-naphthylene group.

  In some embodiments of Formula HT-4, the biphenylene, binaphthylene, and phenylene-naphthylene groups are substituted at one or more positions.

In some embodiments of Formula HT-4, [T ¹ -T ² ] is attached to the base backbone at 4 and 4 ′ positions, referred to as 4,4 ′-(1,1-binaphthylene). 1,1-binaphthylene group.

  In some embodiments, HT is formula HT-5 or formula HT-6.

[Where:
Ar ¹ is an aryl group or a deuterated aryl group,
Ar ² is the same or different at each occurrence and is an aryl group or a deuterated aryl group;
Ar ⁶ is the same or different at each occurrence and is an aryl group or a deuterated aryl group;
Ar ⁷ is an aryl group or a deuterated aryl group,
R ¹⁰ and R ¹¹ are the same or different at each occurrence, and D, F, CN, alkyl, fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy, Deuterated alkyl, deuterated partially fluorinated alkyl, deuterated aryl, deuterated heteroaryl, deuterated amino, deuterated silyl, deuterated germyl, deuterated alkoxy, deuterated aryloxy, Adjacent groups selected from R ¹⁰ and R ¹¹ selected from the group consisting of deuterated fluoroalkoxy, deuterated siloxane, deuterated siloxy, and bridging groups join together to form a condensed ring. Can
b2 is 0 or 1,
g1 is the same or different for each occurrence, is an integer from 0 to 3, and
^* Represents a bond point].

All of the above embodiments for Ar ¹ of formula HT-1 apply equally to Ar ¹ and Ar ⁶ of formula HT-6.

All of the above embodiments for Ar ² of formula HT-1 apply equally to Ar ² of formula HT-5 and formula HT-6.

In some embodiments of Formula HT-5, Ar ⁷ has the formula a or b defined above.

In some embodiments of Formula HT-5, Ar ⁷ is selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, anthranyl, substituted derivatives thereof, and deuterated analogs thereof.

All of the above embodiments for R ^{4 to} R ⁹ of Formula HT-2a apply equally to R ¹⁰ and R ¹¹ of Formula HT-5 and Formula HT-6.

  In some embodiments of Formula HT-5, b2 = 0.

  In some embodiments of Formula HT-5, b2 = 1.

  In some embodiments of Formula HT-5, g2 = 0.

  In some embodiments of Formula HT-5, at least one g2 = 1.

  In some embodiments of Formula HT-5, at least one g 2> 0.

  In some embodiments of Formula HT-6, b2 = 0.

  In some embodiments of Formula HT-6, b2 = 1.

  In some embodiments of Formula HT-6, g2 = 0.

  In some embodiments of Formula HT-6, at least one g2 = 1.

  In some embodiments of Formula HT-6, at least one g2> 0.

  In some embodiments, HT is of formula HT-7.

[Where:
Ar ⁸ is selected from the group consisting of H, D, an aryl group or a deuterated aryl group, provided that when k = 0, Ar ⁸ is aryl or deuterated aryl;
R ¹⁰ and R ¹¹ are the same or different at each occurrence, and D, F, CN, alkyl, fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy, Deuterated alkyl, deuterated partially fluorinated alkyl, deuterated aryl, deuterated heteroaryl, deuterated amino, deuterated silyl, deuterated germyl, deuterated alkoxy, deuterated aryloxy, Adjacent groups selected from R ¹⁰ and R ¹¹ selected from the group consisting of deuterated fluoroalkoxy, deuterated siloxane, deuterated siloxy, and bridging groups join together to form a condensed ring. Can
a2 is an integer of 0 to 4,
g2 is the same or different for each occurrence and is an integer from 0 to 3,
k is an integer from 0 to 2, and
^* Represents a bond point].

In some embodiments of Formula HT-7, Ar ⁸ has the formula a or b defined above.

In some embodiments of Formula HT-7, Ar ⁸ is selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, anthranyl, substituted derivatives thereof, and deuterated analogs thereof.

All of the above embodiments for R ^{4 to} R ⁹ of formula HT-2a apply equally to R ¹⁰ and R ¹¹ of formula HT-7.

  In some embodiments of Formula HT-7, a2 = 0.

  In some embodiments of Formula HT-7, a2 = 1.

  In some embodiments of Formula HT-7, as> 0.

  In some embodiments of Formula HT-7, g2 = 0.

  In some embodiments of Formula HT-7, at least one g2 = 1.

  In some embodiments of Formula HT-7, at least one g2> 0.

All of the embodiments described above for Q ¹ apply equally to Q ² .

  In some embodiments of Formula I, a = 0.

  In some embodiments of Formula I, a = 1.

  In some embodiments of Formula I, a = 2.

  In some embodiments of Formula I, a = 3.

  In some embodiments of Formula I, a = 4.

  In some embodiments of Formula I, a> 0.

In some embodiments of Formula I, a> 0 and R ¹ = D.

In some embodiments of Formula I, a> 0 and at least one R ¹ is 1-12 carbons, in some embodiments 1-8 carbons, in some embodiments. , An alkyl or deuterated alkyl group having 3 to 8 carbons.

In some embodiments of Formula I, a> 0 and at least one R ¹ is 1-12 carbons, in some embodiments 1-8 carbons, in some embodiments. , Alkoxy having 3 to 8 carbons or deuterated alkoxy.

In some embodiments of Formula I, a> 0 and at least one R ¹ consists of methyl, ethyl, propyl, butyl, pentyl, hexyl, trimethylsilyl, triethylsilyl, and deuterated analogs thereof. Selected from the group.

Any of the above-described embodiments of Formula I can be combined with one or more other embodiments as long as they do not conflict with each other. For example, embodiments in which L ¹ = alkyl having 3-8 carbons can be combined with embodiments in which HT has the formula HT-1. The same is true for the other consistent embodiments described above. Those skilled in the art will understand which embodiments contradict each other and, as a result, will readily be able to determine the combination of embodiments contemplated by this application.

  Some non-limiting examples of compounds having Formula I are shown below.

  Any technique that results in a C—C or C—N bond can be used to prepare compounds of Formula I. A variety of such techniques are known, such as Suzuki, Yamamoto, Stille, and metal-catalyzed CN coupling and metal-catalyzed and oxidative direct arylation.

  Benzene-d6 in a similar manner using deuterated precursors or, more commonly, in the presence of a Lewis acid H / D exchange catalyst such as trifluoromethanesulfonic acid, aluminum trichloride or ethylaluminum dichloride. A deuterated compound can be prepared by treating a non-deuterated compound with a deuterated solvent such as.

  A typical preparation is shown in the examples.

  The compound can be formed into layers using solution processing techniques. The term “layer” is used interchangeably with the term “thin film” and refers to a coating covering a desired area. The term is not limited by size. This area can be as large as the entire device, as small as a specific functional area such as an actual display device, or as small as a single subpixel. Layers and thin films can be formed by any conventional deposition technique, including vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer. Continuous deposition techniques include, but are not limited to, spin coating, gravure coating, curtain coating, dip coating, slot die coating, spray coating, and continuous nozzle coating. Discontinuous deposition techniques include, but are not limited to, ink jet printing, gravure printing, and screen printing.

  The novel compounds having formula I can be used as hole transport materials and as hosts for electroluminescent materials. The novel compounds also have utility as materials for subbing layers that improve the deposition of hole transport layers.

3. Polymers and copolymers Also of formula III

[Where:
L ¹ is the same or different at each occurrence and is selected from the group consisting of alkyl, aryl, their substituted derivatives, their deuterated analogs, and combinations thereof;
R ¹ and R ² are the same or different and are H or D;
The group consisting of D, CN, halogen, alkyl, alkoxy, silyl, germyl, deuterated alkyl, deuterated alkoxy, deuterated silyl, and deuterated germyl, wherein R ³ is the same or different for each occurrence Selected from
R ⁴ is selected from the group consisting of H, D, and L ¹ ;
a is an integer from 0 to 4, and
Provided are polymers having at least one monomer unit having ^* denotes a point of attachment.

In some embodiments of Formula III, R ⁴ is H.

In some embodiments of Formula III, R ⁴ is D.

In some embodiments of Formula III, R ⁴ is L ¹ .

R ¹ of formula ^{I, R 2, R 3,} L 1, and all of the above embodiments for a is R ¹ of formula ^{III, R 2, R 3,} L 1, and applies equally to a.
Formula IV

[Where:
A is a monomer unit containing at least one hole transport group;
M1 is a monomer unit having at least three points of attachment in the copolymer;
M2 is an aromatic monomer unit having two points of attachment or a deuterated analog thereof,
E is of formula III-a

A monomer unit having the formula:
L ¹ is selected from the group consisting of alkyl, aryl, substituted derivatives thereof, deuterated analogs thereof, and combinations thereof;
R ¹ and R ² are the same or different and are H or D;
The group consisting of D, CN, halogen, alkyl, alkoxy, silyl, germyl, deuterated alkyl, deuterated alkoxy, deuterated silyl, and deuterated germyl, wherein R ³ is the same or different for each occurrence Selected from
R ^4a is H or D;
a is an integer of 0 to 4,
x, y, z and w are the same or different, are mole fractions, at least x and w are not 0, and
Further provided are copolymers having ^* indicates a point of attachment.

  In some embodiments of Formula I, “A”, “E”, and optional “M1” and “M2” units are arranged in a regular alternating pattern.

  In some embodiments of Formula I, the “A”, “E”, and optional “M1” and “M2” units are arranged in the same block of monomers.

  In some embodiments of Formula I, “A”, “E”, and optional “M1” and “M2” units are randomly arranged.

  In some embodiments, the distribution of monomer segments can be manipulated to optimize the properties of compounds having Formula I for use in electronic devices. In some embodiments, the different distributions can result in non-bonded filling dissimilarities that ultimately determine the relevant film-forming properties.

  In some embodiments, the copolymer having Formula IV is deuterated. In some embodiments, the copolymer is at least 10% deuterated, in some embodiments at least 20% deuterated, and in some embodiments at least 30% deuterated. And in some embodiments at least 40% deuterated, in some embodiments at least 50% deuterated, and in some embodiments at least 60% deuterated. And in some embodiments at least 70% deuterated, in some embodiments at least 80% deuterated, and in some embodiments at least 90% deuterated. And in some embodiments, 100% deuterated.

  Deuteration can be present on one or more of the monomer units A, E, M1 and M2. Deuteration can be on the main chain of the copolymer, on the side groups, or both.

In some embodiments of Formula IV, the copolymer has M _n > 10,000. In some embodiments, the copolymer has M _n > 20,000. In some embodiments, M _n > 50,000. In some embodiments, M _n > 100,000. In some embodiments, M _n > 150,000.

  In some embodiments of Formula IV, x is 0.3 to 0.9, in some embodiments, 0.4 to 0.8, and in some embodiments, 0.5 to 0.80. It is a range.

  In some embodiments of Formula IV, y ranges from 0 to 0.30, in some embodiments, 0.05 to 0.20, and in some embodiments, 0.10 to 0.15. is there.

  In some embodiments of Formula IV, z ranges from 0 to 0.30, in some embodiments, 0.05 to 0.20, and in some embodiments, 0.10 to 0.15. is there.

  In some embodiments of Formula IV, w is 0.05 to 0.30, in some embodiments, 0.10 to 0.20, and in some embodiments, 0.10 to 0.15. It is a range.

  In some embodiments of Formula IV, the monomer unit A is from the group consisting of arylamino, N-heterocyclic, fused hydrocarbon aromatics, substituted derivatives thereof, combinations thereof, and deuterated analogs thereof. Contains selected moieties.

  In some embodiments of Formula IV, monomer unit A is selected from the group consisting of diarylamino, triarylamino, substituted derivatives thereof, and deuterated analogs thereof. In some embodiments, monomer unit A is a monomer comprising at least two arylamino groups.

  In some embodiments of Formula IV, monomer unit A is an N heterocyclic group having one or more nitrogen heteroatoms and no other heteroatoms, or deuterated analogs thereof. .

  In some embodiments, the N heterocyclic group having only nitrogen heteroatoms is carbazole, benzocarbazole, azacarbazole, acridan, indole, indoloindole, indolocarbazole, imidazole, benzimidazole, pyrrolopyrrole, diazine, Derived from a compound selected from the group consisting of pyridine, pyrimidine, pyridazine, pyrazine, triazine, triazolopyridine, quinoline, isoquinoline, substituted derivatives thereof, and deuterated analogs thereof.

  In some embodiments of Formula IV, monomer unit A is an N heterocyclic group having at least one nitrogen heteroatom and at least one oxygen or sulfur heteroatom.

  In some embodiments, the N heterocyclic group is selected from the group consisting of oxazine, phenoxazine, oxazole, benzoxazole, phenothiazine, benzothiazole, benzothiadiazole, substituted derivatives thereof, and deuterated analogs thereof. Derived from the compound.

  In some embodiments of Formula IV, monomer unit A is a hydrocarbon aryl group having a fused ring or a deuterated analog thereof.

  In some embodiments, the hydrocarbon aryl group is a compound selected from the group consisting of fluorene, anthracene, benzoanthracene, triphenylene, indane, indenofluorene, substituted derivatives thereof, and deuterated analogs thereof. Derived from.

  In some embodiments of Formula IV, the monomer unit A is a group consisting of at least one arylamino group and carbazole, benzocarbazole, indolocarbazole, fluorene, substituted derivatives thereof, and deuterated analogs thereof. And a second group derived from a compound selected from.

  In some embodiments of formula IV, monomer unit A is represented by formula A-1

[Where:
Ar ¹ is the same or different at each occurrence and is an aryl or deuterated aryl group;
Ar ² is an aryl or deuterated aryl group,
b1 is 0 or 1, and
^* Represents a bond point].

All of the above embodiments for Ar ¹ , Ar ² , and b1 of Formula HT-1 apply equally to Ar ¹ , Ar ² , and b1 of Formula A-1.

  In some embodiments of Formula IV, monomer unit A is represented by Formula A-1a

[Where:
Ar ^1a and Ar ^2a are the same or different at each occurrence and are derived from a compound selected from the group consisting of fluorene, arylenecarbazole, triarylamine, substituted derivatives thereof, and their deuterated analogs; and
^* Represents a bond point].

  In some embodiments of formula IV, monomer unit A is represented by formula A-2

[Where:
Ar ¹ is the same or different at each occurrence and is an aryl or deuterated aryl group;
Ar ² is the same or different at each occurrence and is an aryl or deuterated aryl group;
Ar ³ is an aryl or deuterated aryl group, and
^* Represents a bond point].

All of the above embodiments for Ar ¹ , Ar ² , and Ar ³ of formula HT-2 apply equally to Ar ¹ , Ar ² , and Ar ³ of formula A-2.

  In some embodiments of formula IV, monomer unit A is represented by formula A-2a

[Where:
Ar ² is the same or different at each occurrence and is an aryl or deuterated aryl group;
R ^{5 to} R ⁹ are the same or different at each occurrence, and D, F, CN, alkyl, fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy, Deuterated alkyl, deuterated partially fluorinated alkyl, deuterated aryl, deuterated heteroaryl, deuterated amino, deuterated silyl, deuterated germyl, deuterated alkoxy, deuterated aryloxy, Selected from the group consisting of deuterated fluoroalkoxy, deuterated siloxane, deuterated siloxy, and bridging groups, adjacent R ⁵ or R ⁹ groups joined together to form a fused 5- or 6-membered aromatic ring Can form
a1 is the same or different for each occurrence and is an integer from 0 to 4;
f is the same or different for each occurrence and is 0 to the maximum number of available binding positions;
g is an integer of 0 to 3,
h and h1 are the same or different, 1 or 2, and
^* Represents a bond point].

  In some embodiments of Formula HT-2a, h1 = 2.

All of the above embodiments for Ar ² , R ^{5 to} R ⁹ , a1, h, and g of Formula HT-2a are similar to Ar ² , R ^{5 to} R ⁹ , a1, h, and g of Formula A-2a Is true.

  In some embodiments of Formula IV, monomer unit A has Formula A-3.

All of the above embodiments for Ar ¹ , Ar ² , and Ar ^{4 in} Formula HT-3 apply equally to Ar ¹ , Ar ² , and Ar ⁴ in Formula A-3.

  In some embodiments of formula IV, monomer unit A is represented by formula A-4

[Where:
Ar ¹ is the same or different at each occurrence and is an aryl group or a deuterated aryl group;
Ar ² is the same or different at each occurrence and is an aryl group or a deuterated aryl group;
Ar ⁵ is the same or different at each occurrence and is selected from the group consisting of phenylene, substituted phenylene, naphthylene, substituted naphthylene, and their deuterated analogs;
T ¹ and T ² are independently the same or different at each occurrence and are conjugated moieties bound in a non-planar configuration, or their deuterated analogs;
d is the same or different for each occurrence and is an integer from 1 to 6;
e is the same or different for each occurrence, is an integer from 1 to 6, and
^* Represents a bond point].

Ar ^1, Ar ^2, Ar ⁵ of Formula ^{HT-4, T 1, T} 2, d, and all of the embodiments described above for e is Ar ¹ of formula ^{A-4, Ar 2, Ar} 5, T 1, T ^{The same} applies to ² , d, and e.

  In some embodiments of formula IV, monomer unit A is represented by formula A-5 or formula A-6.

[Where:
Ar ¹ is an aryl group or a deuterated aryl group,
Ar ² is the same or different at each occurrence and is an aryl group or a deuterated aryl group;
Ar ⁶ is the same or different at each occurrence and is an aryl group or a deuterated aryl group;
Ar ⁷ is an aryl group or a deuterated aryl group,
R ¹⁰ and R ¹¹ are the same or different at each occurrence, and D, F, CN, alkyl, fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy, Deuterated alkyl, deuterated partially fluorinated alkyl, deuterated aryl, deuterated heteroaryl, deuterated amino, deuterated silyl, deuterated germyl, deuterated alkoxy, deuterated aryloxy, Adjacent groups selected from R ¹⁰ and R ¹¹ selected from the group consisting of deuterated fluoroalkoxy, deuterated siloxane, deuterated siloxy, and bridging groups join together to form a condensed ring. Can
b2 is 0 or 1,
g1 is the same or different for each occurrence, is an integer from 0 to 3, and
^* Represents a bond point].

All of the above embodiments for Ar ¹ , Ar ² , Ar ⁶ , Ar ⁷ , R ¹⁰ , R ¹¹ , b2, and g1 of Formula HT-5 and Formula HT-6 are of Formula A-5 and Formula A-6. The same applies to Ar ¹ , Ar ² , Ar ⁶ , Ar ⁷ , R ¹⁰ , R ¹¹ , b2 and g1.

  In some embodiments of formula IV, monomer unit A is represented by formula A-7.

[Where:
Ar ⁸ is selected from the group consisting of H, D, an aryl group or a deuterated aryl group, provided that when k = 0, Ar ⁸ is aryl or deuterated aryl;
R ¹⁰ and R ¹¹ are the same or different at each occurrence, and D, F, CN, alkyl, fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy, Deuterated alkyl, deuterated partially fluorinated alkyl, deuterated aryl, deuterated heteroaryl, deuterated amino, deuterated silyl, deuterated germyl, deuterated alkoxy, deuterated aryloxy, Adjacent groups selected from R ¹⁰ and R ¹¹ selected from the group consisting of deuterated fluoroalkoxy, deuterated siloxane, deuterated siloxy, and bridging groups join together to form a condensed ring. Can
a2 is the same or different for each occurrence and is an integer from 0 to 4;
g2 is an integer of 0 to 3,
k is an integer from 0 to 2, and
^* Represents a bond point].

All of the above-described embodiments for Ar ⁸ , R ¹⁰ , R ¹¹ , a2 and g2 of formula HT-7 apply equally to Ar ⁸ , R ¹⁰ , R ¹¹ , a2 and g2 of formula A-7.

  Monomer unit M1 is a branched monomer unit having at least three points of attachment in the copolymer.

  In some embodiments, monomer unit M1 is aromatic.

  In some embodiments, monomer unit M1 is aromatic with an alkyl branching group.

  In some embodiments, monomer unit M1 is aromatic with an aromatic branching group.

  In some embodiments, monomer unit M1 is a triarylamine group.

  In some embodiments, monomer unit M1 is of the formula VI

[Where:
Z is selected from the group consisting of C, Si, Ge, N, a cycloaliphatic moiety, an aromatic moiety, a deuterated cycloaliphatic moiety, or a deuterated aromatic moiety, wherein A is at least three bond positions Have
Y is a single bond, alkyl, aromatic moiety, deuterated alkyl, or deuterated aromatic moiety, provided that when Y is a single bond, alkyl, or deuterated alkyl, Z is aromatic or deuterated. Provided that it is a hydrogenated aromatic moiety,
s is an integer of the maximum number of available bond positions on 3-Z, and
^* Represents a point of attachment in the copolymer].

  In some embodiments of Formula VI, Z is an aromatic moiety derived from a compound selected from benzene, naphthalene, anthracene, phenanthrene, substituted derivatives thereof, and deuterated analogs thereof.

  In some embodiments, monomer unit M1 is represented by Formula VII, Formula VIII, Formula IX, and Formula X.

[Where:
Ar ⁹ is an aromatic or deuterated aromatic moiety having at least three bond positions;
R ⁶ is the same or different for each occurrence, D, F, CN, alkyl, fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy, deuterated Alkyl, deuterated partially fluorinated alkyl, deuterated aryl, deuterated heteroaryl, deuterated amino, deuterated silyl, deuterated germyl, deuterated alkoxy, deuterated aryloxy, deuterated Selected from the group consisting of fluoroalkoxy, deuterated siloxane, deuterated siloxy, and bridging groups, adjacent R ⁶ groups can be joined together to form a fused 5- or 6-membered aromatic ring ,
p1 is the same or different for each occurrence and is an integer from 0 to 4,
^* Represents a point of attachment in the copolymer].

  Some non-limiting examples of monomer unit M1 are shown below.

  Monomer unit M2 is an optional monomer unit that is aromatic.

  In some embodiments, monomer unit M2 has one of the formulas shown below.

In M2-1 to M2-18,
R ¹² is the same or different at each occurrence and is selected from the group consisting of D, alkyl, silyl, germyl, aryl, deuterated alkyl, deuterated silyl, deuterated germyl, and deuterated aryl;
R ¹³ is the same or different at each occurrence and is selected from the group consisting of H, D, alkyl, and deuterated alkyl;
R ¹⁴ is the same or different at each occurrence and is selected from the group consisting of alkyl, aryl, and their deuterated analogs;
R ¹⁵ is the same or different at each occurrence and is selected from the group consisting of aryl and deuterated aryl;
f is the same or different for each occurrence, 0 to the integer of the maximum number of positions available for the substituent,
t is an integer from 0 to 20, and
^* Represents a connection point.

  In some embodiments of M2-1 to M2-18, f = 0.

In some embodiments of M2-1 to M2-18, at least one f> 0 and R ¹² = D.

In some embodiments of M2-1 to M2-18, at least one f> 0 and R ¹² = 1 alkyl having 1 to 12 carbons, or a deuterated analog thereof.

  Some non-limiting examples of optional monomer unit M2 are shown below.

  Monomer unit E is a monomer having the formula III-a.

  Any of the above-described embodiments of monomer units A, M1, M2 and E can be combined with one or more other embodiments as long as they do not contradict each other.

  Some non-limiting examples of compounds having Formula I are shown below.

  In copolymer H1, z = 0 and no monomer unit M2 is present.

  In one embodiment, the ratio x: y: w = 58: 12: 30.

  In one embodiment, the ratio x: y: w = 76: 12: 12.

  Any technique that produces a C—C or C—N bond and any polymerization technique can be used to produce the copolymer having Formula IV. A variety of such techniques are known, such as Suzuki, Yamamoto, Stille, and metal-catalyzed CN coupling and metal-catalyzed and oxidative direct arylation.

  Benzene-d6 in a similar manner using deuterated precursors or, more commonly, in the presence of a Lewis acid H / D exchange catalyst such as trifluoromethanesulfonic acid, aluminum trichloride or ethylaluminum dichloride. A deuterated compound can be prepared by treating a non-deuterated compound with a deuterated solvent such as.

  The copolymer can be formed into layers using solution processing techniques. Layers and thin films can be formed by any conventional deposition technique, including vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer. Continuous deposition techniques include, but are not limited to, spin coating, gravure coating, curtain coating, dip coating, slot die coating, spray coating, and continuous nozzle coating. Discontinuous deposition techniques include, but are not limited to, ink jet printing, gravure printing, and screen printing.

  The novel copolymers having formula IV can be used as hole transport materials and as hosts for electroluminescent materials. The novel copolymers also have utility in one or more layers between the hole injection layer and the hole transport layer.

4). Electronic devices Organic electronic devices that benefit from having one or more layers containing at least one compound described herein include, but are not limited to (1) devices that convert electrical energy into radiation (eg, Light emitting diodes, light emitting diode displays, lighting devices, luminaires, or diode lasers), (2) devices that detect signals by electronic processes (eg, photodetectors, photoconductive cells, photo resistors, photo switches, phototransistors, phototubes) , Infrared detectors, biosensors), (3) devices that convert radiation into electrical energy (eg, photovoltaic devices or solar cells), (4) convert light of one wavelength into light of longer wavelengths A device (eg, a down-converting phosphor device); and (5) Devices (eg, transistors or diodes) comprising one or more electronic components comprising one or more organic semiconductor layers are included. Other uses of the composition according to the invention include coating materials for memory storage devices, antistatic thin films, biosensors, electrochromic devices, solid electrolyte capacitors, energy storage devices such as rechargeable batteries, and electromagnetic shielding applications Is included.

  One illustration of an organic electronic device structure containing a compound having Formula I or a copolymer having Formula IV is shown in FIG. The device 100 has a first electrical contact layer, an anode layer 110 and a second electrical contact layer, a cathode layer 160, and a photoactive layer 140 therebetween. Additional layers may optionally be present. A hole injection layer 120, sometimes referred to as a buffer layer, may be adjacent to the anode. A hole transport layer 130 containing a hole transport material may be adjacent to the hole injection layer. An electron transport layer 150 containing an electron transport material may be adjacent to the cathode. As an option, the device may include one or more additional hole injection layers or hole transport layers (not shown) next to the anode 110 and / or one or more additional electron injection layers next to the cathode 160. Alternatively, an electron transport layer (not shown) may be used. Layers 120-150 are individually and collectively referred to as organic active layers.

  In some embodiments, to achieve full color, the emissive layer is pixelated in sub-pixel units for each of the different colors. A diagram of a pixelated device containing a compound having Formula I or a copolymer having Formula IV is shown in FIG. Device 200 includes an anode 110, a hole injection layer 120, a hole transport layer 130, an electroluminescent layer 140, an electron transport layer 150, and a cathode 160. The electroluminescent layer is divided into sub-pixels 141, 142, 143 which are repeated throughout the layer. In some embodiments, the subpixels exhibit red, blue and green emissions. Three different sub-pixel units are illustrated in FIG. 2, but two or more sub-pixel units may be used.

  Different layers will now be discussed further with reference to FIG. However, the discussion also applies to FIG. 2 and other configurations.

  In some embodiments, the different layers have thicknesses in the following ranges: anode 110, 500-5000 Å, in some embodiments 1000-2000 Å; hole injection layer 120, 50-2000 Å, some In some embodiments, 200-1000 Å; hole transport layer 130, 50-3000 Å, in some embodiments, 200-2000 Å; photoactive layer 140, 10-2000 Å, in some embodiments, 100-1000 Å An electron transport layer 150, 50-2000 Å, in some embodiments, 100-1000 カ ソ ー ド; cathode 160, 200-10000 Å, in some embodiments, 300-5000 ；. The desired ratio of layer thickness depends on the exact nature of the material used.

  One or more of the novel compounds having Formula I or Formula II may be present in one or more of the electroactive layers of the device. In some embodiments, the novel compounds are useful as hole transport materials in layer 130. In some embodiments, the novel compounds are useful as host materials for the photoactive dopant material in photoactive layer 140. The term “dopant” refers to the electronic properties of a layer containing a host material, or the target wavelength of radiation emission, acceptance, or filtering, the electronic properties of a layer without such material, or radiation. It is intended to mean a material that changes relative to its emission, acceptance, or filtering wavelength. The term “host material” is intended to mean a material to which a dopant is added. The host material may or may not have electronic properties or the ability to emit, accept or filter radiation. In some embodiments, the host material is present at a higher concentration.

  In some embodiments, the organic electronic device comprises an anode, a cathode, and at least one organic active layer therebetween, wherein the organic active layer contains a compound of formula I.

  In some embodiments, the organic electronic device comprises an anode, a cathode, and a photoactive layer therebetween, and further comprises an additional organic active layer containing a compound of formula I. In some embodiments, the additional organic active layer is a hole transport layer.

  In some embodiments, the organic electronic device comprises an anode, a cathode, and at least one organic active layer therebetween, wherein the organic active layer contains a compound of formula I or formula II.

  In some embodiments, the organic electronic device comprises an anode, a cathode, and a photoactive layer therebetween, and further comprises an additional organic active layer containing a compound of formula I or formula II. In some embodiments, the additional organic active layer is a hole transport layer.

  The anode 110 is an electrode that is particularly efficient for injecting positive charge carriers. It can be made from materials containing, for example, metals, mixed metals, alloys, metal oxides or mixed metal oxides, or it can be conducting polymers, and mixtures thereof. Suitable metals include Group 11 metals, Group 4, Group 5, and Group 6 metals, and Group 8 to Group 10 transition metals. If the anode is light transmissive, mixed metal oxides of Group 12, 13, and 14 metals such as indium tin oxide are commonly used. In addition, the anode is “Flexible light-emitting diodes made from solid conducting polymer,” Nature vol. 357, pp 477 479 (11 June 1992), and may contain an organic material such as polyaniline. At least one of the anode and the cathode may be at least partially transparent so that the generated light can be observed.

  The optional hole injection layer 120 contains a hole injection material. The term “hole injection layer” or “hole injection material” is intended to mean an electrical conductor or semiconductor material, including but not limited to sublayer planarization, charge transport and / or charge injection properties, oxygen Or it may have one or more functions in the organic electronic device, including the capture of impurities such as metal ions and other aspects to promote or improve the performance of the organic electronic device. The hole injection material may be a polymer, oligomer, or small molecule, and may be in the form of a solution, dispersion, suspension, emulsion, colloidal mixture, or other composition.

  The hole injection layer can be formed of a polymeric material such as polyaniline (PANI) or polyethylene dioxythiophene (PEDOT), which is often doped with a protonic acid. The protonic acid can be, for example, poly (styrene sulfonic acid), poly (2-acrylamido-2-methyl-1-propanesulfonic acid), and the like. The hole injection layer 120 can contain a charge transfer compound such as copper phthalocyanine and tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ). In some embodiments, the hole injection layer 120 is made from a dispersion of a conductive polymer and a colloid-forming polymeric acid. Such materials are described, for example, in U.S. Patent Application Publication No. 2004-0102577, U.S. Patent Application Publication No. 2004-0127637, and U.S. Patent Application Publication No. 2005-0205860.

  Layer 130 contains a hole transport material. In some embodiments, the hole transport layer contains a compound having Formula I or Formula II.

  In some embodiments, the hole transport layer contains only compounds having Formula I, and there are no additional materials present that substantially alter the operating principle or the distinguishing properties of the layer.

  In some embodiments, the hole transport layer contains only the compound having Formula II, and there are no additional materials present that substantially alter the operating principle or the distinguishing properties of the layer.

  In some embodiments, layer 130 contains other hole transport materials. Examples of hole transport materials for the hole transport layer are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 18, p. 837-860, 1996, Y.M. Summarized in Wang. Both hole transporting small molecules and polymers can be used. Commonly used hole transport molecules include, but are not limited to, 4,4 ′, 4 ″ -tris (N, N-diphenyl-amino) -triphenylamine (TDATA); '' -Tris (N-3-methylphenyl-N-phenyl-amino) -triphenylamine (MTDATA); N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1 '-Biphenyl] -4,4'-diamine (TPD); 4,4'-bis (carbazol-9-yl) biphenyl (CBP); 1,3-bis (carbazol-9-yl) benzene (mCP); 1,1-bis [(di-4-tolylamino) phenyl] cyclohexane (TAPC); N, N′-bis (4-methylphenyl) -N, N′-bis (4-ethylphenyl)-[1,1 '-(3,3'-Dimethyl ) Biphenyl] -4,4′-diamine (ETPD); tetrakis- (3-methylphenyl) -N, N, N ′, N′-2,5-phenylenediamine (PDA); α-phenyl-4-N , N-diphenylaminostyrene (TPS); p- (diethylamino) benzaldehyde diphenylhydrazone (DEH); triphenylamine (TPA); bis [4- (N, N-diethylamino) -2-methylphenyl] (4-methyl Phenyl) methane (MPMP); 1-phenyl-3- [p- (diethylamino) styryl] -5- [p- (diethylamino) phenyl] pyrazolin (PPR or DEASP); 1,2-trans-bis (9H-carbazole) -9-yl) cyclobutane (DCZB); N, N, N ′, N′-tetrakis (4-methylphenyl)- (1,1′-biphenyl) -4,4′-diamine (TTB); N, N′-bis (naphthalen-1-yl) -N, N′-bis- (phenyl) benzidine (α-NPB); And porphyrin compounds such as copper phthaloocyanine. Commonly used hole transport polymers include, but are not limited to, polyvinylcarbazole, (phenylmethyl) polysilane, poly (dioxythiophene), polyaniline, and polypyrrole. In addition, hole transporting polymers can be obtained by doping hole transporting molecules such as those described above into polymers such as polystyrene and polycarbonate. In some cases, triarylamine polymers are used, especially triarylamine-fluorene copolymers. In some cases, the polymers and copolymers are crosslinkable. Examples of crosslinkable hole transport polymers can be found, for example, in US Patent Application Publication No. 2005-0184287 and PCT Application Publication No. WO 2005/052027. In some embodiments, the hole transport layer is a p-type such as tetrafluoro-tetracyanoquinodimethane and perylene-3,4,9,10-tetracarboxylic acid-3,4,9,10-dianhydride. Dopants are doped.

  Depending on the device application, the photoactive layer 140 absorbs light (such as in a down-converting phosphor device), a light-emitting layer activated by an applied voltage (such as in a light emitting diode or light emitting electrochemical cell). A layer of material that emits light with a longer wavelength, or in response to radiant energy (such as in a photodetector or photovoltaic device) and with or without an applied bias voltage It can be a layer of material to be produced.

  In some embodiments, the photoactive layer contains an organic electroluminescent (“EL”) material. Any EL material such as, but not limited to, small molecule organic fluorescent compounds, fluorescent and phosphorescent metal complexes, conjugated polymers, and mixtures thereof can be used in the device. Examples of fluorescent compounds include, but are not limited to, chrysene, pyrene, perylene, rubrene, coumarin, anthracene, thiadiazole, derivatives thereof, and mixtures thereof. Examples of metal complexes include, but are not limited to, metal chelated oxinoid compounds such as tris (8-hydroxyquinolato) aluminum (Alq3); cyclometallated iridium and platinum electroluminescent compounds such as Petrov et al. Iridium and phenylpyridine, phenylquinoline, or phenylpyrimidine ligands as disclosed in US Pat. No. 6,670,645 and PCT Application Publication No. WO 03/063555 and WO 2004/016710. And organometallic complexes described in, for example, PCT Application Publication WO 03/008424, WO 03/091688, and WO 03/040257 And mixtures thereof. In some cases, small molecule fluorescent or organometallic materials are deposited with the host material as a dopant to improve processing and / or electronic properties. Examples of conjugated polymers include, but are not limited to, poly (phenylene vinylene), polyfluorene, poly (spirobifluorene), polythiophene, poly (p-phenylene), copolymers thereof, and mixtures thereof.

  In some embodiments, photoactive layer 140 contains an electroluminescent material in a host material having Formula I. In some embodiments, a second host material is also present. In some embodiments, photoactive layer 140 contains only an electroluminescent material and a host material having Formula I. In some embodiments, the photoactive layer 140 contains only an electroluminescent material, a first host material having Formula I, and a second host material. Examples of second host materials include, but are not limited to, chrysene, phenanthrene, triphenylene, phenanthroline, naphthalene, anthracene, quinoline, isoquinoline, quinoxaline, phenylpyridine, benzodifuran, and metal quinolinate complexes.

  In some embodiments, photoactive layer 140 contains an electroluminescent material in a host material having Formula II. In some embodiments, a second host material is also present. In some embodiments, photoactive layer 140 contains only an electroluminescent material and a host material having Formula II. In some embodiments, the photoactive layer 140 contains only an electroluminescent material, a first host material having Formula II, and a second host material. Examples of second host materials include, but are not limited to, chrysene, phenanthrene, triphenylene, phenanthroline, naphthalene, anthracene, quinoline, isoquinoline, quinoxaline, phenylpyridine, benzodifuran, and metal quinolinate complexes.

Optional layer 150 can function to promote electron transport and also serve as a hole injection layer or as a confinement layer to prevent annihilation of excitons at the layer interface. Preferably, this layer promotes electron mobility and reduces exciton annihilation. Examples of electron transport materials that may be used in the optional electron transport layer 150 include metal chelated oxinoid compounds such as tris (8-hydroxyquinolato) aluminum (AlQ), bis (2-methyl-8-quinolinolato) ( metal quinolate derivatives such as p-phenylphenolato) aluminum (BAlq), tetrakis- (8-hydroxyquinolato) hafnium (HfQ) and tetrakis- (8-hydroxyquinolato) zirconium (ZrQ); and azole compounds, for example 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole (PBD), 3- (4-biphenylyl) -4-phenyl-5- (4-t -Butylphenyl) -1,2,4-triazole (TAZ), and 1,3,5-tri ( Enyl-2-benzimidazole) benzene (TPBI) and the like; quinoxaline derivatives such as 2,3-bis (4-fluorophenyl) quinoxaline and the like; 4,7-diphenyl-1,10-phenanthroline (DPA) and phenanthroline such as 2 , 9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA) and the like; triazines; fullerenes; and mixtures thereof. In some embodiments, the electron transport material is selected from the group consisting of metal quinolates and phenanthroline derivatives. In some embodiments, the electron transport layer further contains an n-dopant. N-dopant materials are known. n-dopants include, but are not limited to, Group 1 and Group 2 metals; Group 1 and Group 2 metal salts such as LiF, CsF, and Cs ₂ CO ₃ ; Group 1 and Group 2 metal organic compounds such as Li quinolate; and Molecular n-dopants such as leuco dyes, metal complexes such as W ₂ (hpp) _{4 where} hpp = 1,3,4,6,7,8-hexahydro-2H-pyrimido- [1,2-a] -Pyrimidine) and cobaltcene, tetrathianaphthacene, bis (ethylenedithio) tetrathiafulvalene, heterocyclic radicals or diradicals, and heterocyclic radicals or diradical dimers, oligomers, polymers, dispiro compounds and polycycles It is.

An optional electron injection layer may be deposited on the electron transport layer. Examples of electron injection materials include, but are not limited to, Li-containing organometallic compounds, LiF, Li ₂ O, Li quinolate, Cs-containing organometallic compounds, CsF, Cs ₂ O, and Cs ₂ CO ₃ . This layer may react with the underlying electron transport layer, the overlying cathode, or both. When an electron injection layer is present, the amount of deposited material is generally in the range of 1-100 inches, and in some embodiments, 1-10 inches.

  The cathode 160 is an electrode that is particularly efficient for injecting electrons or negative charge carriers. The cathode can be any metal or nonmetal having a lower work function than the anode. The material for the cathode can be selected from Group 1 alkali metals (eg, Li, Cs), Group 2 (alkaline earth) metals, rare earth elements and lanthanides, and Group 12 metals including actinides. Materials such as aluminum, indium, calcium, barium, samarium and magnesium, and combinations can be used.

  It is known to have other layers in organic electronic devices. For example, a layer (not shown) between the anode 110 and the hole injection layer 120 that controls the amount of positive charge injected and / or provides layer bandgap matching or functions as a protective layer. possible. Layers known in the art, such as copper phthalocyanine, silicon oxynitride, fluorocarbon, silane, or ultrathin layers of metals such as Pt can be used. Alternatively, some or all of the anode layer 110, the active layers 120, 130, 140, and 150, or the cathode layer 160 can be surface treated to increase charge carrier transport efficiency. The choice of material for each component layer is preferably determined by balancing the positive and negative charges in the emitter layer to provide a device with high electroluminescence efficiency.

  It should be understood that each functional layer can be composed of more than one layer.

  The device layer can be formed by any deposition technique, such as vapor deposition, liquid deposition, and thermal transfer, or a combination of techniques. Substrates such as glass, plastic, and metal can be used. Conventional vapor deposition techniques such as thermal evaporation, chemical vapor deposition and the like can be used. The organic layer is in a suitable solvent using conventional coating or printing techniques such as, but not limited to, spin coating, dip coating, roll-to-roll technology, ink jet printing, continuous nozzle printing, screen-printing, gravure printing, etc. It can be applied from solution or dispersion.

For liquid deposition methods, suitable solvents for a particular compound or related class of compounds can be readily determined by one skilled in the art. For some applications, it is desirable for the compound to be dissolved in a non-aqueous solvent. Such non-aqueous solvents are, for example C ₁ -C ₂₀ alcohol, which may be relatively polar, such as ethers and esters, or for example C ₁ -C ₁₂ alkanes or aromatics, such as toluene, xylene, trifluoroacetic It can be relatively non-polar, such as toluene. Other suitable liquids for use in preparing liquid compositions containing the novel compounds as solutions or dispersions as described herein include, but are not limited to, chlorinated hydrocarbons (eg, methylene chloride). , Chloroform, chlorobenzene), aromatic hydrocarbons (eg, substituted and unsubstituted toluene and xylene), trifluorotoluene, etc., polar solvents (eg, tetrahydrofuran (THP), N-methylpyrrolidone) esters (eg, ethyl acetate) alcohol ( Isopropanol), ketones (cyclopentatone) and mixtures thereof. Suitable solvents for the electroluminescent material are described, for example, in PCT Application Publication No. WO 2007/1457979.

  In some embodiments, the device is fabricated by liquid deposition of a hole injection layer, a hole transport layer, and a photoactive layer, and by vapor deposition of the anode, electron transport layer, electron injection layer, and cathode.

  It should be understood that the efficiency of devices fabricated using the novel compositions described herein can be further improved by optimizing other layers in the device. For example, more efficient cathodes such as Ca, Ba or LiF can be used. Moreover, a modeling base material and the novel hole transport material which brings about the fall of an operating voltage or increases a quantum efficiency are applicable. In addition, additional layers can be added to adjust the energy levels of the various layers to promote electroluminescence.

  In some embodiments, the device in turn has the following structure: anode, hole injection layer, hole transport layer, photoactive layer, electron transport layer, electron injection layer, cathode.

  Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting. All publications, patent applications, patents and other references mentioned herein are incorporated by reference in their entirety.

  The concepts described herein are further illustrated in the following examples, which do not limit the scope of the invention described in the claims.

Synthesis example 1
Not all of the operations described above in the general description or examples are required, and some of the specific operations may not be required, and one or more additional operations may be included in the operations described. Note that this may be done in addition. Furthermore, the order in which work is listed is not necessarily the order in which work is performed.

  In the foregoing specification, the concepts have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the present invention as set forth in the claims below. Accordingly, this description is intended to be illustrative rather than limiting and all such modifications are intended to be included within the scope of the present invention.

  Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, benefits, other advantages and solutions to problems, and any elements that may yield or make more emphasis on benefits, any advantages or problems, are important to any or all claims. Or is required or not interpreted as an essential feature.

  It is to be understood that for clarity, certain features are described herein in the context of separate embodiments and may be provided in combination in a single embodiment. Conversely, various features that are described in the context of a single embodiment for the sake of brevity may also be provided separately or in any subcombination. The use of various ranges of numerical values specified herein are described as approximations as if both the minimum and maximum values within the stated range were preceded by the word “about”. In this way, it is possible to achieve substantially the same results as the values within the range, using slight differences above and below the described range. Also, the disclosure of these ranges is a continuous including all values between the minimum average value and the maximum average value that can occur when some of the components of one value are mixed with some of the components of different values. Is intended to be Further, when broader and narrower ranges are disclosed, it is within the expectation of the present invention and vice versa to match a minimum value from one range to a maximum value from another range.

Claims (4)

Formula I

Wherein Q ¹ and Q ² are the same or different and are H, D, alkyl, deuterated alkyl, aryl, deuterated aryl, and formula II

Selected from the group consisting of: provided that at least one of Q ¹ and Q ² is a group having formula II;
Where
HT is the same or different for each occurrence, is a hole transport group,
L ¹ is the same or different at each occurrence and is selected from the group consisting of alkyl, aryl, their substituted derivatives, their deuterated analogs, and combinations thereof;
R ¹ and R ² are the same or different and are H or D;
The group consisting of D, CN, halogen, alkyl, alkoxy, silyl, germyl, deuterated alkyl, deuterated alkoxy, deuterated silyl, and deuterated germyl, wherein R ³ is the same or different for each occurrence Selected from
a is an integer of 0 to 4,
b is the same or different for each occurrence and is 0 or 1;
^* Indicates a point of attachment]. Formula III

[Where:
L ¹ is the same or different at each occurrence and is selected from the group consisting of alkyl, aryl, their substituted derivatives, their deuterated analogs, and combinations thereof;
R ¹ and R ² are the same or different and are H or D;
The group consisting of D, CN, halogen, alkyl, alkoxy, silyl, germyl, deuterated alkyl, deuterated alkoxy, deuterated silyl, and deuterated germyl, wherein R ³ is the same or different for each occurrence Selected from
R ⁴ is selected from the group consisting of H, D, and L ¹ ;
a is an integer from 0 to 4, and
A polymer having at least one monomer unit having ^* denotes a point of attachment. Formula IV

[Where:
A is a monomer unit containing at least one hole transport group;
M1 is a monomer unit having at least three points of attachment in the copolymer;
M2 is an aromatic monomer unit having two points of attachment or a deuterated analog thereof,
E is of formula III-a

A monomer unit having the formula:
L ¹ is selected from the group consisting of alkyl, aryl, substituted derivatives thereof, deuterated analogs thereof, and combinations thereof;
R ¹ and R ² are the same or different and are H or D;
The group consisting of D, CN, halogen, alkyl, alkoxy, silyl, germyl, deuterated alkyl, deuterated alkoxy, deuterated silyl, and deuterated germyl, wherein R ³ is the same or different for each occurrence Selected from
R ^4a is H or D;
a is an integer of 0 to 4,
x, y, z and w are the same or different, are mole fractions, at least x and w are not 0, and
^* Indicates a point of attachment.   An organic electronic device comprising an anode, a cathode, and at least one organic active layer therebetween, wherein the organic active layer comprises a compound according to any one of claims 1-3. device.

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