KR101573952B1 - Emissive polymeric materials for optoelectronic devices - Google Patents

Abstract

[화학식 II]

상기 식에서,
R¹, R³, R⁴ 및 R⁶은 독립적으로 수소, 알킬, 알콕시, 옥사알킬, 알킬아릴, 아릴, 아릴알킬, 헤테로아릴, 치환된 알킬, 치환된 알콕시, 치환된 옥사알킬, 치환된 알킬아릴, 치환된 아릴, 치환된 아릴알킬 또는 치환된 헤테로아릴이고;
R^1a는 수소 또는 알킬이고;
R²는 알킬렌, 치환된 알킬렌, 옥사알킬렌, CO 또는 CO₂이고;
R^2a는 알킬렌이고;
R⁵는 각각의 경우 독립적으로, 수소, 알킬, 알킬아릴, 아릴, 아릴알킬, 알콕시, 카복시, 치환된 알킬, 치환된 알킬아릴, 치환된 아릴, 치환된 아릴알킬 또는 치환된 알콕시이고;
X는, 2, 5- 또는 2, 7-위치에 존재하는, 할로, 트라이플레이트, -B(OR^1a)₂, 또는

이고;
L은, 페닐피리딘, 톨릴피리딘, 벤조티엔일피리딘, 페닐아이소퀴놀린, 다이벤조퀴노잘린, 플루오렌일피리딘, 케토피롤, 2-(1-나프틸)벤즈옥사졸)), 2-페닐벤즈옥사졸, 2-페닐벤조티아졸, 쿠마린, 티엔일피리딘, 페닐피리딘, 벤조티엔일피리딘, 3-메톡시-2-페닐피리딘, 티엔일피리딘, 페닐이민, 비닐피리딘, 피리딜나프탈렌, 피리딜피롤, 피리딜이미다졸, 페닐인돌, 이들의 유도체 또는 이들의 조합으로부터 유도된다.Polymers comprising at least one structural unit derived from a compound of formula (I) or comprising at least one pendant group of formula (II) may be used in the photoelectric device:
(I)

≪ RTI ID = 0.0 &

In this formula,
R ¹ , R ³ , R ⁴ and R ⁶ are independently selected from the group consisting of hydrogen, alkyl, alkoxy, oxalkyl, alkylaryl, aryl, arylalkyl, heteroaryl, substituted alkyl, substituted alkoxy, Aryl, substituted aryl, substituted arylalkyl or substituted heteroaryl;
R ^1a is hydrogen or alkyl;
R ² is alkylene, substituted alkylene, oxaalkylene, CO or CO ₂ ;
R ^2a is alkylene;
R ⁵ is independently at each occurrence hydrogen, alkyl, alkylaryl, aryl, arylalkyl, alkoxy, carboxy, substituted alkyl, substituted alkylaryl, substituted aryl, substituted arylalkyl or substituted alkoxy;
X is halo, triflate, -B (OR &^lt; ^{1a >} ) ₂ , or

ego;
L is at least one selected from the group consisting of phenylpyridine, tolylpyridine, benzothienylpyridine, phenylisoquinoline, dibenzoquinolines, fluorenylpyridine, ketopyrrol, 2- (1-naphthyl) benzoxazole) And examples thereof include oxazole, 2-phenylbenzothiazole, coumarin, thienylpyridine, phenylpyridine, benzothienylpyridine, 3-methoxy-2-phenylpyridine, thienylpyridine, phenylimine, vinylpyridine, pyridylnaphthalene, pyridyl Pyrrole, pyridyl imidazole, phenyl indole, derivatives thereof, or combinations thereof.

Description

TECHNICAL FIELD [0001] The present invention relates to an electroluminescent polymeric material,

The present invention relates to a polymer having a pendant iridium complex for use in a photoelectric device.

Statement of federally sponsored research and development

The present invention was made with federal assistance under contract number DOE NETL DE-FC26-05NT42343 recognized by the US Department of Energy. The federal government may have certain rights to the invention.

Organic light emitting devices (OLEDs) using thin film materials that emit light when a voltage bias is applied are expected to become a more popular form of flat panel display technology. Possible uses thereof include mobile phones, personal digital assistants (PDAs), computer displays, information displays of vehicles, television monitors as well as general illumination light sources. Because of its bright color, wide viewing angle, compatibility with full motion video, wide temperature range, thin and comfortable form factor, low power requirement and low cost manufacturing process possibility, ) And liquid crystal displays (LCDs). Due to its high luminous efficacy, OLEDs are considered to be capable of replacing incandescent lamps, and possibly even fluorescent lamps, for certain types of applications.

Light emission from an OLED typically occurs through electroluminescence, i.e., light emission from a singlet excited state formed by applying a voltage bias across the electroluminescent material in the ground state. An OLED capable of generating light by electroluminescence, that is, light emission from a triplet excited state formed by applying a voltage bias across the ground state electroluminescent material, which is another mechanism, mainly produces light by electroluminescence Lt; RTI ID = 0.0 > OLED. ≪ / RTI > Since the triplet excited state in most luminescent organic materials tends to be non-radiatively attenuated to the ground state, the emission from the OLED by electroluminescence is limited. Thus, electrophosphorescent materials are expected as key components of OLED devices and other optoelectronic devices that exhibit greater efficiency compared to the state of the art. For example, an OLED capable of producing light by electroluminescence may exhibit a reduction in the amount of energy lost in non-radiative decay processes in the device (compared to OLEDs that produce light primarily by electroluminescence) , It is expected to provide an additional means of controlling the temperature during operation of the OLED.

Improved luminous efficiency has been achieved by incorporating phosphorescent platinum-containing dyes into organic electroluminescent devices such as OLEDs (Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices ", Nature, 154, 1998), phosphorescent iridium-containing dyes have also been used (US Patent Application Publication No. 2003/0096138). Polymeric phosphorescent iridium complexes based on ketopyrrolid ligands are disclosed in co-pending U.S. Patent Application No. 11/504552, filed August 14, 2006, U.S. Provisional Patent Application No. 60/833935, filed July 28, 2006 , Which is incorporated herein by reference in its entirety. Despite previous developments, it is currently of considerable interest to find novel phosphorescent materials that not only increase the efficiency while achieving an improved lifetime of the device, but also provide a better means of controlling the color of the light produced by the OLED .

It has been found that a change in luminescent properties of an iridium (III) dye resulting from a conjugate effect in the solid state can be prevented by separating the iridium dye from the main chain of the polymer as a pendant side chain substituent. Thus, in one aspect, the invention relates to a polymer comprising at least one compound of formula (I), and structural units derived therefrom:

(I)

In this formula,

R ¹ , R ³ , R ⁴ and R ⁶ are independently selected from the group consisting of hydrogen, alkyl, alkoxy, oxalkyl, alkylaryl, aryl, arylalkyl, heteroaryl, substituted alkyl, substituted alkoxy, Aryl, substituted aryl, substituted arylalkyl or substituted heteroaryl;

R ^1a is hydrogen or alkyl;

R ² is alkylene, substituted alkylene, oxaalkylene, CO or CO ₂ ;

R ^2a is alkylene;

R ⁵ is independently at each occurrence hydrogen, alkyl, alkylaryl, aryl, arylalkyl, alkoxy, carboxy, substituted alkyl, substituted alkylaryl, substituted aryl, substituted arylalkyl or substituted alkoxy;

이고;X is halo, triflate, -B (OR &^lt; ^{1a >} ) ₂ , or

ego;

L is at least one selected from the group consisting of phenylpyridine, tolylpyridine, benzothienylpyridine, phenylisoquinoline, dibenzoquinolines, fluorenylpyridine, ketopyrrol, 2- (1-naphthyl) benzoxazole) And examples thereof include oxazole, 2-phenylbenzothiazole, coumarin, thienylpyridine, phenylpyridine, benzothienylpyridine, 3-methoxy-2-phenylpyridine, thienylpyridine, phenylimine, vinylpyridine, pyridylnaphthalene, pyridyl Pyrrole, pyridyl imidazole, phenyl indole, derivatives thereof, or combinations thereof.

In another aspect, the invention is directed to a polymer comprising at least one pendant group of formula < RTI ID = 0.0 >

≪ RTI ID = 0.0 &

In this formula,
R ² , R ³ , R ⁴ , R ⁶ and L are as defined for formula I.

In another aspect, the invention is directed to a photoelectric device comprising a polymer having at least one structural unit derived from a compound of formula (I) or a polymer having at least one pendant group of formula (II).

The present invention relates to a compound of formula I, a polymer derived from said compound, a polymer having a pendant group of formula II, and an optoelectronic device containing said polymers in at least one light emitting layer.

[화학식 Ib]

The structural unit or pendant group may be derived from a fluorene or triarylamine compound. Examples of structural units derived from a fluorene monomer containing a pendant Ir complex include the following structural formulas Ia to Ic:
(Ia)

(Ib)

delete

(Ic)

In this formula,

R ^1b is hydrogen, alkyl, alkoxy, oxaalkyl, substituted alkyl, substituted alkoxy, or substituted oxaalkyl,

R ^1c is hydrogen, alkyl or substituted alkyl.

In many embodiments, R ² is preferably an oxalkylene, especially -CH ₂ CH ₂ O-.

Examples of triarylamine monomers containing a pendant Ir complex include the following formulas < RTI ID = 0.0 >
(IIc)

[화학식 IIe]≪ RTI ID = 0.0 &

[Formula IIe]

In this formula,
Z is O, S or a direct bond.

Polymers derived from compounds of formula (I) or polymers having pendant groups of formula (II) may additionally comprise other monomers, especially those described in US Patent Nos. 5,929,194, 5,948,552, 6,204,515, 6,605,373, 6,815,505, And structural units derived from a fluorene monomer as described in U.S. Patent No. 6,916,902. More particularly, the structural units may be derived from dibromo 9,9-dioctylfluorene monomers. The polymer may comprise structural units derived from one or more triarylamine monomers in addition to or instead of those derived from the fluorene monomers. Suitable triarylamine monomers and polymers containing the triarylamine monomer and the remainder derived from the fluorene monomer are described in U.S. Patent Nos. 5,708,130, 6,169,163, 6,353,083, 6,255,447, 6,255,449, 6,900,285. For example, in addition to residues containing an iridium complex, the polymer may comprise structural units of formula III:

(III)

In particular, the polymer may comprise structural units of the formula (IV)

상기 식에서,
piq는 페닐아이소퀴놀린일이다.(IV)

In this formula,
piq is phenyl isoquinolinyl.

delete

delete

More particularly, the polymer may contain about 95% structural units of formula (III) and 5% structural units of formula (IV) as shown below in formula (V)
(V)

In this formula,
piq is phenyl isoquinolinyl.

.In some embodiments, the pendant group of formula (II) is of formula < RTI ID = 0.0 &
≪ RTI ID = 0.0 &

.

In some of the above embodiments, L is phenylisoquinolinyl (piq) (Formula IIb).

The structural units derived from the compounds of formula (I) or pendant groups of formula (II) may range from about 0.01% to about 50% by weight, especially about 0.1% to about 10% % ≪ / RTI > by weight of the polymer. The polymer typically has a number average molecular weight (Mn) of greater than 2,000 g / mol, especially greater than about 5,000 g / mol, greater than about 15,000 g / mol, more particularly greater than about 25,000 g / mol, as determined by gel permeation chromatography .

An optoelectronic device according to the invention comprises at least one polymer derived from a compound of formula (I) or a polymer having a pendant group of formula (II). The polymer may be a fluorescent light emitting material such as a (co) polymer based on a fluorene monomer such as F8-TFB, a commercially available light emitting polymer such as ADS131BE, ADS231BE, ADS331BE supplied by American Dye Sources, ADS431BE, ADS429BE, ADS160BE, ADS329BE, ADS229BE, ADS129BE, ADS180BE, and BP105 and BP361 available from Sumation Company Ltd. Other materials useful for blending with the polymers of the present invention include oligomeric compounds such as fluorene trimers and derivatives thereof, polymeric or molecular triarylamine materials such as those described in U.S. Patent Nos. 3,265,496 and 4,539,507 , And triarylamines (e.g., ADS254BE, ADS12HTM, and ADS04HTM), commercially available from American Daisoshi, substituted polyphenylene polymers (such as ADS120BE from American Daisoshi) And polymers having oligomeric units linked via non-conjugated linkers, such as those described in WO 2005/0256290.

When the polymer of the present invention is blended with other materials, the lowest triplet energy level of the other material (measured by photoluminescence or other techniques) is lower than the triplet energy of the pendant iridium emitter of the polymer of the present invention Larger is preferred. In particular, the polymer may be blended with one or more fluorescent materials, such as blue-emitting fluorene (co) polymers, typically having a lowest triplet energy of less than the lowest luminous singlet energy level of the polymers of the invention and exhibiting blue luminescence have.

A polymer of the present invention and / or a blend of the polymer and a blue-emitting fluorene (co) polymer is contained in one emissive layer of the device, but contains at least one fluorene polymer or copolymer such as BP105 or F8-TFB It can be disposed adjacent to another light emitting layer to form a two-layer structure. In such devices, the two-layer structure may be formed through several different methods as described in International Patent Application No. PCT / US07 / 68620. For example, the two layers may be insolubilized by first thermal treatment after first layer deposition, or by incorporating a crosslinking polymeric agent in the first layer to join the polymer chains together or to form an interpenetrating network have. Polymerization may be initiated via UV irradiation or thermal activation. The polymerization process may be improved by the addition of small amounts of initiator such as IRGACURE 754, ESACURE TM initiator BPO or AIBN from Sartomer. Alternatively, a second layer may be applied via contact laminating (Ramsdale et al., J. Appl. Phys, vol 92, pg. 4266 (2002)) or from a solvent that does not dissolve the first layer, . If desired, the methods may be applied sequentially to produce a multi-layer structure in which one or more layers comprises one or more polymers of the present invention.

The optoelectronic device according to the present invention additionally comprises at least one photoluminescent ("PL ") material optically coupled with the polymer so that the phosphor material absorbs a portion of the emitted EM radiation and thereby emits EM radiation in a third wavelength range. . ≪ / RTI > Exemplary device structures containing materials for use as PL materials and PL materials are described in U.S. Patent No. 7,063,900, the entire contents of which are incorporated herein by reference.

 The optoelectronic device illustrated as an organic light emitting device typically includes, in its simplest case, a multilayer including an anode layer, a corresponding cathode layer, and an organic electroluminescent layer disposed between the anode and the cathode. (Or "holes" are "injected" into the electroluminescent layer) from the anode while electrons are injected into the electroluminescent layer by the cathode when a voltage bias is applied across the electrode. Luminescence occurs when holes combine with electrons in the electroluminescent layer to form singlet or triplet excitons, which occurs when the singlet excitons transmit energy to the environment by radioactive decay. Triplet excitons, unlike singlet excitons, typically can not be radially attenuated and therefore do not emit light except at cryogenic temperatures. The theoretical considerations are that triplet excitons are generated about three times more often than singlet excitons. Thus, the production of triplet excitons represents a fundamental limitation on efficiency in organic light emitting devices, which typically operate at or near ambient temperature. The polymer according to the invention is formed when the conventional unproductive triplet excitons are encountered and can act as a precursor to a species of luminescent, short-lived excitation state that transfers energy.

Other elements that may be present in the organic light emitting device, in addition to the anode, cathode, and light emitting material include a hole injection layer, an electron injection layer, and an electron transport layer. During the operation of the organic light emitting device including the electron transporting layer, most of the charge carriers (i.e., holes and electrons) present in the electron transporting layer are electrons, and recombination of holes and electrons present in the electron transporting layer This can happen. Additional elements that may be present in the organic light emitting device include a hole transport layer, a hole transporting light emitting layer, a hole blocking layer, and an electron transporting light emitting layer.

The organic electroluminescent layer is a layer in an organic light emitting device that contains both electrons and holes at a considerable concentration in operation and provides sites for exciton formation and light emission. The hole injecting layer is a layer that generally contacts the anode to promote the injection of holes from the anode into the inner layer of the OLED and the electron injecting layer is a layer that generally contacts the cathode and promotes the injection of electrons from the cathode to the OLED. to be. The hole injection layer or the electron transport layer needs to be in contact with the cathode. Often, the electron transporting layer is not an effective hole transporting material, and thus serves to block the movement of holes toward the cathode. The electron transporting layer is a layer that promotes the conduction of electrons from the cathode to the charge recombination site. The hole transport layer is a layer that promotes the conduction of holes from the anode to the charge recombination site during operation of the OLED and does not need to be in contact with the anode. The hole transporting light emitting layer is a layer promoting the conduction of holes to the charge recombination site during operation of the OLED wherein the majority of the charge carriers are holes and not only from recombination of the remaining electrons but also from other charge recombination regions in the device Lt; RTI ID = 0.0 > energy transfer < / RTI > The electron transporting light emitting layer is a layer that promotes the conduction of electrons to the charge recombination site during operation of the OLED wherein the majority of the charge carriers are electrons and not only from recombination of the remaining holes but also from other charge recombination regions in the device Lt; RTI ID = 0.0 > energy transfer < / RTI >

Suitable materials for use as the anode include materials having a bulk conductivity of at least about 100 [Omega] / square when measured by a four-point probe technique. Indium tin oxide (ITO) is often used as the anode because it is substantially transparent to light transmission and thus facilitates the emission of light emitted from the electro-active organic layer. Other materials that may be used as the anode layer include tin oxide, indium oxide, zinc oxide, indium zinc oxide, zinc indium tin oxide, antimony oxide, and mixtures thereof.

Suitable materials for use as the cathode include a zero valent metal capable of injecting a negative charge carrier (electron) into the inner layer (s) of the OLED. The various zero-valent metals suitable for use as the cathode are selected from the group consisting of K, Li, Na, Cs, Mg, Ca, Sr, Ba, Al, Ag, Au, In, Sn, Zn, Zr, Sc, Y, Alloys and mixtures thereof. Alloy materials suitable for use as the cathode layer include Ag-Mg, Al-Li, In-Mg, Al-Ca and Al-Au alloys. A thin layer of a metal (e.g., calcium) or a metal fluoride (e.g., LiF) coated with a thicker layer of a layered non-alloyed structure, such as a zero valent metal (e.g., aluminum or silver) . In particular, the cathode may be composed of a single zerovalent metal, especially an aluminum metal.

Materials suitable for use in the hole injection layer include but are not limited to 3,4-ethylenedioxythiophene (PEDOT), a blend of PEDOT and polystyrene sulfonate (PSS) (HC Stark, Inc., (Commercially available under the trade name BAYTRON TM), and polymers based on thieno [3,4b] thiophene (TT) monomers (commercially available from Air Products Corporation).

Suitable materials for use in the hole transport layer include but are not limited to 1,1-bis ((di-4-tolylamino) phenyl) cyclohexane, N, N'- N, N ', N'-2, N'-tetramethyl-phenyl) Phenyl-3- (p- (di- (dimethylamino) benzylidene) diphenylhydrazone, phenyl- (9H-carbazol-9-yl) cyclobutane, N, N, N ', N < RTI ID = 0.0 > -Tetrakis (4-methylphenyl) - (1,1'-biphenyl) -4,4'-diamine, copper phthalocyanine, polyvinylcarbazole, (phenylmethyl) polysilane; Poly (3,4-ethylenedioxythiophene) (PEDOT), polyaniline, polyvinylcarbazole, triaryldiamine, tetraphenyldiamine, aromatic tertiary amine, hydrazone derivative, carbazole derivative, triazole derivative, Imidazole derivatives, oxadiazole derivatives having an amino group, and polythiophenes as disclosed in U.S. Patent No. 6,023,371.

Using the electron-transporting layer suitable material is poly (9,9-dioctyl fluorene), tris (8-hydroxy-quinol reyito) aluminum (Alq _3), 2,9- dimethyl-4,7-diphenyl- 1,1-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, 2- (4-biphenyl) -5- - (4-tert-butylphenyl) -1,2,4-triazole, 1,3,4-oxadiazole- Containing polymer, a 1,3,4-triazole-containing polymer, a quinoxaline-containing polymer, and cyano-PPV.

Justice

In the context of the present application, "alkyl" is intended to include linear, branched or cyclic hydrocarbon structures and combinations thereof, including lower alkyl and higher alkyl. Preferred alkyl groups are those of C ₂₀ or less. Refers to an alkyl group of one to six carbon atoms, preferably one to four carbon atoms, and includes methyl, ethyl, n-propyl, isopropyl, and n-, Butyl. "Higher alkyl" refers to an alkyl group having 7 or more carbon atoms, preferably 7 to 20 carbon atoms, including n-, sec- and tert-heptyl, octyl, and dodecyl. "Cycloalkyl" is a subset of alkyl and includes cyclic hydrocarbon groups of 3 to 8 carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl and norbornyl. "Alkenyl" and "alkynyl" refer to alkyl groups, in which two or more hydrogen atoms are each replaced by a double or triple bond.

"Aryl" and "heteroaryl" are 5- or 6-membered aromatic or heteroaromatic rings containing 0-3 heteroatoms selected from nitrogen, oxygen or sulfur; A bicyclic 9- or 10-membered aromatic or heteroaromatic ring system containing 0-3 heteroatoms selected from nitrogen, oxygen or sulfur; Or a tricyclic 13- or 14-membered aromatic or heteroaromatic ring system containing 0-3 heteroatoms selected from nitrogen, oxygen or sulfur. The aromatic 6- to 14-membered carbocyclic ring includes, for example, benzene, naphthalene, indane, tetralin and fluorene, and 5- to 10-membered aromatic heterocyclic rings include, for example, imidazole, pyridine, indole , Thiophene, benzopyranone, thiazole, furan, benzimidazole, quinoline, isoquinoline, quinoxaline, pyrimidine, pyrazine, tetrazole and pyrazole.

"Arylalkyl" means an alkyl moiety attached to an aryl ring. Examples are benzyl and phenethyl. "Heteroarylalkyl" means an alkyl moiety attached to a heteroaryl ring. Examples include pyridinylmethyl and pyrimidinylethyl. "Alkylaryl" means an aryl moiety having one or more alkyl groups attached thereto. Examples include tolyl and mesityl.

"Alkoxy" or "alkoxyl" refers to a linear, branched, cyclic structure group of 1 to 8 carbon atoms attached to the parent structure through oxygen and combinations thereof. Examples include methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy and cyclohexyloxy. "Lower alkoxy" refers to a group containing one to four carbons.

"Acyl" refers to saturated, unsaturated and aromatic groups of linear, branched, cyclic structure of 1 to 8 carbon atoms attached to the parent structure through carbonyl functionality and combinations thereof. One or more carbons in the acyl moiety may be substituted with nitrogen, oxygen, or sulfur, so long as the points of attachment to the parent moiety remain in the carbonyl. Examples include acetyl, benzoyl, propionyl, isobutyryl, tert-butoxycarbonyl and benzyloxycarbonyl. "Lower-acyl" refers to a group containing one to four carbons.

"Heterocycle" means a cycloalkyl or aryl moiety in which one or two carbons are replaced by a heteroatom (e.g., oxygen, nitrogen or sulfur). Examples of heterocycles within the scope of the present invention are pyrrolidine, pyrazole, pyrrole, indole, quinoline, isoquinoline, tetrahydroisoquinoline, benzofuran, benzodioxane, benzodioxole Dioxane, tetrahydrofuran, and the like), tetrazole, morpholine, thiazole, pyridine, pyridazine, pyrimidine, thiophene, furan, oxazole, oxazoline, isoxazole, dioxane and tetrahydrofuran.

"Substituted" includes, but is not limited to, alkyl, alkylaryl, aryl, arylalkyl and heteroaryl wherein up to three H atoms of the moiety are substituted with one or more substituents selected from the group consisting of lower alkyl, substituted alkyl, aryl, Alkyl, alkoxy, carbonyl, carboxy, carboxyalkoxy, carboxamido, acyloxy, amidino, nitro, halo, hydroxy, OCH (COOH) ₂ , cyano, primary amino, secondary amino, Amino, alkylthio, sulfoxide, sulfone, phenyl, benzyl, phenoxy, benzyloxy, heteroaryl or heteroaryloxy.

"Haloalkyl" refers to an alkyl residue wherein at least one H atom is replaced by a halogen atom, and the term haloalkyl includes perhaloalkyl. Examples of haloalkyl groups falling within the scope of the present invention include CH ₂ F, CHF ₂ and CF ₃ .

Many of the compounds described herein may contain one or more asymmetric centers and thus may have enantiomeric, diastereoisomeric and other stereoisomeric forms which may be defined as (R) - or (S) - in absolute stereochemistry Can be generated. The present invention is intended to include all such possible isomers and racemic mixtures and optically pure forms thereof. The optically active (R) - and (S) -isomers may be prepared using chiral synthons or may be separated using conventional techniques. Where the compounds described herein contain olefinic double bonds or other geometric asymmetric centers, unless otherwise specified, the compounds are intended to include both E and Z geometric isomers. Likewise, all tautomeric forms are intended to be included.

"Oxalalkyl" refers to an alkyl moiety in which one or more carbons is replaced by oxygen. It is attached to the parent structure through the alkyl moiety. Examples include methoxypropoxy, 3,6,9-trioxadecyl, and the like. The term "oxaalkyl" refers to a compound wherein oxygen is attached to a neighboring atom (forming an ether bond) through a single bond, but does not refer to a double bonded oxygen as found in a carbonyl group. Similarly, "thiaalkyl" and "azalkyl" refer to alkyl moieties wherein one or more carbons are each replaced by sulfur or nitrogen. Examples include ethylaminoethyl and methylthiopropyl.

"Silyl" means an alkyl moiety wherein one to three of the carbons are substituted with a tetravalent silicon and attached to the parent structure through a silicon atom. Siloxy is an alkoxy moiety that is both tetravalent silicon end-capped by an alkyl moiety, an aryl moiety, or a cycloalkyl moiety, and both of the carbons are substituted and attached to the parent moiety through an oxygen atom.

A "bidentate ligand ligand" is a ligand capable of binding to a metal through two sites. Similarly, a "three-coordinate ligand ligand" is a ligand capable of binding to a metal through three sites. The term "cyclometallated ligand" means a bidentate ligand or tridentate ligand ligand which is bonded to a metal atom by a carbon-metal single bond and one or two metal-heteroatom bonds to form a cyclic structure, The heteroatom may be N, S, P, As or O.

Any numerical value recited herein includes all values that increase by one unit from the lower limit to the upper limit, provided that no more than two units are separated between any lower limit and any upper limit. By way of example, the amount of the component or the value of the process variable, for example, the temperature, the pressure, the time and the like is, for example, 1 to 90, preferably 20 to 80, more preferably 30 to 70, Values such as 85, 22 to 68, 43 to 51, 30 to 32 and the like are also expressly recited herein. If the value is less than 1, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1, depending on the case. It is to be understood that this is merely an example of what is specifically contemplated and that the combination of all possible numerical values between the lower and upper limit values listed is also expressly referred to herein in a similar manner.

[Example]

General Procedure for Monomer Making

A preferred synthetic route for preparing the 2,7-dibromo fluorene starting material is described in Chinese Patent No. 1634839 (Scheme 1). This procedure uses bromine in water and provides a high conversion of the fluorene to the desired dibromo product with little or no formation of the monobrominated compound and substantially no by-products. When fluorene is brominated using the method using N-bromosuccinimide in methane sulfonic acid, the under-brominated unknown product is typically present in a substantially greater amount.

[Reaction Scheme 1]

After three large-scale crystallization reactions, 150 g of high quality 2,7-dibromo fluorene (99.8% excess, LC analysis) for use in the subsequent reaction was obtained. A portion of the 2,7-dibromo fluorene was converted to the tosylated ethylene glycol 9,9'-disubstituted fluorene (5) in four steps (Scheme 2).

[Reaction Scheme 2]

(4) with a high conversion (95%) in a substantially shorter reaction time (12 hours) under neutral conditions, by using a slight modification of the synthetic method described in Japanese Patent No. 1997255609 for glycosylation. ≪ / RTI > The tosylated fluorene (5) was used to prepare monomers for incorporation into a polyfluorene material having a covalently bonded pendant benzoyl pyrophoric acid Ir (III) phosphor on the periphery. The benzoyl pyrolic acid Ir (III) phosphor is covalently bonded to the fluorene monomer (6) by replacing the tosyl substituent with a phenolic nucleophile.

[Reaction Scheme 3]

[Reaction Scheme 4]

Example  1: 9- (4- Hexyloxyphenyl ) -9H- Fluorene -9-ol (2)

At reflux for 12 hours and acetone (200 mL) dibromohexane (86.0 g, 520 mmol) and _{K 2 CO 3 (80.0 g,} 580 mmol) 4- bromo-phenol (91.2 g, 527 mmol) using in the By alkylation, bromo- (4-hexyloxy) -benzene was prepared. After removing the salt by filtration, the reaction mixture was concentrated to dryness to give an oil. The oil was dissolved in EtOAc (100 mL), transferred to a separatory funnel and washed with 5% NaOH (4 x 200 mL). An additional 200 mL volume of EtOAc was added to the separatory funnel and the contents were washed with NaHCO ₃ (1 x 200 mL) and finally dried over MgSO ₄ . The EtOAc solvent was removed to give a pale yellow oil which was used without further purification.

A dry 250 mL three-necked flask was charged with a small amount of Mg fractions (2.80 g, 118 mmol) followed by anhydrous THF (100 mL). The iodine crystals were added a little and the heterogeneous mixture was heated to reflux for 15 minutes and then cooled to room temperature. Stirring was stopped, and 1,2-dibromoethane (0.25 mL) was added to the reaction vessel. After 5 minutes, an exothermic reaction occurred and stirring was resumed for 20 minutes. The reaction was then cooled to 20 ° C and bromo (4-hexyloxy) -benzene (27.8 g, 108 mmol) was added over a period of time while the temperature was maintained at 14-18 ° C. The cooling bath was removed and when the temperature of the reaction rose to 28 ° C, the reaction was stirred for an additional 10 minutes. The reaction was cooled to room temperature and the contents were poured into a toluene (250 mL) suspension of 2,7-dibromo fluorene (30.0 g, 90.4 mmol), which was maintained at -10 ° C using a cooling bath and stirred, Lt; / RTI > The cooling bath was removed and the reaction mixture was stirred at room temperature for 20 minutes and subsequently treated with a saturated solution (5 mL) of 20 mL EtOH, and NH ₄ Cl. The reaction mixture was filtered to remove insoluble material and transferred to a separatory funnel containing EtOAc (100 mL) and H ₂ O (100 mL). The layers were separated and the organic layer was washed with H ₂ O (2 × 100 mL) and brine (1 × 100 mL) and dried over MgSO ₄ . The solvent was removed by drying to obtain a crude yellow solid (50.8 g). This crude material was recrystallized from hexane / CH ₂ Cl ₂ to give the product of an off-white microcrystalline material.

Example 2: Synthesis of 9- (4-hexyloxyphenyl) -9 '- (4-hydroxyphenyl) -fluorene (3)

Phenol (24 g, 256 mmol) and 9- (4-hexyloxy-phenyl) -9H- fluoren-9-ol (2) (30.0 g, 55.7 mmol) in CH ₂ Cl ₂ (75 mL) solution of 20 drops Of methanesulfonic acid, whereby the solution turned purple. The reaction was stirred at room temperature until the starting fluorene appeared to be consumed in the TLC analysis. The reaction mixture was transferred to a separatory funnel, washed with a saturated solution of NaHCO ₃ (1 x 200 mL) and H ₂ O (3 x 150 mL), and then the organic layer was dried over MgSO ₄ . The solvent was removed by drying to obtain an oil. The oil was adsorbed onto a silica gel from a CH ₂ Cl ₂ solution and the solvent was removed by drying. The dried silica gel was transferred to a glass fritted funnel (500 mL) containing a charged H ₂ O slurry of silica gel (200 mL) mounted on a vacuum flask. By applying a vacuum to the flask, the contents of the funnel were flushed with H ₂ O to elute the phenol from the silica gel. After removal of the excess phenol, the product was eluted with a CH ₃ CN from the silica gel. The solvent was removed with a rotary evaporator with a bath at 45 占 폚 to give a milky solution (from which a white solid formed). The product was collected by filtration, washed with water and dried. A mixture of the para- and ortho-isomers of the hydroxyphenol adduct (90:10) was isolated.

Example 3 Synthesis of 9- (4-hexyloxyphenyl) -9 '- (4- (2-hydroxyethoxy) phenyl) fluorene (4)

Phenol (3) (33.0 g, 53.7 mmol) was dissolved in xylene (30 mL), dried over MgSO ₄ and filtered. This solution was concentrated on a rotary evaporator until the contents of the flask were 70 g. The xylene solution of phenol (3) was then placed under an inert atmosphere of N ₂ , treated with ethylene carbonate (3.9 mL, 59.0 mmol) and then heated at reflux for 15 h. After this time, the reaction was cooled to room temperature and the solvent was removed to give a yellow oil. Treating the oil by chromatography over SiO ₂ of 2 L, and eluted with CH ₂ Cl _2. After removal of the solvent, the product was isolated as a colorless oil.

Example 4 Synthesis of 9- (4-hexyloxyphenyl) -9 '- (4- (2-p-toluenesulfonylethoxy) phenyl) -fluorene (5)

A toluene solution (200 mL) of ethylene glycol (4) (29.1 g, 44.2 mmol) was treated with p-toluenesulfonyl chloride (13.3 g, 69.8 mmol) and triethylamine (19.4 mL, 140 mmol) Was stirred at room temperature under an inert atmosphere of N ₂ for 60 hours. The reaction mixture was then filtered to remove the triethylamine hydrochloride and concentrated to dryness. Washed and the residue was dissolved in EtOAc, 5% HCl (1 × 100 mL) and saturated _{NaHCO 3 (2 × 200 mL)} , dried over MgSO ₄ and the solvent was removed to dry. The crude oil was chromatographed over 1.4 L of SiO ₂ (CH ₂ Cl ₂ : hexane, 1: 1). After removal of the solvent, the product was isolated as a white amorphous solid.

Example  5: [( piq ) ₂ Ir (7)] - Fluorene  Synthesis of monomer (6)

To a stirred DMF solution (25 mL) containing tosylated fluorene 5 (3.00 g, 4.00 mmol) and benzoyl pyrrole iridium complex 7 (3.00 g, 3.8 mmol) was added solid K ₂ CO ₃ g, 7.24 mmol). After stirring the solution at 80 < 0 > C for 1.5 hours, the reaction was cooled, H ₂ O (75 mL) was added, the red precipitate formed was sonicated, collected by filtration, washed with water and MeOH, It was then dried in air. The product was SiO _2: treated by chromatography through a toluene, which was isolated as after removal of the solvent, a red solid.

Example  6: 2- (4- Hydroxybenzoyl ) - Of pyrrole (7)  synthesis

Trifluoroacetic anhydride (10 mL, 72.0 mmol) was added to a stirred suspension of 4-hydroxybenzoic acid (5.50 g, 40.0 mmol) in CH ₃ CN cooled to 0 ° C. After 15 minutes, the benzoic acid dissolved. To this solution cooled to 0 C was added at this temperature 1- (p-tolylsulfonyl) pyrrole (8.85 g, 40.0 mmol) and then enough CH ₂ Cl ₂ to dissolve the pyrrole. While rapidly stirring, to the reaction mixture, it was added a further volume of trifluoro-acetic anhydride (10 mL, 72.0 mmol) and then _{H 3 PO 4 (2 mL,} 37.0 mmol). The reaction mixture was stirred at room temperature for 12 hours, additional trifluoroacetic anhydride (6 mL, 43.2 mmol) and 4-hydroxybenzoic acid (4.00 g, 29.0 mmol) were added and stirring continued for 12 hours. After this time, the solvent was removed by drying, and the residue was suspended in 5% NaOH (250 mL) and stirred overnight. The suspension was removed by filtration and the filter cake was washed with 5% NaOH (250 mL). To the filtrate, a saturated solution of NaHCO ₃ (200 mL) was added and the pH of the solution was neutralized by adding concentrated HCl. The pink microcrystalline material formed was collected by filtration, washed with water and dried.

Example  7: [( piq ) ₂ Ir (7)] Synthesis of (8)

Solid sodium hydride (288 mg, 12.0 mmol) was added to stirred, cooled (-10 C) EtOH solution (100 mL) containing Ketopyrrol 7 (1.20 g, 6.40 mmol) The solution turned from yellow to orange. The solution was stirred for 5 minutes and then [(piq) ₂ Ir (μ-Cl)] ₂ (3.33 g, 2.56 mmol) was added and the mixture was then heated to reflux for 10 hours. The reaction mixture was cooled to room temperature and the red precipitate was collected by filtration. The product was washed with EtOH and dried in air.

Example 8: Preparation of 9,9-dioctylfluorene-triarylamine copolymer (formula V)

All monomers were dried in a vacuum oven at < RTI ID = 0.0 > 50 C < / RTI > for 2 hours and then weighed. A 50 mL two-necked flask equipped with a nitrogen inlet to a bubbler and a magnetic stirrer was charged with all monomers, tri-o-tolylphosphine and 15 to 18 mL of toluene. The solution was degassed with argon for 5 to 10 minutes, then Pd (OAc) ₂ was added and the remaining funnel was used to wash the weighing funnel. At the same time, in separate vials, the aqueous component was degassed with argon. After degassing for at least 15 minutes, the aqueous component was added to the organic solution and the flask was immersed in an oil bath at 70 占 폚. Stirring was continued under a positive pressure of nitrogen for 16-20 hours and at this point the solution was warmed to room temperature and 20 mg of phenylboric acid was added. The flask was again immersed in a heating bath and stirred for an additional 3 hours under nitrogen. Again, the mixture was cooled and then diluted with 10 mL each of toluene and water. The mixture was transferred to a separatory funnel, the aqueous phase discarded and the organic phase washed with 3 x 50 mL of water and 1 x 50 mL of saturated NaCl. The organic solution was then passed through a funnel containing Celite and Drierite, and the filtered solution was stirred with the amine-functional silica gel for at least 30 minutes. Again, the solution was filtered, concentrated to a volume of 20 to 30 mL on a rotary evaporator, and then loaded onto a toluene saturated silica gel cartridge (about 20-30 g silica / g polymer - note 6). The polymer was eluted from the column using toluene (about 100 mL), and the toluene solution was concentrated to about 20 mL. The polymer was isolated by precipitation of this solution in 10 volumes of methanol with vigorous stirring. The polymer was collected by filtration, washed with methanol and dried in a vacuum oven at 40-50 < 0 > C. The yield after drying was 403 mg (55%). The gel permeation chromatography showed Mw 92.4 K and Mn 23.0 K for polystyrene standards.

Example  9: Device manufacturing

On a clean, UV-ozone treated, 2.5 cm x 2.5 cm ITO patterned glass substrate, a PEDOT / PSS (Baytron P VP 8000, available from HCS Stark, Inc.) (3,4-ethylenedioxythiophene) -poly (styrenesulfonate)] was deposited by spin coating. Subsequently, the coated substrate was baked on a hot plate at 160 DEG C for 30 minutes. Then, a hole transport layer of F8-TFB (octylfluorene-triarylamine copolymer, obtained from Sumation, Inc.) having a thickness of about 10 to 20 nm was coated with a PEOOT / PSS coated And then spin-coated on the substrate. Subsequently, the F8-TFB-PEDOT / PSS coated substrate was baked on a hot plate at 170 DEG C for 30 minutes under argon. On the F8-TFB layer, the last layer of the electroluminescent polymer BP104 (Sumation) and the 1: 1 blend of the polymer of Example 8 was deposited via spin coating from a xylene solution. This layer had a thickness of about 40 to 50 nm. The coated substrate was then placed in a bell jar evaporator and the system pumped until a pressure of about 1 x ^10-6 torr was obtained. Subsequently, a layer of sodium fluoride of about 3 nm thickness (as measured through a calibrated quartz crystal microbalance) was deposited by physical vapor deposition on top of the final layer of the coated substrate. Subsequently, a layer of aluminum metal about 130 nm thick was deposited on the top of the sodium fluoride by evaporation under reduced pressure to form the cathode element of the OLED.

The luminance and current versus applied voltage of each device were measured using a Keithley 236 Source Measure unit and a silicon diode coupled to a picoammeter (Keithley). The current response of the diode was converted to the OLED luminance (cd / m ² ) by calibrating the silicon diode for the Minolta LS 100 luminance meter and measuring the active area of the OLED. The luminance ("cd / A") measures how effectively the injected charge is converted into visible light, and the LPW measures the power efficiency measure (how much visible light is generated for a particular amount of input power) to be. The LPW data includes the effect of both the operating voltage and charge on the visible light conversion efficiency. The combination of Cd / A and LPW data represents a relatively efficient operation of the device, which comprises a polymeric material and which is compatible with the low voltage operation of the device.

The color of the light (EL spectrum) emitted from each OLED device sample was measured using a calibrated spectrometer during operation of the device from about 390 nm to about 750 nm at a current density of about 1 mA. Blue luminescence from the BP 104 material and red luminescence from the red luminescent polymer material occurred. The luminescence from this particular device is dominated by the red luminescent compound, indicating that the performance shown in the LPW and Cd / A graphs is an indicator of the performance of the side branch emissive polymer.

While only certain features of the invention have been illustrated and described herein, many modifications and variations will occur to those skilled in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of the invention.

Claims (19)

delete delete delete delete A compound of formula (Ic)
(Ic)

In this formula,
R < ^{1c >} is hydrogen, alkyl or substituted alkyl,
piq is phenyl isoquinolinyl. A polymer comprising at least one structural unit derived from a compound according to claim 5. A polymer comprising at least one pendant group of formula < RTI ID = 0.0 > (IIb)
≪ RTI ID =

In this formula,
piq is phenyl isoquinolinyl. 8. The method of claim 7,
Further comprising a structural unit derived from at least one fluorene monomer. 8. The method of claim 7,
A polymer comprising additionally a structural unit derived from dibromo 9,9-dioctylfluorene monomer. 8. The method of claim 7,
Further comprising a structural unit derived from at least one triarylamine monomer. delete delete delete delete delete delete 8. The method of claim 7,
Polymers comprising structural units of formula (III): < EMI ID =
(III)

. 8. The method of claim 7,
Polymers comprising structural units of formula (IV)
(IV)

In this formula,
piq is phenyl isoquinolinyl. 8. The method of claim 7,
Polymers comprising structural units of the formula V:
(V)

In this formula,
piq is phenyl isoquinolinyl.