KR20180066115A - 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. An organic electronic device comprising an anode, a cathode, and at least one organic active layer therebetween, wherein an organic active layer comprises a hole transporting material is also disclosed.

Description

Crosslinkable hole transport material

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

In organic electronic devices such as OLEDs that make up an organic light emitting diode (" OLED ") display, 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-transmitting electrical contact layer when a voltage is applied across the electrical contact layer.

It is well 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.

The device using the electroluminescent material mainly comprises at least one charge transport layer, and the charge transport layer is located between the photoactive layer (for example, the light emitting layer) and the contact layer (hole injection contact layer). One device may include two or more contact layers. The hole transport layer may be located between the photoactive layer and the hole injection contact layer. The hole injection contact layer may be referred to as an anode. The electron transporting layer may be located between the photoactive layer and the electron injection contact layer. The electron injection contact layer may be referred to as a cathode.

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

Compounds having formula (I) are provided.

(I)

Wherein Q ¹ and Q ² are the same or different and are selected from the group consisting of H, D, alkyl, deuterated alkyl, aryl, deuterated aryl, and groups having formula (II)

≪ RTI ID = 0.0 &

With the proviso that at least one of Q ¹ and Q ² is a group having the formula II;

here,

HT is in each case the same or different and is a hole transport;

L ¹ is the same or different in each case and 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;

R ³ is in each case the same or different and is selected from the group consisting of D, CN, halogen, alkyl, alkoxy, silyl, germyl, deuterated alkyl, deuterated alkoxy, deuterated silyl, and deuterated germyl;

a is an integer of 0 to 4;

b are each the same or different and are 0 or 1;

* Indicates the attachment point.

Polymers having at least one monomer unit of formula (III) are also provided.

(III)

here,

L ¹ is the same or different in each case and 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;

R ³ is in each case the same or different and is selected from the group consisting of D, CN, halogen, alkyl, alkoxy, silyl, germyl, deuterated alkyl, deuterated alkoxy, deuterated silyl, and deuterated germyl;

R ⁴ is selected from the group consisting of H, D, and L ¹ ;

a is an integer of 0 to 4;

* Indicates the attachment point.

Copolymers having formula IV are also provided.

(IV)

here,

A is a monomeric unit containing at least one hole-transporting group;

M1 is a monomer unit having at least three points of attachment in the copolymer;

M2 is an aromatic monomer unit having two attachment points or a deuterated analogue thereof;

E is a monomer unit having the formula III-a;

[Formula III-a]

here,

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;

R ³ is in each case the same or different and is selected from the group consisting of D, CN, halogen, alkyl, alkoxy, silyl, germyl, deuterated alkyl, deuterated alkoxy, deuterated silyl, and deuterated germyl;

R ^4a is H or D;

a is an integer of 0 to 4;

x, y, z, and w are the same or different and have a molar fraction, and at least x and w are not 0;

* Indicates the attachment point.

Also provided is 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).

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.

Implementations are illustrated in the accompanying drawings to facilitate understanding of the concepts presented herein.
Figure 1 includes an illustration of an example of an organic electronic device.
Figure 2 includes an illustration of another example of an organic electronic device.
Those skilled in the art will appreciate that the objects are shown in the drawings in a concise and clear manner and are not necessarily drawn to scale. For example, the dimensions of some objects in the figures may be exaggerated relative to other objects to aid understanding of the embodiments.

Compounds having formula (I) as described in detail herein are provided.

Polymers having at least one monomer unit having formula (III), as described in detail herein, are provided.

Copolymers having formula (IV) as 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 implementations have been described above and are merely illustrative and not restrictive. After reading this specification, those skilled in the art will appreciate that other aspects and embodiments are possible without departing from the scope of the present invention.

Other features and advantages of any one or more embodiments will be apparent from the following detailed description and claims. The detailed description first deals with definitions and descriptions of terms, followed by compounds, copolymers, electronic devices, and finally embodiments.

1. Definitions and Explanations of Terms

Before describing the embodiments described below in detail, some terms are defined or explained.

As used herein, the term " alkyl " includes both branched and straight-chain saturated aliphatic hydrocarbon groups. Unless otherwise indicated, the term is also intended to include cyclic groups. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, 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 have 1, 2, and 3 substituents. 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 from 1 to 20 carbon atoms. In other embodiments, the alkyl group has from 1 to 6 carbon atoms. The term is intended to include heteroalkyl groups. The 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 pi electrons. The term is intended to include both aromatic compounds having only carbon and hydrogen atoms and heteroaromatic compounds in which at least one of the carbon atoms in the cyclic group is replaced by another atom such as nitrogen, oxygen, sulfur, and the like.

The term " aryl " or " aryl group " means a moiety derived from an aromatic compound. Group " derived from a compound refers to a radical formed by the removal of one or more H or D. [ The aryl group may be a single ring (monocyclic ring), or a multiple ring which is condensed or covalently linked to each other (heterocyclic). Examples of the aryl moiety are phenyl, 1-naphthyl, 2-naphthyl, dihydronaphthyl, tetrahydronaphthyl, biphenyl, anthryl, phenanthryl, fluorenyl, indanyl, biphenylenyl, Thienyl, acenaphthylenyl, and the like. In some embodiments, the aryl group has 6 to 60 ring carbon atoms; And in some embodiments have from 6 to 30 ring carbon atoms. The term is intended to include heteroaryl groups. The heteroaryl group may have from 3 to 50 ring carbon atoms; In some embodiments, it may have 4 to 30 ring carbon atoms.

The term " alkoxy " is intended to mean an -OR group wherein R is alkyl.

The term " aryloxy " refers to the group -OR where R is aryl.

Unless otherwise indicated, all groups may be substituted or unsubstituted. An optionally substituted group, such as, but not limited to, alkyl or aryl, may be substituted with one or more substituents which may be the same or different. Suitable substituents D, alkyl, aryl, nitro, ^{cyano, -N (R 7) (R} 8), halo, hydroxy, carboxy, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, heteroaryl, (O) ₂ -N (R ') (R "), -C (= O) -NR ₂ R ₃ , (R ") (R") (R ") (R") (R " -S (O) _s -aryl wherein s = 0-2 or -S (O) _s -heteroaryl wherein s = 0-2. Each R 'and R " , Optionally substituted alkyl, cycloalkyl, or aryl group. R 'and R ", together with the nitrogen atom to which they are attached, may form a ring system in certain embodiments. The substituent may be a bridging group.

The term " charge transport " when referring to a layer, material, member or structure is intended to mean that such layer, material, member or structure has such a layer, material, Thereby facilitating the movement of the charge. The hole transport material promotes the positive charge, and the electron transport material promotes the negative charge. Although the luminescent material may have some charge transporting properties, the term " charge transporting layer, charge transporting material, charge transporting member, or charge transporting structure " is intended to include layers, materials, no.

The term " compound " is intended to mean an uncharged material consisting of a molecule further comprising an atom that can not be separated from the molecule by physical means without breaking the chemical bond. The term is intended to include oligomers and polymers.

The term " crosslinkable group " or " crosslinking group " is intended to mean a group on a compound or polymer chain that can be linked to another compound or polymer chain via heat treatment, initiator use, or exposure to radiation wherein the linkage is a covalent bond. In some embodiments, the radiation is ultraviolet or visible. Examples of the crosslinkable group include vinyl, acrylate, perfluorovinyl ether, 1-benzo-3,4-cyclobutane, o-quinodimethane group, siloxane, cyanate group, cyclic ether (epoxide) , And acetylene groups.

The term " electroactive " when referring to a layer or material is intended to refer to a layer or material that facilitates the operation of the device electronically. Examples of electroactive materials include, but are not limited to, a substance that conducts, injects, transports, or blocks charges that may be electrons or holes, or that exhibits a change in concentration of electron-hole pairs or emits radiation upon receiving radiation It is not. Examples of inactive materials include, but are not limited to, planarizing materials, insulating materials, and environmental barrier materials.

The prefix " fluoro " is intended to indicate that at least one hydrogen in one group has been replaced by fluorine.

The prefix "Hetero" indicates that one or more carbon atoms have been replaced with other atoms. In some embodiments, the heteroatom is O, N, S or a combination thereof.

The term " liquid composition " is intended to mean 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 a liquid medium in which the material is suspended to form a suspension or emulsion.

The term " photoactive " means that it emits light when activated by an applied voltage (such as in a light emitting diode or a chemical cell), emits light after absorbing the photons (as in a downconverting phosphorescent device) ) Refers to a material or layer that generates a signal in the presence or absence of an applied bias voltage in response to radiant energy.

The term " silyl " refers to the R ₃ Si- group wherein R is H, D, C1-20 alkyl, fluoroalkyl, or aryl. In some embodiments, at least one carbon at the R alkyl group is substituted with Si. In some embodiments, the silyl groups are (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 (RO) ₃ Si- groups wherein R is H, D, C1-20 alkyl, or fluoroalkyl.

When the phrase " adjacent to " is used to refer to a layer in a device, it does not necessarily mean that one layer is next to another layer. On the other hand, the phrase " adjacent R group " is used to refer to the adjacent R group in the formula (i.e., the R group on the atom bound by the bond).

In this specification, unless explicitly stated otherwise or contrary to the context of the usage, the embodiment of the subject matter encompasses, includes, nests, contains, possesses, consists of, or consists of, or consists of, One or more features or elements other than those explicitly mentioned or described may be present in embodiments. Alternate embodiments of the disclosed subject matter are described as consisting essentially of a particular feature or element, which feature or element does not substantially change the working principle or distinct feature of the embodiment. Still other alternative embodiments of the subject matter described are described as consisting of certain features or elements, and only those features or elements that are specifically mentioned or described are present in such an embodiment or its non-substantial variation.

Also, unless explicitly stated to the contrary, "or" refers to a comprehensive logical conjunction, not an exclusive logical conjunction. For example, condition A or B satisfies either: A is true (or exists), B is false (or nonexistent), A is false (or nonexistent) , And both A and B are true (or present).

In addition, singular nouns are used to describe the elements and components described herein. This is merely to provide a general sense of convenience and scope of the invention. This description should be read to include one or at least one, and the singular also includes the plural unless it is expressly meant to be singular.

Group (group) number corresponding to the periodic table column (column) within the elements may be found in [CRC Handbook of Chemistry and Physics, 81 st Edition (2000-2001)] " new notation (New Notation)" as shown in use rules do.

Unless otherwise defined, 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 incorporated by reference in their entirety, unless the specific phrase is cited. In case of conflict, the present specification, including definitions, will prevail. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

Much of the details of specific materials, processing operations, and circuitry, to the extent not described herein, are conventional and can be found in textbooks and other materials in the art of organic light emitting diode displays, photodetectors, photovoltaics, and semiconductor devices.

2. Compound

The compounds described herein have the general formula (I).

(I)

Wherein Q ¹ and Q ² are the same or different and are selected from the group consisting of H, D, alkyl, deuterated alkyl, aryl, deuterated aryl, and groups having formula (II)

≪ RTI ID = 0.0 &

With the proviso that at least one of Q ¹ and Q ² is a group having the formula II;

here,

HT is in each case the same or different and is a hole transport;

L ¹ is the same or different in each case and 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;

R ³ is in each case the same or different and is selected from the group consisting of D, CN, halogen, alkyl, alkoxy, silyl, germyl, deuterated alkyl, deuterated alkoxy, deuterated silyl, and deuterated germyl;

a is an integer of 0 to 4;

b are each the same or different and are 0 or 1;

* Indicates the attachment 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 by deuterium (" D "). The term " deuterated analogue " refers to a structural analog of a compound or group in which one or more available hydrogens are replaced by deuterium. Deuterated compounds or deuterated analogs are present at least 100 times the level at which deuterium is present in nature. In some embodiments, the compound is at least 10% deuterated. "% Deuterated" or "% deuterated" means that the ratio of neutrons to the sum of protons and neutrons is expressed as a percentage. In some embodiments, the compound is at least 10% deuterated; In some embodiments at least 20% deuterated; In some embodiments at least 30% deuterated; At least 40% deuterated in some embodiments; At least 50% deuterated in some embodiments; In some embodiments at least 60% deuterated; In some embodiments at least 70% deuterated; In some embodiments at least 80% deuterated; In some embodiments at least 90% deuterated; 100% deuterated in some embodiments.

The deuterated material may be less sensitive to decomposition by holes, electrons, excitons, or a combination thereof. Deuteration can potentially inhibit decomposition of the compound during operation of the device, which in turn can lead to improved device life. In general, this improvement is achieved without sacrificing other device characteristics. In addition, deuterated compounds often have greater air resistance than non-hydrogenated analogs. This may lead to greater process tolerances both for the manufacture and purification of the material and in the formation of electronic devices using the material.

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 is a 1-12 carbon alkyl or deuterated alkyl group having gt; In some embodiments, an alkyl or deuterated alkyl group having from 1 to 8 carbons; And in some embodiments an alkyl or deuterated alkyl group having 3 to 8 carbons.

In some embodiments of formula I, Q ¹ is a hydrocarbon aryl or deuterated analogs having 6 to 60 ring carbon; In some embodiments, is a hydrocarbon aryl or deuterated analogue having 6 to 30 ring carbons; In some embodiments, is a hydrocarbon aryl or deuterated analogue having from 10 to 20 ring carbons.

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

In some embodiments of formula I, Q ¹ is selected from the group consisting of naphthyl, anthracenyl, 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 condensation ring.

In some embodiments of formula I, Q < ¹ > has the formula a.

(A)

here,

R ²⁰ is the same or different in each occurrence and is selected from the group consisting of D, alkyl, alkoxy, siloxane, silyl, germyl, and deuterated analogues thereof;

p is the same or different in each occurrence and is an integer from 0 to 4;

q is an integer from 0 to 5;

r is an integer from 1 to 5;

* Indicates the attachment point.

In some embodiments of formula I, Q < ¹ > has the formula b.

[Formula b]

Here, 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 from 3 to 60 ring carbons or a deuterated analog thereof. In some embodiments, the heteroaryl has from 3 to 30 ring carbons; And in some embodiments has 5 to 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 selected from the group consisting of pyrrole, pyridine, pyrimidine, carbazole, imidazole, benzimidazole, imidazolobenzimidazole, triazole, benzotriazole, triazolopyridine, indolocarbazole, A group derived from a compound selected from the group consisting of phenanthroline, quinoline, isoquinoline, quinoxaline, indole, indole indole, substituted derivatives thereof, and deuterated analogues thereof.

In some embodiments of formula I, Q < ¹ > is a group having formula (II) as 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 from 1 to 12 carbon alkyl or deuterated alkyl group having gt; In some embodiments, an alkyl or deuterated alkyl group having from 1 to 8 carbons; And in some embodiments an alkyl or deuterated alkyl group having 3 to 8 carbons.

In some of the formula II embodiments, and b = ^1, L 1 is a hydrocarbon aryl or deuterated analogs having 6 to 60 ring carbon; In some embodiments, is a hydrocarbon aryl or deuterated analogue having 6 to 30 ring carbons; In some embodiments, is a hydrocarbon aryl or deuterated analogue having from 10 to 20 ring carbons.

And In some embodiments of formula II, b = ^1, L 1 is a hydrocarbon aryl group, or a deuterated analog having at least one condensed ring.

In some embodiments of formula II, b = 1 and L ¹ is selected from the group consisting of naphthyl, anthracenyl, naphthylphenyl, phenylnaphthyl, fluorenyl, substituted derivatives thereof, and deuterated analogs thereof. do.

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

In some embodiments of formula II, b = 1 and L &^lt; 1 > has the formula c.

(C)

Here, R ²⁰ , p, r and * are the same as in formula (a).

In some embodiments of formula II, b = 1 and L &^lt; 1 > has the formula d.

[Chemical formula d]

Here, R ²⁰ , p, r and * are the same as in formula (a).

In some embodiments of formula II, b = 1 and L ¹ is selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, substituted derivatives thereof, and deuterated analogs thereof. do. 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 &^lt; 1 ^> is heteroaryl having 3 to 60 ring carbons or a deuterated analog thereof. In some embodiments, the heteroaryl has from 3 to 30 ring carbons; And in some embodiments has 5 to 20 ring carbons.

In some embodiments of formula II, b = 1 and L &^lt; 1 ^> is N-heteroaryl or a deuterated analog thereof.

In some embodiments of formula II, HT comprises a moiety selected from the group consisting of arylamino, N-heterocyclic, aromatic condensed hydrocarbons, substituted derivatives thereof, combinations thereof, and deuterated analogs thereof.

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 comprising 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 a deuterated analog thereof.

In some embodiments, the N-heterocyclic group having only the nitrogen heteroatom (s) is selected from carbazole, benzocarbazole, azacavazole, acridan, indole, indoloindol, indolocarbazole, imidazole, benzimidazole Derived from a compound selected from the group consisting of pyrrolopyrrole, diazine, pyridine, pyrimidine, pyridazine, pyrazine, triazine, triazolopyridine, quinoline, isoquinoline, substituted derivatives thereof and deuterated analogues thereof do.

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 ≪ / RTI >

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

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

In some embodiments of formula II, HT is selected from compounds selected from the group consisting of at least one arylamino group and a carbazole, benzocarbazole, indolocarbazole, fluorene, substituted derivatives thereof, and deuterated analogs thereof. Derived second group.

In some embodiments, HT has the formula HT-1.

[Formula HT-1]

here,

Ar ¹ is aryl or a deuterated aryl group;

Ar ² is the same or different in each case and is an aryl or deuterated aryl group;

b1 is 0 or 1;

* Indicates the attachment point.

In formula (I), when HT has the formula HT-1 and b1 = 0, b = 1.

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, anthracenyl, substituted analogues 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 selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, carbazolyl, combinations of these covalently linked groups, substituted derivatives thereof, and deuterated analogs thereof ≪ / RTI >

In some embodiments, HT has the formula HT-1a.

[Formula HT-1a]

here,

Ar ^1a and Ar ^2a are the same or different in each case and are derived from a compound selected from the group consisting of fluorene, arylene carbazole, triarylamine, substituted derivatives thereof, and deuterated analogs thereof;

* Indicates the attachment point.

In some embodiments, HT has the formula HT-2.

[Formula HT-2]

here,

Ar ¹ is aryl or a deuterated aryl group;

Ar ² is the same or different in each case and is an aryl or deuterated aryl group;

Ar ³ is selected from the group consisting of aryl, (CR ' ₂ ) _r , adamantyl, dicyclichexyl, a bicyclic group having an aliphatic ring connected through a single atom, substituted derivatives thereof, and deuterated analogs thereof;

R 'is the same or different in each occurrence and is H, D, alkyl, fluoroalkyl, aryl, deuterated alkyl, deuterated fluoroalkyl, and deuterated aryl;

* Indicates the attachment 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, anthracenyl, substituted derivatives thereof, and deuterated analogs thereof.

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

In some embodiments, HT has the formula HT-2a.

[Formula HT-2a]

here,

Ar ² is the same or different in each case and is an aryl or deuterated aryl group;

R ⁵ to R ⁹ are independently in each occurrence the same or different and are selected from the group consisting of D, F, CN, alkyl, fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, alkoxy, aryloxy, fluoroalkoxy, Silane, siloxane, deuterated alkyl, deuterated partially fluorinated alkyl, deuterated aryl, deuterated heteroaryl, deuterated amino, deuterated silyl, deuterated germyl, deuterated alkoxy, deuterated aryloxy, deuterated fluoro Wherein the adjacent R ⁵ or R ⁹ groups may be bonded to each other to form a condensed 5- or 6-membered aromatic ring;

a1 is the same or different in each case and is an integer of 0 to 4;

b3 is 0 or 1;

f is the same or different in each case, is not less than 0 and not more than the maximum number of available bonding sites;

g is an integer from 0 to 3;

h is 1 or 2;

* Indicates the attachment 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 of Ar < ² > is an aryl group having no condensation ring.

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; A derivative thereof having at least one substituent selected from the group consisting of alkyl, alkoxy, and silyl; And deuterated analogs thereof.

In some embodiments of formula HT-2a, R ⁵ to 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 al are 0.

In some embodiments of formula HT-2a, at least one al is greater than zero.

In some embodiments of formula HT-2a, all f is zero.

In some embodiments of formula HT-2a, at least one f is greater than zero.

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 has the formula HT-3.

[Formula HT-3]

here,

Ar ¹ is aryl or a deuterated aryl group;

Ar ² is the same or different in each case and is an aryl or deuterated aryl group;

Ar ⁴ is aryl or a deuterated aryl group;

* Indicates the attachment point.

All embodiments described above for Ar ¹ and Ar ² in the general formula HT-1 is equivalent for Ar ¹ and Ar ² in the general formula HT-3.

In some embodiments of formula HT-3, Ar ⁴ is a condensed hydrocarbon aryl group having 10 to 36 ring carbons, a substituted derivative thereof, or a deuterated analog thereof.

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

In some embodiments, HT has the formula HT-4.

[Formula HT-4]

here,

Ar ¹ is the same or different in each case, and is an aryl group or a deuterated aryl group;

Ar ² is the same or different in each case and is an aryl group or a deuterated aryl group;

Ar ⁵ is the same or different in each case and is selected from the group consisting of phenylene, substituted phenylene, naphthylene, substituted naphthylene, and deuterated analogs thereof;

T ¹ and T ² are independently in each case the same or different and are a conjugated moiety connected in non-planar form, or a deuterated analog thereof;

d is the same or different in each occurrence and is an integer from 1 to 6;

e is an integer from 1 to 6;

* Indicates the attachment point.

In some embodiments of formula HT-4, at least one Ar ⁵ is phenyl substituted with 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.

In the formula HT-4, any aromatic ring 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, a C _1-12 alkyl group, a C _1-12 alkoxy group, a silyl group, a germyl group, and a deuterated analogue 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-mentioned embodiments for Ar ¹ and Ar ² in formula HT- ¹ apply equally to Ar ¹ and Ar ² in 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 the formula HT-4, T ¹ and T ² are conjugate moieties. In some embodiments, T ¹ and T ² are aromatic moieties 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, anthracenyl, and deuterated analogues thereof.

In some embodiments of the 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 compound backbone. The term " biphenyl " is intended to mean a group having two phenyl units linked by a single bond. The biphenylene group may be attached to one of the 2, 3-, 4-, or 5-positions and to one of the 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 a substituent at least in 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 compound backbone. The term " binaphthyl " is intended to mean a group having two naphthalene units linked by a single bond. In some embodiments, the binaphthylene group is attached to one of the 3-, 4-, 5-, 6-, or 7-positions and to one of the 3'-, 4'-, 5'-, 6'or 7'- 1,1'-binaphthylene adhered to the compound skeleton.

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 a 1,1-binaphthylene group attached to the backbone of the group at the 4 and 4'-positions (4,4 '- (1,1- Binaphthylene)).

In some embodiments, HT has the formula HT-5 or the formula HT-6.

[Formula HT-5]

[Formula HT-6]

here,

Ar ¹ is an aryl group or a deuterated aryl group;

Ar ² is the same or different in each case and is an aryl group or a deuterated aryl group;

Ar ⁶ in each case is the same or different 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 in each occurrence and are selected from the group consisting of D, F, CN, alkyl, fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, alkoxy, aryloxy, fluoroalkoxy, Siloxane, deuterated alkyl, deuterated partially fluorinated alkyl, deuterated aryl, deuterated heteroaryl, deuterated amino, deuterated silyl, deuterated germyl, deuterated alkoxy, deuterated aryloxy, deuterated fluoroalkoxy , Deuterated siloxane, deuterated siloxy, and a bridging group, and adjacent groups selected from R ¹⁰ and R ¹¹ may combine with each other to form a condensed ring;

b2 is 0 or 1;

g1 is the same or different in each occurrence and is an integer from 0 to 3;

* Indicates the attachment point.

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

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

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

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

All of the above-mentioned embodiments for R ⁴ to R ⁹ in formula HT-2a apply equally to R ¹⁰ and R ¹¹ in 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 is 1.

In some embodiments of formula HT-5, at least one g2 is greater than zero.

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 is 1.

In some embodiments of formula HT-6, at least one g2 is greater than zero.

In some embodiments, HT has the formula HT-7.

[Formula HT-7]

here,

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 in each occurrence and are selected from the group consisting of D, F, CN, alkyl, fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, alkoxy, aryloxy, fluoroalkoxy, Siloxane, deuterated alkyl, deuterated partially fluorinated alkyl, deuterated aryl, deuterated heteroaryl, deuterated amino, deuterated silyl, deuterated germyl, deuterated alkoxy, deuterated aryloxy, deuterated fluoroalkoxy , Deuterated siloxane, deuterated siloxy, and a bridging group, and adjacent groups selected from R ¹⁰ and R ¹¹ may combine with each other to form a condensed ring;

a2 is an integer of 0 to 4;

g2 is the same or different in each occurrence and is an integer from 0 to 3;

k is an integer of 0 to 2;

* Indicates the attachment point.

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

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

All of the above-mentioned embodiments for R ⁴ to R ⁹ in formula HT-2a apply equally to R ¹⁰ and R ¹¹ in 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 is 1.

In some embodiments of the formula HT-7, at least one g2 is greater than zero.

All of the implementations 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 at least one R < ¹ >

In some embodiments of formula I, a> 0, at least one R ¹ is an alkyl or a deuterated alkyl group having 1 to 12 carbons; In some embodiments, an alkyl or deuterated alkyl group having from 1 to 8 carbons; And in some embodiments an alkyl or deuterated alkyl group having 3 to 8 carbons.

In some embodiments of formula I, a> 0, at least one R ¹ is an alkoxy or deuterated alkoxy group having 1 to 12 carbons; In some embodiments is an alkoxy or deuterated alkoxy group having 1 to 8 carbons; And in some embodiments is an alkoxy or deuterated alkoxy group having 3 to 8 carbons.

In some embodiments of formula I, a> 0 and at least one R ¹ is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, trimethylsilyl, triethylsilyl, .

Unless mutually exclusive, any of the above embodiments of Formula I may be combined with one or more other embodiments. For example, an embodiment wherein L < ¹ > is alkyl having 3 to 8 carbons can be combined with an embodiment in which HT has the formula HT-1. This applies equally to other implementations not mutually exclusive discussed above. Those of ordinary skill in the art will readily understand which embodiments are mutually exclusive and therefore can readily determine the combinations of embodiments contemplated in the present application.

Some non-limiting examples of compounds having Formula I are as follows.

The compounds of formula I may be prepared using any technique that produces C-C or C-N bonds. Various such techniques are known, such as Suzuki, Yamamoto, Stille, and metal-catalyzed C-N coupling as well as metal-catalyzed direct oxidation of the metal.

The deuterated compounds can be prepared in a similar manner using deuterated precursor materials or, more generally, the deuterated compounds can be reacted with Lewis acids H / D such as trifluoromethanesulfonic acid, aluminum trichloride or aluminum dichloride With a deuterated solvent such as benzene-d6 in the presence of an exchange catalyst.

Exemplary fabrication is provided in the examples.

The compounds may be formed into layers using solution treatment techniques. The term " layer " is used interchangeably with the term " film " and refers to a coating that covers a desired area. The term is not limited by size. The area may be as large as the entire device, as small as a particular functional area, such as an actual visual display, or as small as a single sub-pixel. The layers and films may 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. Non-continuous deposition techniques include, but are not limited to, inkjet printing, gravure printing, and screen printing.

The novel compounds having the formula (I) can be used as a hole transport material and can be used as a host for an electroluminescent material. The novel compounds also have utility as a material for the priming layer which improves the deposition of the hole transport layer.

3. Polymers and copolymers

Polymers having at least one monomer unit having the formula (III) are also provided.

(III)

here,

L ¹ is the same or different in each case and 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;

R ³ is in each case the same or different and is selected from the group consisting of D, CN, halogen, alkyl, alkoxy, silyl, germyl, deuterated alkyl, deuterated alkoxy, deuterated silyl, and deuterated germyl;

R ⁴ is selected from the group consisting of H, D, and L ¹ ;

a is an integer of 0 to 4;

* Indicates the attachment point.

In some embodiments of formula III, R < ⁴ >

In some embodiments of formula III, R < ⁴ >

In some embodiments of formula III, R < ⁴ > is L < ^{1 &} gt ;.

All embodiments described above for ^{R 1, R 2, R 3} , L 1, and a in formula (I) apply equally to ^{R 1, R 2, R 3} , L 1, and a in Formula III.

Copolymers having formula IV are also provided.

(IV)

here,

A is a monomeric unit containing at least one hole-transporting group;

M1 is a monomer unit having at least three points of attachment in the copolymer;

M2 is an aromatic monomer unit having two attachment points or a deuterated analogue thereof;

E is a monomer unit having the formula III-a;

[Formula III-a]

here,

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;

R ³ is in each case the same or different and is selected from the group consisting of D, CN, halogen, alkyl, alkoxy, silyl, germyl, deuterated alkyl, deuterated alkoxy, deuterated silyl, and deuterated germyl;

R ^4a is H or D;

a is an integer of 0 to 4;

x, y, z, and w are the same or different and have a molar fraction, and at least x and w are not 0;

* Indicates the attachment point.

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, "A", "E", and optional "M 1" and "M 2" units are aligned with similar monomeric blocks.

In some embodiments of formula I, "A", "E", and optional "M1" and "M2" units are randomly arranged.

In some embodiments, the distribution of the monomer segments can be adjusted to optimize the properties of the compounds having Formula I for use in electronic devices. In some embodiments, different distributions may result in differences in non-associativity fillings that ultimately determine the associated film 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; In some embodiments at least 30% deuterated; At least 40% deuterated in some embodiments; At least 50% deuterated in some embodiments; In some embodiments at least 60% deuterated; In some embodiments at least 70% deuterated; In some embodiments at least 80% deuterated; In some embodiments at least 90% deuterated; 100% deuterated in some embodiments.

Deuteration may be present in one or more of the monomer units A, E, M 1 and M 2. Deuteration can be present in the copolymer backbone, in the pendant group, or in both.

In some embodiments of formula IV, the copolymer has a M _n of greater than 10,000. In some embodiments, the copolymer has a M _n of greater than 20,000; In some embodiments have M _n >50,000; In some embodiments have M _n >100,000; In some embodiments it has a M _n of greater than 150,000.

In some embodiments of formula IV, x ranges from 0.3 to 0.9; In some embodiments in the range of 0.4 to 0.8; And in some embodiments in the range of 0.5 to 0.80.

In some embodiments of formula IV, y ranges from 0 to 0.30; In some embodiments in the range of 0.05 to 0.20; And in some embodiments in the range of 0.10 to 0.15.

In some embodiments of formula IV, z ranges from 0 to 0.30; In some embodiments in the range of 0.05 to 0.20; And in some embodiments in the range of 0.10 to 0.15.

In some embodiments of formula IV, w ranges from 0.05 to 0.30; In some embodiments in the range of 0.10 to 0.20; And in some embodiments in the range of 0.10 to 0.15.

In some embodiments of formula IV, monomeric unit A comprises a moiety selected from the group consisting of arylamino, N-heterocyclic, aromatic condensed hydrocarbons, substituted derivatives thereof, combinations thereof, and deuterated analogs thereof .

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

In some embodiments of formula IV, monomeric unit A is an N-heterocyclic group having one or more nitrogen heteroatoms and no other heteroatoms, or a deuterated analog thereof.

In some embodiments, the N-heterocyclic group having only the nitrogen heteroatom (s) is selected from carbazole, benzocarbazole, azacavazole, acridan, indole, indoloindol, indolocarbazole, imidazole, benzimidazole Derived from a compound selected from the group consisting of pyrrolopyrrole, diazine, pyridine, pyrimidine, pyridazine, pyrazine, triazine, triazolopyridine, quinoline, isoquinoline, substituted derivatives thereof and deuterated analogues thereof do.

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 ≪ / RTI >

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

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

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

In some embodiments of formula IV, monomer unit A has the formula A-1.

[A-1]

here,

Ar ¹ is the same or different in each case and is an aryl or deuterated aryl group;

Ar ² is aryl or a deuterated aryl group;

b1 is 0 or 1;

* Indicates the attachment point.

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

In some embodiments of formula IV, monomer unit A has the formula A-1a.

[Formula A-1a]

here,

Ar ^1a and Ar ^2a are the same or different in each case and are derived from a compound selected from the group consisting of fluorene, arylene carbazole, triarylamine, substituted derivatives thereof, and deuterated analogs thereof;

* Indicates the attachment point.

In some embodiments of formula IV, monomer unit A has the formula A-2.

[A-2]

here,

Ar ¹ is the same or different in each case and is an aryl or deuterated aryl group;

Ar ² is the same or different in each case and is an aryl or deuterated aryl group;

Ar ³ is aryl or a deuterated aryl group;

* Indicates the attachment point.

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

In some embodiments of formula IV, monomer unit A has the formula A-2a.

[Formula A-2a]

here,

Ar ² is the same or different in each case and is an aryl or deuterated aryl group;

R ⁵ to R ⁹ are independently in each occurrence the same or different and are selected from the group consisting of D, F, CN, alkyl, fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, alkoxy, aryloxy, fluoroalkoxy, Silane, siloxane, deuterated alkyl, deuterated partially fluorinated alkyl, deuterated aryl, deuterated heteroaryl, deuterated amino, deuterated silyl, deuterated germyl, deuterated alkoxy, deuterated aryloxy, deuterated fluoro Wherein the adjacent R ⁵ or R ⁹ groups may be bonded to each other to form a condensed 5- or 6-membered aromatic ring;

a1 is the same or different in each case and is an integer of 0 to 4;

f is the same or different in each case, is not less than 0 and not more than the maximum number of available bonding sites;

g is an integer from 0 to 3;

h and h1 are the same or different and are 1 or 2;

* Indicates the attachment point.

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

All of the above-mentioned embodiments for Ar ² , R ⁵ to R ⁹ , a1, h, and g in the formula HT-2a are Ar ² , R ⁵ to R ⁹ , a1, h, and g .

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

[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 has the formula A-4.

[A-4]

here,

Ar ¹ is the same or different in each case, and is an aryl group or a deuterated aryl group;

Ar ² is the same or different in each case and is an aryl group or a deuterated aryl group;

Ar ⁵ is the same or different in each case and is selected from the group consisting of phenylene, substituted phenylene, naphthylene, substituted naphthylene, and deuterated analogs thereof;

T ¹ and T ² are independently in each case the same or different and are a conjugated moiety connected in non-planar form, or a deuterated analog thereof;

d is the same or different in each occurrence and is an integer from 1 to 6;

e is the same or different in each case, is an integer of 1 to 6,

* Indicates the attachment point.

Formula ^{HT-4 Ar 1, Ar 2} , in the ^{Ar 5, T 1, T 2} , d, and e all the embodiments described above for the ^{Ar 1, Ar 2, Ar 5} , T 1 in the formula A-4 , T ² , d, and e.

In some embodiments of formula IV, monomer unit A has formula A-5 or formula A-6.

[A-5]

[A-6]

here,

Ar ¹ is an aryl group or a deuterated aryl group;

Ar ² is the same or different in each case and is an aryl group or a deuterated aryl group;

Ar ⁶ in each case is the same or different 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 in each occurrence and are selected from the group consisting of D, F, CN, alkyl, fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, alkoxy, aryloxy, fluoroalkoxy, Siloxane, deuterated alkyl, deuterated partially fluorinated alkyl, deuterated aryl, deuterated heteroaryl, deuterated amino, deuterated silyl, deuterated germyl, deuterated alkoxy, deuterated aryloxy, deuterated fluoroalkoxy , Deuterated siloxane, deuterated siloxy, and a bridging group, and adjacent groups selected from R ¹⁰ and R ¹¹ may combine with each other to form a condensed ring;

b2 is 0 or 1;

g1 is the same or different in each occurrence and is an integer from 0 to 3;

* Indicates the attachment point.

All of the above-mentioned embodiments for Ar ¹ , Ar ² , Ar ⁶ , Ar ⁷ , R ¹⁰ , R ¹¹ , b2 and g1 in the formula HT-5 and the formula HT- The same applies to Ar ¹ , Ar ² , Ar ⁶ , Ar ⁷ , R ¹⁰ , R ¹¹ , b 2, and g 1 in FIG.

In some embodiments of formula IV, monomer unit A has the formula A-7.

[A-7]

here,

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 in each occurrence and are selected from the group consisting of D, F, CN, alkyl, fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, alkoxy, aryloxy, fluoroalkoxy, Siloxane, deuterated alkyl, deuterated partially fluorinated alkyl, deuterated aryl, deuterated heteroaryl, deuterated amino, deuterated silyl, deuterated germyl, deuterated alkoxy, deuterated aryloxy, deuterated fluoroalkoxy , Deuterated siloxane, deuterated siloxy, and a bridging group, and adjacent groups selected from R ¹⁰ and R ¹¹ may combine with each other to form a condensed ring;

a2 is the same or different in each occurrence and is an integer of 0 to 4;

g2 is an integer of 0 to 3;

k is an integer of 0 to 2;

* Indicates the attachment point.

All embodiments described above for ^{Ar 8, R 10, R 11} , a2, and g2 of the formula HT-7 is the same for ^{Ar 8, R 10, R 11} , a2, and g2 of the formula A-7 do.

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

In some embodiments, monomeric unit M1 is aromatic.

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

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

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

In some embodiments, monomer unit M1 has formula VI.

(VI)

here,

Z is selected from the group consisting of C, Si, Ge, N, a cyclic aliphatic moiety, an aromatic moiety, a deuterated cyclic aliphatic moiety, or a deuterated aromatic moiety, A has at least three bond positions;

Y is a single bond, an alkyl, an aromatic moiety, a deuterated alkyl, or a deuterated aromatic moiety, provided that when Y is a single bond, alkyl, or deuterated alkyl, Z is an aromatic or deuterated aromatic moiety;

s is an integer equal to or greater than 3 and equal to or less than the maximum number of available binding sites in Z;

* Indicates the 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, the monomer unit M1 has one of the formulas (VII), (VIII), (IX), and (X).

(VII)

(VIII)

(IX)

(X)

here,

Ar ⁹ is an aromatic moiety or a deuterated aromatic moiety having at least three bonding positions,

R ⁶ is independently the same or different in each case and, D, F, CN, alkyl, fluoroalkyl, aryl, heteroaryl, amino, silyl, germanate wheat, alkoxy, aryloxy, fluoroalkyl-alkoxy siloxane, siloxane Deuterated alkyl, deuterated partially fluorinated alkyl, deuterated aryl, deuterated heteroaryl, deuterated amino, deuterated silyl, deuterated germyl, deuterated alkoxy, deuterated aryloxy, deuterated fluoroalkoxy, Deuterated siloxane, deuterated siloxy, and a bridging group, adjacent R ⁶ groups may combine with each other to form a condensed 5- or 6-membered aromatic ring;

p1 is the same or different in each occurrence and is an integer from 0 to 4;

* Indicates the point of attachment in the copolymer.

Some non-limiting examples of monomer unit M1 are as follows.

The monomer unit M2 is an optional monomer unit which is aromatic.

In some embodiments, monomeric unit M2 has one of the following formulas:

In M2-1 to M2-18:

R ¹² is the same or different in 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 in each occurrence and is selected from the group consisting of H, D, alkyl, and deuterated alkyl;

R < ¹⁴ > are the same or different in each occurrence and are selected from the group consisting of alkyl, aryl, and deuterated analogues thereof;

R < ¹⁵ > is the same or different in each occurrence and is selected from the group consisting of aryl and deuterated aryl;

f is the same or different in each case and is an integer equal to or greater than 0 and equal to or less than the maximum number of available positions for the substituent;

t is an integer from 0 to 20;

* Indicates the attachment point.

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

In the M2-1 to M2-18 some embodiments, at least one f is greater than zero and the R ¹² = D.

M2-1 to M2-18 at a part of the implementation, the at least one f is greater than 0, R ¹² is alkyl, or a deuterated analog having one to 12 carbon atoms.

Some non-limiting examples of the optional monomer unit M2 are as follows.

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

Unless mutually exclusive, any of the above embodiments for monomer units A, M1, M2, and E may be combined with one or more other embodiments.

Some non-limiting examples of compounds having Formula I are as follows.

In copolymer H1, z = 0 and monomer unit M2 is absent.

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

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

Any of the techniques for producing C-C or C-N bonds and known polymerization techniques can be used to prepare copolymers having formula IV. Various such techniques are known, such as Suzuki, Yamamoto, steel, and metal-catalyzed C-N coupling as well as metal-catalyzed direct oxidation of the catalyst.

The deuterated compounds can be prepared in a similar manner using deuterated precursor materials or, more generally, the deuterated compounds can be reacted with Lewis acids H / D such as trifluoromethanesulfonic acid, aluminum trichloride or aluminum dichloride With a deuterated solvent such as benzene-d6 in the presence of an exchange catalyst.

The copolymer may be formed into a layer using solution processing techniques. The layers and films may 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. Non-continuous deposition techniques include, but are not limited to, inkjet printing, gravure printing, and screen printing.

The novel copolymer having the formula (IV) can be used as a hole transport material and as a host for an electroluminescent material. The novel copolymers also have utility within one or more layers between the hole injection layer and the hole transport layer.

4. Electronic devices

Organic electronic devices that may have the advantage of having at least one layer comprising at least one compound as described herein include (1) devices that convert electrical energy to radiation (e.g., light emitting diodes, light emitting diode displays, Devices, light fixtures, diode lasers); (2) a device (e.g., a photodetector, a photoconductive battery, a photoresistor, an optical switch, a phototransistor, an optical tube, an IR detector, a biosensor) for detecting a signal through an electronic process; (3) a device (e.g., a photovoltaic device or a solar cell) that converts radiation to electrical energy; (4) a device (e.g., a downconverting phosphorescent device) that converts light of one wavelength into light of a longer wavelength; And (5) an apparatus (e.g., transistor or diode) comprising one or more electronic components comprising one or more organic semiconductor layers. Other uses for compositions according to the present invention include coating materials for memory storage devices, antistatic membranes, biosensors, electrochromic devices, solid electrolyte capacitors, energy storage devices such as rechargeable batteries, and electromagnetic shielding applications.

An example of an organic electronic device structure comprising a compound having Formula I or a copolymer having Formula IV is shown in FIG. The device 100 has a first electrical contact layer that is an anode layer 110, a second electrical contact layer that is a cathode layer 160, and a photoactive layer 140 therebetween. Additional layers may optionally be present. Adjacent to the anode, there may be a hole injection layer 120, sometimes referred to as a buffer layer. Adjacent to the hole injecting layer, there may be a hole transporting layer 130 including a hole transporting material. Adjacent to the cathode, there may be an electron transporting layer 150 comprising an electron transporting material. Alternatively, the apparatus may be provided with at least one additional hole injection layer or hole transport layer (not shown) beside the anode 110, and / or at least one additional electron injection layer or electron transport layer (not shown) next to the cathode 160 . Layers 120-150 are individually and collectively referred to as an organic active layer.

In some implementations, to achieve full color, the emissive layer is pixelated in subpixel units for each different color. An example of a pixelating device comprising a compound having the formula (I) or a copolymer having the formula (IV) is shown in FIG. The 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 subpixels 141, 142 and 143 which are repeated across the layer. In some embodiments, the sub-pixels exhibit red, blue, and green emission. Although two different subpixel units are shown in FIG. 2, two or more subpixel units may be used.

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

In some embodiments, the different layers have the following thickness ranges: anode 110, 500-5000 A, in some embodiments 1000-2000 A; Hole injection layer 120, 50 to 2000 ANGSTROM, in some embodiments 200 to 1000 ANGSTROM; Hole transport layer 130, 50 to 3000 ANGSTROM, in some embodiments 200 to 2000 ANGSTROM; Photoactive layer 140, 10 to 2000 Angstroms, in some embodiments 100 to 1000 Angstroms; Electron transport layer 150, 50 to 2000 ANGSTROM, in some embodiments 100 to 1000 ANGSTROM; The cathode 160, 200 to 10000 angstroms, and in some embodiments 300 to 5000 angstroms. The desired ratio of layer thickness will depend on the exact nature of the material used.

At least one of the novel compounds having Formula I or Formula II described herein may be present in one or more of the electroactive layers of the device. In some embodiments, the novel compound is useful as a hole transport material in layer 130. In some embodiments, the novel compound is useful as a host material for the photoactive dopant material of the photoactive layer 140. The term " dopant " refers to the electronic characteristic (s) of the layer, or the target wavelength (s) of radiation emission, reception or filtering, in the layer comprising the host material, ), Or the wavelength (s) of radiation emission, light reception or filtering. 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 property (s), or the ability to emit, receive, 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 comprises a compound of formula (I).

In some embodiments, the organic electronic device further comprises an anode, a cathode, and a photoactive layer therebetween, and further comprises an additional organic active layer comprising 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 comprises a compound of formula (II).

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

The anode 110 is a particularly efficient electrode for injecting positive charge carriers. This may, for example, consist of a material containing metals, mixed metals, alloys, metal oxides, or mixed metal oxides, or may be conductive polymers and mixtures thereof. Suitable metals include Group 11 metals, Groups 4, 5, and 6 metals, and Group 8-10 transition metals. When the anode is translucent, mixed metal oxides of Group 12, Group 13 and Group 14 metals such as indium-tin-oxide are generally used. The anode is described in " Flexible light-emitting diodes made from soluble conducting polymer ", Nature vol. 357, pp 477 479 (June 11, 1992)). At least one of the anode and the cathode must be at least partially transparent so that the generated light can be observed.

The optional hole injection layer 120 includes a hole injection material. The term " hole injecting layer " or " hole injecting material " is intended to mean an electrically conductive or semiconductive material and may include one or more functions in the organic electronic device, such as lower layer planarization, charge transport and / , Removal of impurities such as oxygen or metal ions), and may have other aspects for facilitating or enhancing the performance of organic electronic devices. The hole injecting material may be a polymer, a low polymer, or a small molecule and may be in the form of a solution, dispersion, suspension, emulsion, colloid mixture, or other composition.

The hole injection layer may 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 may be, for example, poly (styrenesulfonic acid), poly (2-acrylamido-2-methyl-1-propanesulfonic acid) or the like. The hole injection layer 120 may include a charge transport compound such as copper phthalocyanine and tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ). In some embodiments, the hole injection layer 120 is made of a dispersion of a conductive polymer and a colloid-forming polymeric acid. Such materials are described, for example, in U.S. Published Patent Applications 2004-0102577, 2004-0127637, and 2005-0205860.

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

In some embodiments, the hole transport layer comprises only the compound having Formula I, and no additional material that substantially changes the operating principle or characteristic properties of the layer is present in the hole transport layer.

In some embodiments, the hole transport layer comprises only a compound having formula (II), and no additional material that substantially changes the operating principle or characteristic properties of the layer is present in the hole transport layer.

In some embodiments, layer 130 comprises another hole transport material. 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. Wang et al. Both small molecules and polymers that transport holes can be used. Commonly used hole transporting molecules include, but are not limited to, 4,4 ', 4 "-tris (N, N-diphenyl-amino) -triphenylamine (TDATA) , 4 " -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); alpha-phenyl-4-N, N-diphenylaminostyrene (TPS); p- (diethylamino) benzaldehyde diphenylhydrazone (DEH); Triphenylamine (TPA); Bis [4- (N, N-diethylamino) -2-methylphenyl] (4-methylphenyl) methane (MPMP); 1-phenyl-3- [p- (diethylamino) styryl] -5- [p- (diethylamino) phenyl] pyrazoline (PPR or DEASP); 1,2-trans-bis (9H-carbazol-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 (? -NPB); And porphyrin compounds such as copper phthalocyanine. Commonly used hole transporting polymers include, but are not limited to, polyvinylcarbazole, (phenylmethyl) polysilane, poly (dioxythiophene), polyaniline, and polypyrrole. It is also possible to obtain a hole transporting polymer by doping a hole transporting molecule as mentioned above to a polymer such as polystyrene and polycarbonate. In some cases, triarylamine polymers, particularly triarylamine-fluorene copolymers, are used. In some cases, the polymer and the copolymer are crosslinkable. Examples of crosslinkable hole transport polymers can be found, for example, in US Published Patent Application 2005-0184287 and in published PCT Application WO 2005/052027. In some embodiments, the hole transport layer is formed by p-dopants such as tetrafluorotetracyanoquinodimethane and perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride Doped.

Depending on the use of the device, the photoactive layer 140 may be a light emitting layer that is activated by an applied voltage (such as in a light emitting diode or a light emitting electrochemical cell), a light absorbing layer that absorbs light (such as in a downconverting phosphorescent device) A layer of light emitting material, or a layer of material that generates a signal in the presence or absence of an applied bias voltage in response to radiant energy (such as in a photodetector or photovoltaic device).

In some embodiments, the photoactive layer comprises an organic electroluminescent (" EL ") material. Any EL material that can be used in the device includes, but is not limited to, small molecule organic fluorescent compounds, fluorescent and phosphorescent metal complexes, conjugated polymers, and mixtures thereof. 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 metal chelate oxinoid compounds such as tris (8-hydroxyquinolato) aluminum (Alq3); Cyclometallated iridium and platinum electroluminescent compounds such as the complexes of iridium with phenylpyridine, phenylquinoline, or phenylpyrimidine ligands disclosed in Petrov et al., U.S. Patent 6,670,645 and published PCT applications WO 03/063555 and WO 2004/016710, And organometallic complexes as described, for example, in published PCT applications WO 03/008424, WO 03/091688, and WO 03/040257, and mixtures thereof. In some cases, the small molecule fluorescent or organometallic material is deposited as a dopant with the host material to enhance processing and / or electronic properties. Examples of conjugated polymers include poly (phenylene vinylene), polyfluorene, poly (spirobifluorene), polythiophene, poly (p-phenylene), copolymers thereof, and mixtures thereof , But is not limited thereto.

In some embodiments, the photoactive layer 140 comprises an electroluminescent material in a host material having Formula I. In some embodiments, a second host material is also present. In some embodiments, the photoactive layer 140 comprises only an electroluminescent material and a host material having the formula (I). In some embodiments, photoactive layer 140 comprises only an electroluminescent material, a first host material having Formula I, and a second host material. Examples of the second host material include chromene, phenanthrene, triphenylene, phenanthroline, naphthalene, anthracene, quinoline, isoquinoline, quinoxaline, phenylpyridine, benzodifuran, and metal quinolinate complexes, But is not limited thereto.

In some embodiments, photoactive layer 140 comprises 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 comprises only an electroluminescent material and a host material having Formula II. In some embodiments, photoactive layer 140 comprises only an electroluminescent material, a first host material having Formula II, and a second host material. Examples of the second host material include chromene, phenanthrene, triphenylene, phenanthroline, naphthalene, anthracene, quinoline, isoquinoline, quinoxaline, phenylpyridine, benzodifuran, and metal quinolinate complexes, But is not limited thereto.

The selective layer 150 may function not only to facilitate transport of electrons but also to function as a hole injection layer or a confinement layer to prevent excitation of the excitons at the layer interface. Preferably, this layer promotes electron mobility and reduces exciton emission. Examples of electron transport materials that can be used in the selective electron transport layer 150 include tris (8-hydroxyquinolato) aluminum (AlQ), bis (2-methyl-8-quinolinolato) ) Metal quinolate derivatives such as aluminum (BAlq), tetrakis- (8-hydroxyquinolato) hafnium (HfQ), and tetrakis- (8-hydroxyquinolato) zirconium Chelate oxinoid compounds; 3- (4-biphenyl) -4-phenyl-5- (4-phenylphenyl) -1,3,4-oxadiazole (PBD) (4-t-butylphenyl) -1,2,4-triazole (TAZ), and 1,3,5-tri (phenyl-2-benzimidazole) benzene (TPBI); Quinoxaline derivatives such as 2,3-bis (4-fluorophenyl) quinoxaline; Phenanthrolines such as 4,7-diphenyl-1,10-phenanthroline (DPA) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); Triazine; Fullerene; And mixtures thereof. In some embodiments, the electron transporting material is selected from the group consisting of metal quinolate and phenanthroline derivatives. In some embodiments, the electron transporting layer further comprises an n-dopant. N-dopant materials are well known. The n-dopant is a Group 1 and Group 2 metal; Group 1 and Group 2 metal salt, such as LiF, CsF, and Cs ₂ CO _3; Group 1 and Group 2 metal organic compounds such as Li quinolate; And a molecular n-dopant such as a leuco dye, a metal complex such as W ₂ (hpp) ₄ (hpp = 1,3,4,6,7,8-hexahydro-2H-pyrimido- [ Polymer, a disilo compound, a polymer, a disulfone compound, a heterocyclic compound, or a heterocyclic compound or a di-radical, ≪ / RTI > and polycycles.

A selective electron injecting layer may be deposited on the electron transporting layer. Examples of electron injecting 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 can react with the electron transport layer at the bottom, the cathode at the top, or both. When an electron injection layer is present, the amount of material deposited is typically in the range of 1 to 100 A, and in some embodiments in the range of 1 to 10 A.

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

Organic electronic devices are known to have other layers. For example, between the anode 110 and the hole injection layer 120, there may be a layer (not shown) for controlling the injection amount of positive charge and / or providing bandgap matching of the layer, or for functioning as a protective layer have. A layer known in the art such as an ultra-thin layer of metal such as copper phthalocyanine, silicon oxynitride, fluorocarbon, silane, or 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 may be surface treated to increase charge carrier transport efficiency. The choice of material for each constituent layer is preferably determined by balancing positive and negative charges in the emitter layer to provide a device with high electroluminescent efficiency.

It is understood that each functional layer can consist of more than one layer.

The device layer may be formed by any deposition technique or combination of techniques, including vapor deposition, liquid deposition and thermal transfer. Substrates such as glass, plastic, and metal may be used. Conventional vapor deposition techniques such as thermal evaporation and chemical vapor deposition can be used. The organic layer can be formed into a solution or dispersion in a suitable solvent using conventional coating or printing techniques including, but not limited to, spin coating, dip coating, roll-to-roll technology, inkjet printing, continuous nozzle printing, screen printing, and gravure printing, / RTI >

In the case of liquid deposition processes, suitable solvents for certain compounds or related classes of compounds can be readily determined by those skilled in the art. For some applications, the compound is preferably dissolved in a non-aqueous solvent. Such non-aqueous solvents may be relatively polar, such as C ₁ to C ₂₀ alcohols, ethers, and acid esters, or may be relatively polar, such as C ₁ to C ₂₀ alkanes, or aromatics such as toluene, xylene, and trifluorotoluene It can be non-polar. Other liquids suitable for use in preparing liquid compositions as solutions or dispersions, such as those described herein, including the novel compounds include aromatic hydrocarbons, such as chlorinated hydrocarbons (e.g., methylene chloride, chloroform, chlorobenzene) (Isopropanol), ketones (such as cyclopentane, cyclohexanone, and the like), hydrocarbons such as substituted and unsubstituted toluene and xylene, polar solvents such as tetrahydrofuran (THP), N-methylpyrrolidone) ), And mixtures thereof. Suitable solvents for electroluminescent materials are described, for example, in published PCT application WO 2007/145979.

In some embodiments, devices are fabricated by vapor deposition of a hole injection layer, a hole transport layer, and a photoactive layer and by vapor deposition of an anode, an electron transport layer, an electron injection layer, and a cathode.

It is understood that the efficiency of a device made with the novel compositions described herein can be further improved by optimizing other layers in the device. For example, a more efficient cathode such as Ca, Ba or LiF may be used. Molded substrates and novel hole transport materials that reduce operating voltage or increase quantum efficiency are also applicable. Additional layers may be added to match the energy levels of the various layers and facilitate electroluminescence.

In some embodiments, the device has the following structure in order: an anode, a hole injection layer, a hole transport layer, a photoactive layer, an electron transport layer, an electron injection layer, a 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.

Example

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

Synthesis Example 1

It should be noted that not all of the actions described above in the general description or the examples are required, that some of the specific actions may not be required, and that one or more additional actions other than those described may be performed. Also, the order in which actions are listed is not necessarily the order in which they are performed.

In the foregoing specification, the concepts have been described with reference to specific embodiments. However, it will be understood by those skilled in the art that various changes and modifications may be made therein without departing from the scope of the invention as set forth in the following claims. Accordingly, the specification and drawings are to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of the invention.

Benefits, other advantages, and solutions to problems have been described above with regard to specific implementations. It should be understood, however, that it is not intended to exclude any feature (s) capable of generating, or making clear, any benefit, advantage, solution to a problem, and any benefit, advantage, Features, or essential features thereof.

It should be appreciated that for clarity, certain features described herein in the context of separate implementations may be provided in combination in a single embodiment. Conversely, for brevity, the various features described in the context of a single embodiment may be provided separately or in any subcombination. Use of the various ranges of numerical values recited herein is approximated as if the word "about" preceded both the minimum and maximum values within the stated range. In this way, slight deviations above and below the stated range can be used to achieve substantially the same result as values in the range. The disclosure of these ranges is also intended to be a continuous range including all values between the minimum and maximum mean values, including fractional values that may appear when some of the components of one value are mixed with components of the other. Also, when broader and narrower ranges are disclosed, it is within the spirit of the present invention to match a minimum value of one range to a maximum value of another range and vice versa.

Claims (4)

Compounds of formula I:
(I)

Wherein Q ¹ and Q ² are the same or different and are selected from the group consisting of H, D, alkyl, deuterated alkyl, aryl, deuterated aryl, and groups having formula (II)
≪ RTI ID = 0.0 &

With the proviso that at least one of Q ¹ and Q ² is a group having the formula II;
here,
HT is in each case the same or different and is a hole transport;
L ¹ is the same or different in each case and 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;
R ³ is in each case the same or different and is selected from the group consisting of D, CN, halogen, alkyl, alkoxy, silyl, germyl, deuterated alkyl, deuterated alkoxy, deuterated silyl, and deuterated germyl;
a is an integer of 0 to 4;
b are each the same or different and are 0 or 1;
* Indicates the attachment point. Polymers having at least one monomer unit having the formula (III)
(III)

here,
L ¹ is the same or different in each case and 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;
R ³ is in each case the same or different and is selected from the group consisting of D, CN, halogen, alkyl, alkoxy, silyl, germyl, deuterated alkyl, deuterated alkoxy, deuterated silyl, and deuterated germyl;
R ⁴ is selected from the group consisting of H, D, and L ¹ ;
a is an integer of 0 to 4;
* Indicates the attachment point. Copolymers having the general formula IV:
(IV)

here,
A is a monomeric unit containing at least one hole-transporting group;
M1 is a monomer unit having at least three points of attachment in the copolymer;
M2 is an aromatic monomer unit having two attachment points or a deuterated analogue thereof;
E is a monomer unit having the formula III-a;
[Formula III-a]

here,
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;
R ³ is in each case the same or different and is selected from the group consisting of D, CN, halogen, alkyl, alkoxy, silyl, germyl, deuterated alkyl, deuterated alkoxy, deuterated silyl, and deuterated germyl;
R ^4a is H or D;
a is an integer of 0 to 4;
x, y, z, and w are the same or different and have a molar fraction, and at least x and w are not 0;
* Indicates the attachment point. 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 to 3.

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