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Definitions

• OLEDs Organic Light Emitting Diodes
• An OLED is formed by sandwiching a fluorescent or phosphorescent organic film between two electrodes, at least one of which is transparent. Holes from the anode and electrons from the cathode recombine in the organic film and produce light, ⁇ f the organic film is a polymer film the device is a polymer-OLED or p-OLED.
• the emissive layer will often be comprised of several substances or components, including one or more charge carriers, a fluorescent or phosphorescent material, and a more or less inert matrix.
• charge carriers e.g., one or more organic light-emitting materials
• a fluorescent or phosphorescent material e.g., a fluorescent organic light-emitting material
• a more or less inert matrix e.g., a fluorescent or phosphorescent material
• inert matrix e.g., a more or less inert matrix.
• Materials with lower energy excited states may be, for example, impurities, defects, or excimers. It often occurs that the matrix has a first triplet excited state that is lower in energy or only slightly above the emissive material's excited state and a first kinglet-excited state that is higher than the emissive material's excited state. It would be desirable to -reduce or eliminate energy transfer from the desired excited state to other lower energy excited states and to eliminate energy transfer from the desired excited state to the triplet state of the matrix material.
• radical anions As electrons propagate through the emissive layer, they take the form of anions or radical anions. Radical cations may dissociate into a cation and a free radical, while radical anions may dissociate into an anion and a free radical, Cations, radical cations, anions, radical anions, and free radicals are all reactive species and may undergo unwanted chemical reactions with one another or with nearby neutral molecules. Such chemical reactions alter the electronic properties of the emissive layer and can lead to decreases in brightness, efficiency, and (ultimately) device failure. For this reason, it would be desirable to reduce or eliminate chemical reactions of these active species in OLEDs and p-OLEDs.
• polyfluorene blue phosphors are not suitable for commercial p-OLED applications. For this reason, it would be desirable to improve emissive materials, especially those that emit in the blue color range.
• the emissive center is typically a special repeat unit selected to have a first singlet-excited state of appropriate energy to emit green or red.
• the emissive center is typically one or more adjacent phenylene (or bridged biphenylene) repeat units.
• the phenylene (or bridged biphenylene) backbone has the lowest singlet-excited state out of all the repeat units or other materials present. That is, the majority repeat unit is the emitter. This means that excited states spend most of their time on the majority repeat unit. Since excited states are more reactive than ground states the majority repeat units are prone to undergo undesiced reactions.
• One aspect provided in the present invention are polymer materials having twisted biarylene units that increase the first singlet- and triplet-excited states relative to similar polymers lacking such sterically twisted structures.
• Another aspect provided in the present invention is a polymer material having sterically twisted biarylene units that are suitable as host matrix-es for fluorescent and phosphorescent emitters for use in p-OLED applications.
• Another aspect provided in the present invention is an oligomeric material comprised of sterically twisted biarylene units that are suitable as host matrixes for fluorescent and phosphorescent emitters for use in p-OLED applications.
• Another aspect provided in the present invention is a copolymer material comprised of sterically twisted biarylene repeat units and fluorescent or phosphorescent repeat units.
• Another aspect provided in the present invention is a copolymer comprised of
• One object of the present invention is to provide a blue emissive polymer with a long lifetime.
• the lifetime to half brightness starting at 100 cd/m 2 should be greater than 1,000 hours, preferably greater than 2,000 hours, more preferably greater than 5,000 hours, -even more preferably greater than 10,000 hours, and yet more preferably greater than 20,000 hours.
• P-OLED devices are often tested at higher initial brightness as an accelerated ageing test.
• the lifetime to half brightness starting at 1,000 cd/m 2 should be greater than 100 hours, preferably greater than 200 hours, more preferably greater than 500 hours, even more preferably greater than 1,000 hours, and yet more preferably greater than 2,000 hours.
• the short lifetime of current state-of-the-art blue emissive polyphenylenes and bridged polyphenylene is likely due to the polymer serving as the emissive center. If the polymer itself has the lowest lying singlet level, then it must carry the exciton (excited state) for a longer period of time than if it transfers its energy to an emitter with a lower level. Having this exciton reside on the polymer for long periods of time has several deleterious effects. First, since the excited state is a very chemically reactive species, an opportunity is provided for the majority of repeat unit of the polymer backbone to react irreversibly.
• the time that the excited state -spends on the main polymer repeat unit is increased, further increasing the chance of side reactions.
• Designing a useful polymer in which the bulk of the backbone -structure does not serve as the emitting unit in p-OLED applications has met with limited success.
• moderate slight twist twist units in these systems generally have only small hydrogen s ⁇ bstituents at positions ortho to the polymer backbone, which also give rise to increased conjugation and lower energy.
• one or two out of the four ortho positions is substituted with a straight chain alkyl or alkoxy group, causing some twist.
• groups larger than n-alkyl are used, or three or four of the ortho positions are substituted, and larger twists, approaching 90° are generated, and a significant increase in bandgap results. '
• a key aspect of this invention are sterically twisted polyarylene polymer systems that offer higher energy repeat units. This is accomplished by decreasing both the conjugation of the polyarylene repeat by forcing adjacent aryl groups out of planarity.
• the twist angle between the rings shown depends on the size of substituents R 2 , R' 2 , R 6 and R' 6 .
• the rings will have a large enough twist (called herein a “Sterically Twisted' Biarylene” (STB) group, unit, or repeat unit) to be useful for the practice of the present invention if:
• R 2 , R 2 , R 6 and R' 6 are not -H and at least one of R 2 , R 2 , R 6 and R 6 is selected from the group consisting of-CR 7 RgR 9 , -OR 1 O - NR 10 R 1I , -SR 1O , -SiR 11 Ri 2 Ri 3 , and bridging with either R 3 , R 3 , R 5 and R' 5 respectively, where R 7 is selected from the group consisting of -H, alkyl, aryl, heteroalkyl, heteroaryl, fluoro, chloro, alkoxy, aryloxy, cyano, fluoroalkyl, fluoroaryl, where R 8 and R 9 are independently selected from the group consisting of alkyl, aryl, heteroalkyl, heteroaryl, fluoro, chloro, alkoxy, aryloxy, cyano, fluoroalkyl, fluoroaryl, where R 10 is selected from the group consisting
• R 2 , R 2 , R 6 and R' 6 are not -H, and optionally, any OfR 2 , R 2 , R 6 a nd R' 6 may -form a bridge or multiple bridges with R 3 , R ⁇ ,
• R 5 and R'5 respectively, and any R 3 , R' 3 , R 5 and R'5 may form a bridge or multiple bridges with R groups on repeat units adjacent to those shown in General Structure I 5 and any -carbon atom and its associated R group in the rings of General Structure 1 may be replaced by nitrogen to form a heterocycle, and any of R 7 , R 8 , R 9 R 10 , and R 11 may form a bridge or multiple bridges with any other R group, and where here and throughout fluoroalkyl and fluoroaryl may be mono, di, poly, or per fluorinated.
• R 3 , R' 3 , R 5 and R' 5 may be any group, including but not limited to H, alkyl, aryl, heteroalkyl, heteroaryl, fluoro, chloro, alkoxy, aryloxy, cyano, fluoroalkyl, fluoroaryl, ester, amide, imide, thioalkyl, thioaryl, alkylketone, and arylketone.
• -S-CH CH-
• a non-limiting example OfR 3 bridging to an adjacent repeat unit is:
• R 6 is methyl and R' 2 is isopropyl.
• R 30 , R 31 , R32, R33, R34, R34, R'30, R'31, R'32, R'33, R'34, and R' 35 are independently selected from the group consisting of hydrogen, alkyl, aryl, heteroalkyl, heteroaryl, fluoroakyl, fluoroaryl, alkylketone, aryl ketone, alkoxy, and aryloxy,
• X and X' are independently selected from the group consisting of C, N, O, Si, P, and S, if X is C and R 35 and R' 3 s are H then R 30 and R 31 are not H 5 if X is N or P then R 30 is nil and R 31 has a secondary or tertiary carbon bonded to X, if X 1 is N or P then R' 3 0 is nil and R'31 has a secondary or tertiary carbon bonded to X', if X is O or S then R 3 o and R 31 are nil and R 32 has a secondary or tertiary carbon bonded to X, if X' is O or S then R' 3 o and R' 31 are nil and R' 32 has a secondary or tertiary carbon bonded to X, if X' is O or S then R' 3 o and R' 31 are nil and R' 32 has a secondary or tertiary carbon
• a 33 , A 34 , A 35 , A' 33 , A' 34 , and A' 35 are independently -selected from C or N, where if A is N the corresponding R is nil, any of R 3 O-R 33 independently may be bridging with one another,
• R 34 may be bridging with R 35 , any of R' 3 o-R' 33 independently may be bridging with one another,
• R'34 may be bridging with R'35, and any of R 33 , R 34 , R' 33 and R' 34 may be bridging with a repeat unit adjacent to the dyad.
• the R groups may form saturated or unsaturated fused rings. For example, forming naphthyl or phenanthryl repeat units.
• a significant portion of the repeat units be arylene or other conjugated units (e.g. ethylene, acetylene, arylamine, thiophene), preferably more than 25% of the units will be arylene or other conjugated units, more preferably more than 45% and most preferably more than 65%.
• a significant portion of the dyads should be sterically twisted dyads represented by Structure 7, preferably more than 10% of the dyads, more preferably more than 20%, even more preferably more than 30%, yet more preferably more than 40%.
• sterically twisted dyads may be incorporated into the instant polymers, including but not limited to 50% of the dyads, 75% of the dyads, and even 100% of the dyads.
• a homopolymer may have 50% of the dyads twisted, or more.
• a homopolymer may have a random regio-chemistry such that not all dyads are head-to-head or head-to-tail, and the number of twisted dyads may have a statistical distribution.
• the arylene group may be a bicyclic or polycyclic fused ring group, and may contain heteroatoms.
• the polymers may be prepared by any of various aryl-aryl coupling methods, preferably by Suzuki coupling.
• the general monomer structure is:
• X and Y are selected independently from Cl, Br, I 5 B(OH) 2 , B(ORi 2 ⁇ , and OS(O) 2 RiS, where Ri 2 is alkyl, aryl, and the two Ri 2 may be bridging to form a ring, and Rn is alkyl, aryl, fluoroalkyl and fluoroaryl, preferably fluoroalkyl.
• X and Y may also be selected from MgX 5 ZnX 5 Li, Sn(R 14 )3 and the like, where X is halogen, for example, for use in Yamamoto coupling polymerization, Negishi coupling polymerization, or Stille coupling polymerization, where R 14 is selected independently from
• the singlet and triplet states of polymers comprising sterically twisted arylene repeat units are higher than those of conventional polyarylenes, polyphenylenes, and polyfluorenes.
• the singlet energy may be greater than approximately 3 eV (413 nm), preferably greater than about 3.1 eV (400 nm), and more preferably greater than about 3.2 eV (388 nm).
• Polymers comprising sterically twisted biarylene segments may also contain emissive repeat units with singlet energy in the visible, IR or UV range.
• the emissive repeat unit may have peak emission of about 410 nm to 450 nm that will -emit blue light.
• These blue emissive repeat units maybe present at a relatively small mole fraction, preferable less than 10 mole %, more preferably less than 8 mole %, even more preferably less man about 6 mole %, yet more preferably less than 5 mole %.
• Lower levels of blue emissive repeat units may also be practical, including less than 4 mole %, less than 2 mole %, less than 1 mole % and even less than 0.5 mole %.
• emissive repeat units may be protected, using methods known in the art, to prevent reaction of these units with one another or other components of the emissive layer.
• the emissive repeat unit may have large inert substituents including but not limited to alkyl, aryl, heteroalkyl, and heteroaryl.
• inert substituents include but are not limited to f-butyl, phenyl, pyridyl, cyclohexyloxy, and trimethylsilyl.
• Attaching inert substituents at reactive positions on the unit can also stabilize emissive units; For example, it is known that the triphenylamine cations reacts primarily at the 4, 4', and 4" -positions of the phenylene units (those para to the nitrogen). It is also known that substituting these positions with, for example, alkyl groups prevents these reactions and greatly increases the lifetime of the radical cation.
• alkyl e.g. methyl, J-butyl
• Emissive units can also be made stable if they are able to delocalize charge, over a larger number of atoms. For example, a triphenylamine cation is more stable than an alkyldiphenylamine cation since the charge on the former delocalizes over three phenyl rings, as opposed to only two phenyl rings in the latter. Finally, incorporating bulky groups on adjacent repeat units can protect emissive repeat units. [0028] This combination of twisting of adjacent arylene units, transfer of energy to a minority emissive repeat unit, and protection of emissive units leads to longer OLED and p- OLED device lifetimes. Additionally, raising the singlet- and triplet-energy levels of the polymer or oligomer by sterically twisting reduces or eliminates non-radiative pathways and increases brightness and efficiency.
• One embodiment of this invention involves a homopolymer or copolymer having a molecular weight of greater than about 1,000 comprising a twisted biphenyl unit having the structure:
• R2, R'2, R6 and R'6 are as defined above, for example, R2, R'2, R6 and R'6 are all i-propyl.
• the Sterically Twisted Biarylene (STB) polymers are non-linear and contain branch points.
• One advantage of non-linear polymers is that polymer mixtures or blends are easier to prepare. For example, if two dendrimeric or hyperbranched polymers have dissimilar cores but similar shells they will tend to be miscible.
• Another advantage is that the central core is protected by an outer shell structure.
• a further advantage is that the electronic properties of the core and one or more shells may be varied independently, for example, a hyperbranched polymer might have an emissive core, a hole transporting inner shell, and an electron transporting outer shell. Light branching or crosslinking also maybe advantageous for control of MW and viscosity.
• a non-limiting example of a STB polymer having a branched structure is given by:
• the branched polymers of the present invention may be prepared by the inclusion of a trifunctional or polyfunctional monomer along with the difunctional monomers.
• Structure 13 may be prepared by Suzuki coupling of the following monomers and endcapping agent:
• the degree of branching may be controlled by adjusting the relative amount of tribromophenylamine. It will be also understood that the molecular weight is controlled by the relative amount of endcapping agent and the ratio of d ⁇ boronic ester monomers and dibromo monomers.
• One unusual feature of Suzuki polymerization is that the monomer ratio giving the highest MW is often offset in favor of the diboronic ester. This is likely due to some homocoupling of boronic esters.
• One reasonably skilled in the art will know how to adjust the monomer ratio, the amount of endcapping agent, and the amount of crosslinking- monomer to obtain a higher or lower MW.
• the present invention also relates to linear polymers comprising sterically twisted arylene units and reactive end groups or side groups that may be induced to form non-linear structures through reaction at the reactive end groups or side groups.
• Polymers having reactive side groups are disclosed in U.S. 5,539,048 and 5,830,945 incorporated herein in full by reference.
• Polymers having reactive end groups are disclosed in U.S. 5,670,564; 5,824,744; 5,827,927; and 5,973,075 all incorporated herein in full by reference.
• TSTon-limitirig ' example ' s ' of STB polymers having a reactive side group are given by:
• Branched, hyperbranched, and dendritic polymer may also have reactive groups.
• polymers having reactive side groups or reactive end groups may be crosslinked into an insoluble network, sometimes called thermosets.
• Crosslinked polymers offer several advantages over uncrosslinked polymers, especially for applications in the area of OLEDs and p-OLEDs.
• p-OLEDs typically consist of multiple layers polymers, each being very thin, typically between 50 nm and 1,000 nm.
• polymer layers must be deposited over previously formed polymer layers. The underlying layer must not dissolve in or be disturbed by the polymer solution being applied to form the upper layer.
• One method to prevent disturbance of the lower layers is to crosslink the lower layers prior to application of upper layers.
• the nonlinear, crosslinked layers are impervious to solvent and subsequent processing steps.
• Polymers and co-polymers of the present invention may be linear, branched, hyperbranched, dentritic, graft, comb, star, combinations of these or any other polymer structure.
• Polymers of the present invention may be regio-regular, regio-random or combination.
• Polymers of the present invention may be head-to-head, head-to-tail, or mixed head-to-head/head-to-tail.
• Co-polymers of the present invention may be alternating, random, block, or combination of these.
• Polymers of the present invention may be chiral or contain chiral repeat units.
• a polymer comprises at least one Sterically Twisted Biarylene (STB) repeat unit, at least one luminescent compound, L, and optionally other repeat units Q.
• STB Sterically Twisted Biarylene
• the luminescent dye may be incorporated into the polymer in any fashion.
• Non- limiting examples of structural types include:
• Q is nil, or any conjugated repeat unit, where structures I-V are copolymers they may be any combination of alternating, block, or random, L is any luminescent compound or group, and where if L is part of a polymer chain backbone as in structure I L is divalent, if L is attached to a polymer as in structures H-V L is monovalent, and if part of a blend as in structure V, zero valent (i.e. not sharing any bonds with the STB polymer chain) and in Structure II L may be chemically attached directly to the aromatic ring or to any of R 2 , R' 2 , Re and R' 6 .
• the structure may represent homopolymers, for example the STB units and Q are perfectly alternating, co-polymers comprising any number of types of repeat units, random, block, regio-regular, regio-random, graft, comb, branched, hyperbranched, dendritic, crosslinked or any combination of structures.
• JNon-limitmg examples of conjugated repeat units, Q include:
• the luminescent unit, L 3 is a divalent unit, and is part of the main chain.
• luminescent unit, L is a monovalent unit appended from any position of the STB unit, including any position on me biarylene moiety and any position on any of the bridging moieties.
• the luminescent unit, L is a monovalent unit appended from at least one of the repeat units Q.
• the luminescent unit, L is an end group.
• the luminescent compound is not chemically attached to the polymer, but is present as a component of a polymer blend or mixture.
• the luminescent compound may be a small molecule that is dissolved in the polymer matrix.
• the luminescent compound is an oligomer or polymer blended in with the STB containing polymer.
• L is part of a blend or mixture other compounds may be present to increase solubility or compatibility of L with the STB containing polymer.
• L need not be fully soluble or compatible with the STB containing polymer if the fabrication method results in a non-equilibrium state wherein L is trapped in the polymer and kinetically prevented from crystallizing or separating.
• At least one STB unit on the average in each polymer chain there will be at least 10 mol% STB units, more preferably at least 20 mol% STB units, and most preferably at least 25 mol% STB units. There may be up to 99.99 mol% STB units. There may be anywhere between 0 and 99 mol% Q units, preferably between 0 and 50 mol%. There may be 0.01 to 50 mol% luminescent units L, more preferably between about 0.1 and 25 mol%, even more preferably between about 0.2 and 15 mol% luminescent L units, and most preferably between about 0.5 mol% and 5 mol% luminescent L units.
• the luminescent component, L will have an emission at longer wavelength (lower energy) than the STB polymer component.
• the luminescent component L
• the luminescent component, L will have an emission at longer wavelength (lower energy) than the STB polymer component.
• the luminescent material if a luminescent material of lower energy is embedded in a matrix that is luminescent at higher energy (in the absence of L), then energy is transferred from the matrix to the luminescent material and emission from the luminescent material dominates.
• all or part of the luminescence of the matrix may be quenched by L, preferably 20%, more preferably 40%, even more preferably 60%, yet more preferably 80%, even yet more preferably 90%, even more preferably 95%, and most preferably more than 99% of the matrix luminescence is quenched (or otherwise reduced) by the presence of L. It may be that within experimental error 100% of the luminescence of the matrix is quenched by L.
• Luminescent materials, groups, dyes, or pigments may be selected from any luminescent material, group, dye or pigment known in the art.
• a non-limiting example of a luminescent dyes is stilbene:
• each ring may have 0-5 R 17 groups which may be monovalent or divalent, or may provide a link to a polymer, and where any two R 17 -R 19 taken together may be bridging.
• Monovalent R means the group R has only one linking bond. Non-limiting examples of monovalent R are methyl, hexyloxy, and 4- ⁇ -butylphenyl.
• Divalent R means the group R has two linking bonds. Non-limiting examples of divalent R are -CH 2 - (methylene), - CH 2 CH 2 CH 2 - (1 ,3-propylene), 1 ,2- phenylene, and -OCH 2 CH 2 O- (ethylenedioxy).
• a specific monovalent stilbene is (R 17 is alkyloxy, R 1S is cyano, and a second R 17 is divalent alkyl providing a link to the polymer chain):
• luminescent dyes are: anthracene, tetracene, phenanthrene, naphthalene, fluorene, bisnaphthalene, biphenyl, terphenyl, quaterphenyl, bisthiophene, bisquinoline, bisindene, and the like, where any of the hydrogens may be independently substituted by monovalent or divalent R, or may provide a link to a polymer, where any two R taken together may be bridging.
• luminescent dyes include:
• the relevant energy level of the STB polymer is also the triplet level. That is, the lowest triplet level of the STB polymer must have a higher energy than the triplet of the luminescent material. This limit on the triplet level is much more restrictive, since the triplet is nearly always lower than the singlet level. Nevertheless, the triplet level is expected to increase with the singlet level, and a "bluer'Or higher energy triplet emitter can be supported with the STB polymers of the present invention than with the corresponding less twisted or untwisted polymer.
• a green triplet emitter with a STB polymer where the ⁇ corresponding untwisted or less twisted polymer cannot because its triplet is too low.
• a phosphorescent emitter is bound to or mixed with a STB polymer.
• a green emitting iridium bisphenylpyridine emitter is coordinated to an acetylacetone group linked to a STB polymer to provide a green emitting
• One way to determine if a luminescent compound is useful in the practice of the present invention is to compare the visible emission spectrum of the polymer in the presence of L to that of the polymer in the absence of L.
• Useful L will effectively quench the polymer matrix photoluminescence or electroluminescence.
• the emission spectrum of the polymer in the presence of L will have average energy in the visible range (400 nm to 650 nm) red-shifted by at least 4 nm from the polymer without L, more preferably at least 8 nm, even more preferably at least 12 nm, and most preferably at least 20 nm.
• the wavelength scale is not linear in energy it may be preferable to use energy units where the emission spectrum of the polymer in the presence of L will have average energy in the visible range (400 nm to 650 nm) red-shifted by at least 0.025 eV from the polymer without L, more preferably at least 0.050 eV, even more preferably at least 0.075 eV, and most preferably at least 0.125 eV.
• L is part of the polymer (for example, as a repeat unit, a side group, or an end group) the comparison will necessarily be to a different polymer lacking any L groups or units, for example, if L is a side group or end group it may be replaced with H or phenyl.
• L is part of the polymer there may be other unavoidable changes that could also affect the emission spectrum, for example, molecular weight, or distance between STB units, however, typically the mol% L will be low and such effects will be minimal.
• Another way to determine the ability of a luminescent compound, group or repeat unit L to be useful in the practice of the present invention is to compare the visible emission spectrum of a luminescent model compound L 1 having phenyl groups where the luminescent compound was attached to the polymer chain, with the visible emission spectrum of a STB model compound Fn-S IB-Ph, having a single STB unit terminated with phenyl groups.
• L' will be identical to L where L is a compound not attached to the STB polymer chain.
• To be useful L must have a lower emission energy than Ph-STB-Ph.
• the luminescent compound, unit, or group L will be protected through incorporation of sterically bulky groups.
• the bulky groups protect L by preventing close approach to another L or polymer chain.
• the stabilizing effect of bulky groups is well known and it will be understood by one reasonably skilled in the art how to design a molecule L to have steric bulk.
• the luminescent compound, unit or group L will be protected through the placement of inert groups at active positions.
• inert groups For example, it is well known that the radical cation of triphenylamine is very reactive and reacts rapidly with neutral triphenylamine to form tetraphenylbenzidene. However, substitution of the three hydrogens para to the nitrogen with methyl results in the very stable tri-/>-tolylamine radical cation.
• active positions in a material for example, by alkylation and location of the alkyl groups, and to prepare protected versions of those materials.
• Protective groups include but are not limited to, alkyl, aryl, halo (preferably F and Cl), cyano, alkoxy, aryloxy, heteroalkyl, and heteroaryl.
• Degradation will be lower if the polymer is below T g during use of the device. Thus L will be protected by use of relatively stiff repeat units and side chain, and avoiding flexible groups such as long alkyl chains.
• the STB polymers of the instant invention may have repeat units, side groups or end groups that aid in charge transport. These repeat units or groups may aid electron transport or hole transport.
• Non-limiting examples of hole transport units are triarylamines, benzidenes, and dialkoxyarenes.
• Non-limiting examples of repeat unit Q shown above are good hole transport units.
• Non-limiting examples of electron transport units are oxadiazoles, benzoxazoles, perfluoroarenes, and quinolines.
• Some of the non-limiting examples of repeat unit Q shown above are good electron transport units.
• Any of the divalent structures shown for Q may be used as monovalent groups, e.g. end groups or side groups, by replacing one of the two linkages with - H or -Ph (Le. phenyl).
• the amount of charge transport units or groups may vary from zero to 99%, preferably less than 75%, more preferably less than 50%.
• charge transport groups include about 5 mol%, 10 mol%, 15 mol%, 20 mol%, 25 mol%, 30 mol% and 35 mol%.
• One skilled in the art will know how to prepare a series of polymers having various amounts of charge transport units and test their properties by measurement of charge mobility, for example, by time of flight measurement, or by measuring the efficiencies of p-OLEDs prepared from them. It has been suggested that a good luminescent layer will carry electrons and holes equally well, and it is desirable to adjust hole and electron mobility to be equal through addition or subtraction of charge transport units or groups.
• the STB polymers of the instant invention may be used in layers of OLEDs and p- OLEDs other than the luminescent layer, for example, in a charge transport layer.
• the charge carrying ability of a conjugated polymer may be enhanced by the incorporation of easily reducible repeat units (enhanced electron transport), or easily oxidizable repeat units (enhances hole transport), or both.
• Polymer compositions comprising easily oxidizable triarylamines are disclosed in U.S. 6,309,763 which is incorporated herein by reference.
• Polymer compositions comprising electron transport units are disclosed in U.S. 6,353,083 which is incorporated herein by reference.
• Additional carrier transporting repeat units useful in the practice of the present invention are disclosed in U.S. 2002/0064247 and U.S. 2003/0068527 also incorporated herein by reference.
• the charge carrying layers of OLEDs and p-OLEDs may have additional functionality, for example, but not limited to, blocking charge carriers of the opposite type, blocking excitons, planarizing the structure, providing means for light to escape the device, and as buffer layers.
• the polymers and oligomers of the present invention may be blended or mixed with other materials, including but not limited to, polymeric or small molecule charge carriers, light scatterers, crosslinkers, surfactants, wetting agents, leveling agents, T g modifiers, and the like.
• other materials including but not limited to, polymeric or small molecule charge carriers, light scatterers, crosslinkers, surfactants, wetting agents, leveling agents, T g modifiers, and the like.
• the monomers of the present invention may be prepared by any methods known in the art.
• Patent application U.S. 2004/0135131 discloses many aryl compounds and their synthesis and is incorporated herein by reference.
• the polymers of the instant invention may be prepared by any method of aryl coupling polymerization, including but not limited to, Colon reductive coupling of aryldihalides with zinc or other reducing metals catalyzed by nickel or other transition metal, Yamamoto reductive coupling of aryldihalides with an equivalent of nickel (0), Yamamoto coupling of aryl halides and aryl grignards with a nickel catalyst, Stille coupling of aryl halides with aryl tin reagents typically catalyzed with Pd, Suzuki coupling of aryl halides with aryl boronic acids or esters catalyzed with Pd metal, Pd complexes or salts, Negishi coupling of aryl halides with aryl zinc reagents typically catalyzed with Pd, Kumada catalytic coupling of aryl halides with aryl grignards or aryl lithium reagents, oxidative
• the polymers of the instant invention also may be prepared by any other methods, such as, but not limited to Diels- Alder type condensation of a bis-diene with a bis-dienophile as disclosed for example by Schilling et al, Macromolecules, Vol. 2, pp 85-88, 1969, incorporated herein by reference.
• the polymers of the instant invention also may be prepared by graft and block methods, for example, wherein an intermediate polymer or oligomer is first formed and arms or chain extensions of another type of polymer are grown off the intermediate polymer.
• Graft co-polymers and block co-polymers may be useful, for example, to control the polymer morphology, or to prevent close approach of polymer chains, or crystallization. Grafts and blocks also may be used to control charge transport, for example, by incorporation of grafts or blocks of hole and/or electron transporting chains, Luminescent groups may be incorporated through the use of grafting or block copolymerization.
• L ⁇ o ⁇ j Monomers useiui tor the practice of the present invention include, but are not limited to, compositions represented by:
• R m may be independently hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, and substituted heteroaryl
• R n may be independently alkylene, substituted alkylene, and 1,2-arylene
• Z 1 and Z 2 are independently chosen from the group consisting of halogen atoms, — ArCl, —
• ArBr — ArI, — CORm, ArC0R m , boron dihalides, borontrihalide salts, boronic acids, boronic esters, where the boronic acids or esters may be, but are not limited to
• Non-limiting examples of R m are ethyl, phenyl, and 2-pyridyl.
• Non-limiting examples of R n are ethylene (-CH 2 CH 2 -), propylene (-CH 2 CH 2 CH 2 -), tetramethylethylene, and 1,2-phenylene.
• a non-limiting example of a borontrihalide salt is the tetrabutylammonium salt of -BFj(-).
• Monomers useiul tor preparing the polymers of the present invention include:
• Z 1 and Z 2 are independently chosen from the group consisting of halogen atoms, -ArCl, -ArBr, -ArI, — COR m , ArCOR 1n , B(OR m ) 2 , — ArB(OR m ) 2 ,
• Monomers may be prepared by any method. For example,
• dibromo monomer ii a. (BOMe) 3i b. H 2 O diboronate ester monomer Hi ethylene glycol, -H 2 O terphenyl monomers may be prepared by Suzuki coupling followed by bromination to dibromomonomer and conversion of the dibromide into the diboronic ester.
• the known 1,4- diiodo-2,5- diisopropylbenzene may also be used as a monomer, or converted to a diboronic acid or ester.
• the known 4,4"-dibromoterphenyl may be alkylated or dialkylated to give a dibromo monomer, and this may be converted to a diboronic acid or ester monomer.
• Other monomers and their method of preparation will be apparent to one reasonably skilled in the art.
• any of the dibromo-monomers may be polymerized with, for example, toluene 2,5- bis(l,3,2-dioxaborolane-2-yl), and 4-f-butyl-4',4"-dibromotriphenylamine (typically 5 to 20 mol%) using Pd(PPh 3 ) 4 (0.5 mol%) and Na 2 CO 3 (2 eq) in toluene/water or in dimethylacetamide. It is preferred to add benzene boronic acid as an endcap. [0072] It is desirable for the polymers of the present invention to have good electron and hole transport properties.
• co-polymers comprising STB units and good hole transporting and/or electron transporting units.
• Good hole transporting units will be relatively easy to oxidize, show reversible electrochemistry, and be relatively stable in the oxidized state.
• Hole transport units should have higher bandgap than the emitter.
• the hole transport unit will impart upon the polymer a reversible oxidation in the range of 0.2 to 2 V vs the AgZAgNO 3 reference electrode (about 1 to 2.8 V vs the normal hydrogen electrode (NHE)) when measured, for example, by cyclic voltammetry (CV), either in solution or as a film in an electrolyte that can swell the film (for example acetonitrile), and at a scan rate of about 10 mV/sec.
• CV peak-to-peak separation will be less than 80 mV, more preferably less than 70 mV and most preferably less than 60 mV.
• Electron transport units should be relatively easy to reduce, show reversible electrochemistry, have higher bandgap than the emitter, and be relatively stable in the reduced state.
• the hole transport unit will impart upon the polymer a reversible oxidation in the range of between -1.3 and -2.8V vs the AgZAgNO 3 reference electrode (about -0.5 to -2 V vs NHE when measured, for example, by cyclic voltammetry (CV), either in solution or as a film in an electrolyte that can swell the film, and at a scan rate of about 10 mVZsec. More preferably in the range -1.5 to -2.5 V vs AgZAgNO 3 .
• the CV peak- to-peak separation will be less than 80 mV, more preferably less than 70 mV and most preferably less than 60 mV.
• luminescent means the property of emitting light upon stimulation. Stimulation may be by electromagnetic radiation of any frequency, including visible light (photoluminescent), X-rays, gamma rays, infra-red, and ultra-violet, by electron beam, by heat or by any other energy source.
• Luminescent and photoluminescent include fluorescent and phosphorescent. Fluorescence is luminescence having a short decay time, and generally refers to luminescence from an excited singlet state to the ground state, or any highly allowed transition.
• Phosphorescence is luminescence having a long decay time, and generally refers to luminescence from an excited triplet state to a singlet ground state, or to a forbidden transition.
• transition metals includes group IIIB, IVB, VB, VIB 5 VIIB,
• Dyad as used herein refers to two aryl repeat units, where the ortho substituents are those ortho to the bond joining the two aryl units. In counting dyads in a polyarylene each aryl unit will appear in two dyads.
• a secondary carbon is one which is directly bonded to exactly two other carbon atoms:
• a tertiary carbon is one which is directly bonded to exactly three other carbon atoms.
• a quaternary carbon is one which is directly bonded to exactly four other carbon atoms.

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