WO2010123692A1 - Optoelectronic devices and organic compounds used therein - Google Patents

Abstract

An optoelectronic device comprises a cathode; an electron-transporting layer comprising a compound of formula I; formula I a light emitting-layer, and an anode; wherein R1 and R2 are independently at each occurrence, hydrogen, a C rC2U aliphatic radical a CyC2U aromatic radical or a d~ C-JO cycloaliphatic radical; R3 is H or alky]; a and b are, independently at each occurrence 0, or an integer ranging from 1 to 3; n is 2 or 3; and Ar is an aryl.

Description

OPTOELECTRONIC DEVICES AND ORGANIC COMPOUNDS USED THEREIN

BACKGROUND

[0001 ] The invention relates generally to optoelectronic devices and compounds used therein as, e.g., electron-transporting materials.

[0002] Optoelectronic devices, e.g. Organic Light Emitting Devices (OLEDs). which make use of thin film materials that emit light when subjected to a voltage bias, are expected to become an increasingly popular form of flat panel display technology. This is because OLEDs have a wide variety of potential applications, including cell phones, personal digital assistants (PDAs), computer displays, informational displays in vehicles, television monitors, as well as light sources for general illumination. Due to their bright colors, wide viewing angle, compatibility with full motion video, broad temperature ranges, thin and conformable form factor, low power requirements and the potential for low cost manufacturing processes. OLEDs are seen as a future replacement technology for cathode ray tubes (CRTs) and liquid crystal displays (LCDs). Due to their high luminous efficiencies, OLEDs are seen as having the potential to replace incandescent, and perhaps even fluorescent, lamps for certain types of applications.

[0003] OLEDs possess a sandwiched structure, which consists of one or more organic layers between two opposite electrodes. For instance, multi-layered devices usually comprise at least three layers: a hole injection/transport layer, an emissive layer and an electron transport layer (ETL). Furthermore, it is also preferred that the hole injection/transport layer serves as an electron blocking layer and the ETL as a hole blocking layer. Single-layered OLEDs comprise only one layer of materials between two opposite electrodes.

BRIEF DESCRIPTION

[0004] In one aspect, the invention relates to an optoelectronic device comprising: a cathode: an electron-transporting layer comprising a compound of formula I:

formula I a Iight emittιng-layer; and an anode, wherein

R¹ and R² are independently at each occurrence, hvdrogen. a C₁-C₂₀ aliphatic radical, a C₃-C₂₀ aromatic radical, or a C₃-C₂₀ cycloaliphatic radical.

R~ is H or alkyl; a and b are. independently at each occurrence 0, or an integer ranging from 1 to

3. n is 2 or 3. and

Ar is an aryl.

[0005] In another aspect, the invention relates to an organic compound of formula I

DETAILED DESCRIPTION

[0006] Organic compounds of formula I have properties suitable for use in electron- transporting layers of optoelectronic devices, e g . organic light emitting deuces (OLEDs) or photovoltaic devices.

[0007] In one aspect the present invention relates to compounds of formula II, and optoelectronic devices having an electron-transporting layer containing these compounds

[0008] In another aspect, the present invention relates to compounds of formula 111. and optoelectronic devices having an electron-transporting layer containing these compounds

[0009] In vet another aspect, the present invention relates to compounds of formula IV. and optoelectronic devices having an electron-transporting layer containing these compounds

[0010] In yet another aspect, the present invention relates to compounds of formula V. and optoelectronic devices having an electron-transporting layer containing these compounds

wherein R⁴ and R⁵ are independently a C₁-C₂₀ aliphatic radical, a C₃-C₂₀ aromatic radical, a C₃-C₂₀ cycloaliphatic radical, or R⁴ and R⁵. taken together, form a 10- to 13- membered bicyclic or tricyclic aromatic or heteroaromalic ring system

[0011] According to some aspects of the invention. R⁴ and R⁵ may independently be a C₆-C₂₀ aliphatic radical, a C₆-C₂₀ aromatic radical, or a C₆-C₂₀ cycloaliphatic radical, or R⁴ and R⁵ taken together, form a 10- to 13-membered bicyclic or tricyclic aromatic or heteroaromatic ring system.

[0012] In yet another aspect, the present invention relates to compounds of formula VI. and optoelectronic devices having an electron-transporting layer containing these compounds

[0013] For the compounds of formula I to IV. Ar may be

. wherein R⁶ and R⁷ are independently a C₁-C₂₀ aliphatic radical, a C₃-C₂₀ aromatic radical, or a C₃-C₂₀ cycloalφhatic radical [0014] In some embodiments. Ar may be

wherein R is independently at each occurrence a direct bond.or an alkyl and c is an integer ranging from 2 to 6.

[0015] In some embodiments, Ar is independently chosen from

[0016| Examples of groups that may be used as Ar include

[0017| In some embodiments, R³ may be methyl. Examples of the organic compounds of formula I to VI include:

[0018| In particular embodiments, the organic compounds of formulas I to VI are chosen from

[0019] The compounds of formula I to Vl may be prepared by employing Suzuki cross-coupling reactions. General procedure for Suzuki cross-coupling reactions includes mixing an aryl halide and ary! borate (or boronic acid) in a suitable solvent, in the presence of a base and Pd catalyst. The reaction mixture is heated under an inert atmosphere for a period of time. Suitable solvents include but are not limited, to Dioxane, THF, EtOH. toluene and mixtures thereof. Exemplary bases include Na₂CO₃, K₂CO₃, CS₂CO₃, Potassium phosphate and hydrates thereof. The bases can be added to the reaction as a solid powder or as an aqueous solution. The most commonly used catalysis include Pd(PPh3)₄, or Pd(OACh, Pd(dba)2 with the addition of a secondary ligand. Exemplary ligands include dialkylphosphinobiphenyl ligands, such as structures VII-XI shown below, in which Cv is cvclohexvl.

[0020| In general there are al least hvo methods that may be used Io convert an aryl halide into its corresponding aryl borate. One method involves the generation of a carbanion using either BuLi to elTect a lithio-halogen exchange or by using Mg to generate a Grignard reagent, followed by quenching of the carbanion with a borate such as tri methyl borate, triethyiborate or tri(isopropyl)borate and the like. A typical procedure involves combining the starting materials in dry solvents such as THF or diethylether under anhydrous and inert conditions. The reaction is cooled to - 100°C or -80°C and BuLi is added dropwise and stirred at this temperature for a certain period of time (1-5 hours). After which time the intermediate carbanion is quenched with a suitable borate ester. The reaction mixture is allowed to warm to room temperature (RT). and. after stirring for 30 minutes at RT, the mixture is treated with a solution of saturated NH₄Cl (0.5 mL) and concentrated to dryness to afford a crude product.

[002I | The second method employs Pd-catalyzed borylation. A typical procedure includes combining an aryl halide and pinacolate diborane, anhydrous base and a dialkylphosphinobiphenyl ligand under dry and inert atmospheric conditions. The flask is protected from the atmosphere and charged with anhydrous solvent. After the solution is degassed for 15-30 minutes, the reaction mixture is charged with Pd catalyst and heated at reflux for an extended period by monitoring the disappearance of the starting aryl halide. Afterwards, the reaction mixture is cooled to RT and filtered. Upon concentration, the crude reaction product is afforded. Exemplary anhydrous bases include NaHCO₃, KHCO₃, and KOAc. Exemplary ligands include dialkylphosphinobiphenyl ligands, such as structures VII-XI and trans- dichlorobis(triphenylphosphine)palladium(II). [0022] An optoelectronic dev ice, e g . an OLED or a photovoltaic device, typically includes in the simplest case, an anode lav er and a corresponding cathode layer with an organic electroluminescent lav er disposed between said anode and said cathode When a voltage bias is applied across the electrodes, electrons are iniecied by the cathode into the electroluminescent laver while electrons are removed from (or "holes" are " injected" into) the electroluminescent layer from the anode Light emission occurs as holes combine with electrons within the electroluminescent lav er to form singlet or tπplet excitons. light emission occurring as singlet and/or tπplet excitons decay to their ground states v ia radiative decav

[0023| Other components which mav be present in an OLED in addition to the anode, cathode and light emitting material include a hole injection lav er an electron injection lav er, and an electron transport lav er The electron transport lav er need not be in direct contact w ith the cathode, and frequently the electron transport layer also serves as a hole locking layer to prevent holes migrating toward the cathode Additional components which mav be present in an organic light-emitting device include hole transporting layers, hole transporting emission (emitting) layers and electron transporting emission (emitting) layers

[0024| In one embodiment, an optoelectronic dev ice of the invention may be a fluorescent OLED compπsing a singlet emitter In another embodiment, the OLEDs may be a phosphorescent OLED comprising at least one tπplet emitter In another embodiment, the OLEDs comprise at least one singlet emitter and at least one triplet emitter The OLEDs mav contain one or more, any or a combination of blue, v ellow. orange, red phosphorescent dyes, including complexes of transition metals such as Ir. Os and Pt In particular, electrophosphorescent and eleclrofluorescent metal complexes, such as those supplied bv American Dv e Source. Inc . Quebec. Canada may be used Organic compounds of the formula 1 to VI mav be pait of electron transporting layer, or electron injection layer of an OLED

[0025J The organic electroluminescent laver. i e . the emissiv e lav er. is a lav er within an organic light emitting device which when in operation contains a significant concentration of both electrons and holes and provides sites for excilon formation and light emission A hole injection laver is a layer in contact w ith the anode which promotes the injection of holes from the anode into the interior layers of the OLED. and an electron injection layer is a layer in contact with the cathode that promotes the injection of electrons from the cathode into the OLED. an electron transport layer is a layer which facilitates conduction of electrons from the cathode and/or the electron injection layer to a charge recombination site During operation of an organic light emitting device comprising an electron transport layer, the majoπt} of charge carriers (i e holes and electrons) present in the electron transport layer are electrons and light emission can occur through recombination of holes and electrons present in the emissive laver A hole transporting layer is a layer which when the OLED is in operation facilitates conduction of holes from the anode and/or the hole injection layer to charge recombination sites and which need not be in direct contact with the anode A hole transporting emission layer is a layer in which when the OLED is in operation facilitates the conduction of holes to charge recombination sites, and in which the majoπts of charge carriers are holes, and in which emission occurs not onh through recombination with residual electrons, but also through the transfer of energ> from a charge recombination -cone elsewhere in the device An electron transporting emission layer is a layer in which when the OLED is in operation facilitates the conduction of electrons to charge recombination sites, and in sshich the majoπts of charge earners are electrons, and in sshich emission occurs not onls through recombination w ith residual holes, but also through the transfer of energj from a charge recombination zone elsesshere in the des ice

[0026| Materials suitable for use as the anode includes mateπals has ing a bulk resistivity of preferred about 1000 ohms per square, as measured bs a four-point probe technique Indium tin oxide (ITO) is frequenth used as the anode because it is substantialls transparent to light transmission and thus facilitates the escape of light emitted from electro-active organic layer Other materials, which mas be utilized as the anode layer, include tin oxide, indium oxide, zinc oxide, indium zinc oxide, zinc indium tin oxide, antimons oxide and mixtures thereof

[0027| Materials suitable for use as the cathode include general electrical conductors including, but not limited to metals and metal oxides such as ITO etc svhich can iniect negative charge carriers (electrons) into the inner layer(s) of the OLED Various metals suitable for use as the cathode include K. Li. Na Cs. Mg. Ca. Sr. Ba Al. Ag. Au, In, Sn. Zn. Zr, Sc. Y. elements of the lanthanide series, allo> s thereof, and mixtures thereof Suitable allo> materials for use as the cathode layer include Ag-Mg. Al-Li. In-Mg, Al-Ca. and Al-Au alloy s Layered non-alloy structures may also be employed in the cathode, such as a thin layer of a metal such as calcium, or a metal fluoride, such as LiF. co\ ered by a thicker layer of a metal, such as aluminum or silver In particular, the cathode may be composed of a single metal, and especially of aluminum metal

[0028] Organic compounds of formula 1 to VI may be used in electron transport layers in place of or in addition to traditional materials such as poly9,9-dιoctyl fluorene). tris(8-hydroxyquinolato) aluminum (AIq₃)- 2,9-dimethy 1-4 7-dipheny l- 1 I - phenanthrohne. 4,7-diphenyl-1.10-phenanthroIine. 2-(4-biphenylyl))-5-(4-l- butylphenyl)-l.3.4-oxadiazole, 3-(4-biphenylyl )-4-phenyl-5-(4-t-butylphenyl- 1.2.4- triazole. 1.3.4-oxadiazole -containιng poh mers. 1.3.4-triazole-comaining poh mers. quinoxaline-containing polymers, and cyano-PPV

[0029) Materials suitable for use in hole transporting layers include l, l-bis((di-4- tolylamino) phenyl)cyclohexane N.N'- bis(4-meth\ lphem l)-N.N'-bis(4-eth> lphem I)- ( 1,1'-(3.3'-dimethy l)biphenyl)-4.4'-diamine. tetrakis-(3-meth\ lphem l)-N.N.N'.N'-2 5- phem lenediamine phenyl l-4-N.N-diphenylaminosty rene. p-(diethy lamino) benzaldehyde dιphenyl dragone ttriphenylamine,. l -phenyl-3-(p-

(diethylamιno)styryl)-5-(p-(dιeth\ lamιno)phenyl)yrazoline 1 2-lrans-bis(9H- carbazol-9-\ l)cyclobulane. N.N.N'.N'-telrakis(4-meth\ lphem l)-( 1.1 '-biphenyl)-4 4'- diamine copper phthalocyanine polyvinylcarbazole. (phenyl/methyl)polysιlane. pol\ (3.4- ethylendioxythιophene) (PEDOT) polvanihne. polyvynylcarbazole triaryldiamine. tetraphenyldiamine. aromatic tertian amines, hydrazone derivatives, carbazole derivatives, triazole derivatives. imidazole derivatives. oxadιazole derivatives having an amino group, and polythiophenes as disclosed in U S Pat No 6.023.371 [0030] Materials suitable for use in the light emitting layer include electroluminescent poh mers such as polyfluorenes. preferabK polv(9.9-dioct\ I fluorene) and copoK nners thereof, such as poI\ (9.9'-dioch inuorene<O-bis-N.N

lphenyl)diphen\ larrune) (F8-TFB). pol\ (vinylcarbazole) and poh phem lene\ in\ lene and their deπ\ atι\ es In addition, the light emitting layer mav include a blue, \ ello\v, orange, green or red phosphorescent dv e or metal complex, or a combination thereof Materials suitable for use as the phosphorescent d> e include, but are not limited to. lns(l- phem lisoquinoline) indium (III) (red d\ e) tπs(2-phen> lp\ πdine) indium (green d\ e) and Indium (IFI) bis(2-(4.6-dιfluorephen\ l)p\ πdinato-N C2) (blue d\ e) Commerciallv a\ aιlable electrofluorescenl and electrophosphorescent metal complexes from ADS (Ameπcan

es Source, lnc ) ma> also be used ADS green d\ es include ADS060GE, ADS06I GE. ADS063GE. and ADS066GE. ADS078GE. and ADS090GE ADS blue

es include ADS064BE. ADS065BE. and ADS070BE ADS red d\es include ADS067RE. ADS068RE. ADS069RE. ADS075RE. ADS076RE. ADS067RE. and ADSO77RE

[0031] Organic compounds of formula I to VI ma\ form part of the electron transport lav er Thus, in one aspect, the present invention relates to more efficient optoelectronic de\ ices, e g , OLEDs comprising organic compounds of formula I to VI The OLEDs ma> be phosphorescent containing one or more, am or a combination of, blue, vellow. orange, red phosphorescent d> es

DEFINITIONS

100321 As used herein, the term "aromatic radical^" refers to an amrs of atoms ha\ ing a \ alence of at least one comprising at least one aromatic group The arra\ of atoms ha\ ing a valence of at least one compπsing at least one aromatic group mav include heteroatoms such as nitrogen sulfur, selenium, silicon and ow gen. or ma> be composed exclusn eh of carbon and hydrogen As used herein, the term " aromatic radical^" includes but is not limited to phenvl. p\ πd\ l. furam l thienyl, naphthx l. phem lene. and biphem I radicals As noted, the aromatic radical contains at least one aromatic group The aromatic group is invariabK a c\ clic structure hax ing 4n+2 "delocalized^" electrons where "n^" is an integer equal to I or greater, as illustrated b\ phen\ 1 groups (n = 1). thiem 1 groups (n = 1) furanvl groups (n = I ) naphth\ 1 groups (n = 2) azulen\l groups (n = 2) and anthracenes 1 groups (n = 3) The aromatic radical ma\ also include nonaromalic componenls For example, a benz> I group is an aromatic radical which comprises a phem I ring (the aromatic group) and a melh\ lene group (the nonaromatic component) SimilarK a telrahx dronaphthx 1 radical is an aromatic radical comprising an aromatic group (C₆H-,) fused to a nonaromatic component -(CH₂).»- For convenience, the term "aromatic radical^" is defined herein to encompass a wide range of functional groups such as alk\ I groups, alkem I groups alk\n\l groups. haloalk\l groups, haloaromatic groups conjugated dieml groups alcohol groups, ether groups. aldeh\des groups, ketone groups carbowlic acid groups, acyl groups (for example carboxjlic acid dernatnes such as esters and amides), amine groups, nitro groups and the like For example, the 4-meth\lphen\l radical is a C7 aromatic radical compπsing a meth\l group, the meth>l group being a functional group which is an alkλl group Similarh. the 2-nitrophem 1 group is a CV. aromatic radical compπsing a nitro group, the nitro group being a functional group Aromatic radicals include halogenated aromatic radicals such as 4- tπfluorometh\lphen\l. hexafluorotsoprop\hdenebis(4-phen-lΛlo\\) (1 e.

-OPhC(CF^PhO-). 4-chloromethλlphen-l->l, 3-lπfluoro\in\l-2-thιen\l. 3- tπchlorometrnlphen-l-N I (1 e . 3-CChPh-). 4-(3-bromoprop-l-\ l)phen- 1 -\ 1 (1 e .4- BrCH₂CH₂CH₂Ph-). and the like Further examples of aromatic radicals include 4- alh lox\ phen- 1 -ox\ .4-aminophen-l-\l (ιe. 4-H₂NPh-) 3-aminocarbon\lphen-l-\l (1 e . NH₂COPh-).4-ben/co\lphen-l-\l. dic\anometh\lidenebis(4-phen-l-\lo\\) (1 e . -OPhC(CN)₂PhO-). 3-meth\lphen-l-\l. meth\lenebis(4-phen-l-\lox\) (1 e . - OPhCH₂PhO-). 2-eth\lphen-I-\l. phemlethenyl, 3-form\ l-2-lhienx 1. 2-hex\l-5- furaml. hexameth\lene-1.6-bis(4-phen-l-\loxy) (ie, -OPh(CH₂)₆PhO-). 4- h\drox\meth> lphen-1-vl (1 e . 4-HOCH₂Ph-). 4-mercaptometh\ lphen-l-\l (1 e . 4- HSCH₂Ph-). 4-meth\lthiophen-l-\I (1 e . 4-CH_^1SPh-). 3-methoxyphen-l-\l. 2- melhox\carbonylphen-lΛ lox> (eg meth\l salic\l), 2-nilrometh\lphen-l-\l (1 e . 2- NO₂CH₂Ph).3-tπmethylsilvlphen-l-vl.4-t-bunldιmethylsilylphenl-l-\l.4-\ιnvlphen- 1-\1. \ in\ lidenebιs(phen\ 1) and the like The term "a C-, - do aromatic radical^" includes aromatic radicals containing at least three but no more than IO carbon atoms The aromatic radical l-imida7ol\l (CNHhN₂-) represents a CN aromatic radical The benzvl radical (C7H₇-) represents a C7 aromatic radical

[0033| The term 'heteroaromatic πng" refers to a mono\alent 5 or 6 membered monocyclic heteroaromatic πng containing carbon atoms and one or more heteroatoms selected from the group consisting of owgen. nitrogen and sulfur Representative examples of heteroaromatic groups are included thioazole. p\πdin>l. furam 1. p\ πd\ I. pv rroK 1. pyrazinvl. p% πmidim I. pv πdazin\ 1, thiem I (or thiophem 1). thiazohl. imidazoM p\razoKI tπazohl. tetrazohl oxazohl. isooxazoh 1 o\adiazol> 1. isolhιazol\ 1. and lhiadιazol\ I

[0034| As used herein the term "c> cloaliphatic radical^" refers to a radical having a \alence of at least one. and comprising an array of atoms which is c\ die but which is not aromatic As defined herein a "c\cloahphatic radical^" does not contain an aromatic group A "c\ cloaliphatic radical may comprise one or more nonc\chc components For example, a c\ clohexv Imethv 1 group (CcHi 1CH₂-) is an c\ cloaliphatic radical which compπses a csclohewl πng (the arra\ of atoms which is c.vclic but which is not aromatic) and a meth\lene group (the noncvclic component) The c> cloaliphatic radical ma> include heteroatoms such as nitrogen sulfur, selenium, silicon and oxvgen. or ma> be composed exclusneh of carbon and h\drogen For convenience, the term c> cloaliphaiic radical^" is defined herein to encompass a wide range of functional groups such as alk> 1 groups alkeml groups, alkvml groups. haloalk\l groups, conjugated diem I groups, alcohol groups ether groups aldehxde groups, ketone groups, carboxslic acid groups ac\l groups (for example carbowlic acid derivatives such as esters and amides), amine groups, nitro groups, and the like For example, the 4-methylc>clopent-l-\l radical is a Cr, c\ cloaliphatic radical comprising a meth\l group, the meth\l group being a functional group which is an alk\l group Sirrularl\. the 2-nιtroc>clobut-l-\ 1 iadical is a C₄ c\ cloaliphaiic radical comprising a nitro group, the nitro group being a functional group A c\ cloaliphatic radical ma\ comprise one or moie halogen atoms which max be the same or different Halogen atoms include, for example, fluoπne. chlorine, bromine, and iodine C\ cloaliphatic radicals comprising one or more halogen atoms include 2-tnfluorometrr\lc>clohe\-l-\l, ^bromodifluorometrnlcNcloocl-l-vl. 2- chlorodifluoromethylcycloriex-l-yl, he.\afluoroisopropylidene-2.2-bis (cyclohex-4-yl) (i.e., -C₆HioC(CF_?)2 C₆Hi₀-X 2-chiorometh\ϊcyclohex- l -yl, 3- difluoromethylenecyclohex-I -yl, 4-trichloromethylcyclohex- l -yloxy, 4- bromodichloromelhylcyclohex- 1 -ylthio, 2-bromoethy lcyclopent- 1 -yl. 2- bromopropylcyclohex- l -yloxy (e.g. CHiCHBrCH₂C₆HiOO-). and lhe like. Further examples of cycloaliphatic radicals include 4-allyϊoxycyclohex- l -yl, 4- aniinocyclohex-1-yl (i.e... H₂NC₆H₁₀-), 4-aminocarbonylcyclopent-l-yl (i.e.. NH₂COC₅Hx-), 4-acetyloxycyclohex-l -yl. 2,2-dicyanoisopropylidenebis(cycloheχ-4- yloxy) (i.e., -OC₆Hi_OC(CN)₂CnH_1OO-), 3-methylcyclohex- l-yl, methyIenebis(cyclohex-4-yloxy) (i.e., -OC₆H _IOCH₂C₆H _IOO-), I -ethylcyclobut- 1 -yl, cyclopropylethenyl, 3-fbrmyl-2-terahydrofuranyl, 2-hexyl-5-tetrahydrofuranyl, hexamelhylene-l ,6-bis(cyclohex-4-yIoxy) (i.e., -O C₆HiO(CH₂)OC₆H₁OO-), 4- hydroxymethylcyclohex- 1 -yl (i.e., 4-HOCH₂C₆H 10-). 4-mercaptomethylcyclohex- 1 -y 1 (i.e.. 4-HSCH₂C₆HiO-), 4-methyllhiocyclohex-l -yl (i.e., 4-CH^SC₆H₁₀-), 4- melhoxycyclohex-1 -yl, 2-methoxycarbonylcyclohex-l -yloxy (2-CH^OCOC₆H ₁0O-), 4-nitromethylcyclohex- l-yl (i.e., NO₂CH₂C₆HiO-), 3-trimethylsilylcyclohex-l -yl, 2-t- bulyldimethylsilylcyclopent- 1 -yl, 4-trimethoxysilylethvlcyclohex- 1 -y I (e.g. (CH₃O)₅SiCH₂CH₂C₆Hi₀-), 4-vinylc) clohexen- 1 -yl, vinylidenebis(cyclohexyl)_? and the like. The term "a C3 - C 10 cycloaliphatic radical^" includes cycloaliphatic radicals containing at least three but no more than 10 carbon atoms. The cycloaliphatic radical 2-tetrahydrofuranyl (C₄H7O-) represents a C4 cycloaliphatic radical. The cyclohexy I methyl radical (C₆HnCH₂-) represents a C₇ cycloaliphatic radical.

[0035| As used herein the term "aliphatic radical^" refers to an organic radical having a valence of at least one consisting of a linear or branched array of atoms which is not cyclic. Aliphatic radicals are defined to comprise at least one carbon atom. The array of atoms comprising the aliphatic radical may include heteroatoms such as nitrogen, sulfur, silicon, selenium and oxygen or may be composed exclusively of carbon and hydrogen. For convenience, lhe term "aliphatic radical^" is defined herein to encompass, as part of the "linear or branched array of atoms which is not cyclic^" organic radicals substituted with a wide range of functional groups such as alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, conjugated dienyi groups, alcohol groups, ether groups, aldeh\ de groups, ketone groups, carbow lie acid groups. ac\ l groups (for example carbox\ lιc acid deriv atives such as esters and amides), amine groups, nitro groups, and the like For example, the 4-meth\ 1 pent- 1 -y I radical is a Ce aliphatic radical comprising a meth\ l group, the methyl group being a functional group which is an alk\ l group Similarly, the 4-nitrobut- l-yl group is a C4 aliphatic radical composing a nitro group, the nitro group being a functional group An aliphatic radical ma> be a haloalk> 1 group which comprises one or more halogen atoms which ma> be the same or different Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine Aliphatic radicals comprising one or more halogen atoms include the alk\ l halides tπfluoromethvl. bromodifluorometh\ l. chlorodifluorometh\ l, hexafluoroisopropylidene, chlorometh> 1. difluorovim lidene. tπchloromethλ l. bromodichloromethyl, bromoethv l. 2-bromotπmeth> lene (e g - CH2CHBrCH2-). and the like Further examples of aliphatic radicals include alls I. ammocarbom 1 (1 e . -CONH2). carbom l. 2.2-dιc\ anoιsoprop\ lιdene (1 e . - CH₂C(CN)₂CH₂-). meth\ I (1 e . -CH-,). melh\ lene (1 e . -CH₂-). eth> I. ethylene, forrm I (1 e -CHO). hex> l. he\ameth\ lene. h\ drox> methyl (1 e -CH₂OH). mercaptometh\ 1 (i e . -CH₂SH). meth\ llhio (1 e . -SCH-,). meth> lthιometh> 1 (1 e . -CH₂SCHi). methoχ\ . methox) carbom 1 (ι e . CH-OCO-) . nitrometh\ l (ι e . -CH₂NO₂). thiocarbonyl. tπmeth> IsiK l (1 e . (CHO'-Si-). l-butx ldimeth> lsil> I. 3- lπmeth\ o\\ sil\ prop\ l (1 e . (CH^OhSiCH₂CH₂CH₂-). \ in\ l. \ 1n\ l1dene. and the like B\ wav of further example, a Ci - do aliphatic radical contains at least one but no more than I O carbon atoms A meth> l group (1 e . CH^-) is an example of a Ci aliphatic radical A dec\ l group (1 e . CH~,(CH2)c>-) is an example of a do aliphatic radical

[0036| The term ' heteroan I^" as used herein refers to aromatic or unsaturated πngs in which one or more carbon atoms of the aromatic nng(s) are replaced b\ a heleroatom(s) such as nitrogen. ox\ gen. boron, selenium, phosphorus, silicon or sulfur Heleroaπ l refers to structures that ma\ be a single aromatic ring, multiple aromatic πng(s) or one or more aromatic πngs coupled to one or more non-aromatic πng(s) In structures ha\ ιng multiple rings, the πngs can be fused together linked co\ alentl\ . or linked to a common group such as an ether. meth\ lene or ethy lene moiety The common linking group ma\ also be a carbom I as in phem I p\ πdvl ketone As used herein, rings such as ihiophene. pv πdine. ιso\azole. p\ razole. p\ rrole. furan. etc or benzo-fused analogues of these rings are defined b\ the term "heleroan I ^""

[0037| The term "arv r is used herein to refer to an aromatic substituent which max be a single aromatic πng or multiple aromatic πngs which are fused together, linked co\ alently. or linked to a common group such as an ether, methy lene or ethylene moiet} The aromatic πng(s) may include phem I. naphth\ l. anthracenvl. and biphem l. among others In particular embodiments, aryls ha\ e between 1 and 200 carbon atoms, between 1 and 50 carbon atoms or between 1 and 20 carbon atoms

(0038) The term "alk> I^" is used herein to refer to a branched or unbranched. saturated or unsaturated acx clic

drocarbon radical Suitable alk\ l radicals include, for example. meth\ 1, eth\ 1.

1. i-prop\ I. 2-propen\ 1 (or alh I). \ in\ I.

I. t- butyl. l-buh l (or 2-meth\ lprop\ 1). etc In particular embodiments, alks ls ha\ e between I and 200 carbon atoms, between 1 and 50 carbon atoms or between I and 20 carbon atoms

[0039| The term

cloalk> l^" is used herein to refer to a saturated or unsaturated CN clic non-aromatic h> drocarbon radical hav ing a single ring or multiple condensed rings Suitable c\ cloalk\ l radicals include, for example. c\ clopenv\ l. c> clohexvl. c\ cloocten\ l. bιc\ clooct> l. etc In particular embodiments. Cλ cloalkv ls ha\ e between 3 and 200 carbon atoms, between 3 and 50 carbon atoms or between 3 and 20 carbon atoms

[0040| Am numerical values recited herein include all v alues from the lower v alue to the upper value in increments of one unit prov ided that there is a separation of at least 2 units between anv lower \ alue and am higher value As an example, if it is stated that the amount of a component or a \alue of a process v ariable such as. for example, temperature, pressure, lime and the like is. for example, from I to 90. preferably from 20 to 80. more preferably from 30 to 70. it is intended that values such as 15 to 85. 22 to 68. 43 to 51. 30 to 32 etc are expressK enumerated in this specification For v alues which are less than one. one unit is considered to be 0 0001 0 001. 0 01 or C) I as appropriate These are onl\ examples of what is specificalh intended and all possible combinations of numerical values between the lowest value and the highest \alue enumerated are to be considered to be expressh stated in this application in a similar manner

EXAMPLES

[0041 | Examples 1 -16 describe the sy ntheses of compounds of the inv ention and intermediates used in making them All reagents were purchased from Aldrich Chemical Co . Milwaukee. Wl. USA unless other w ise specified and were used w ithout further purification All compounds were characteπzed b\ ¹H-NMR and found to correspond to the structures shown

EXAMPLE I S\ nthesis of compound 1

[0042| 4-bromo-3-meth> 1 phem I dιaza-carbazole(compound 9. 0 338 g. 0 1 mmol) and 0.25 g (0 05 mol) of 9.9-dιhexv lfluorene-2.7-diboronιc acid bιs(eth\ IgK col) ester (compound 10) were placed into a 50 mL of three neck flask 10 mL of dioxane and 10 mL of K2CO, (2N aqueous solution) were added to the flask The mixture was evacuated and filled w ith argon three times and then a \er\ small pinch of Pd(PPhOa was added The mixture was stirred and ev acuated and filled with argon three limes The flask was immersed in an oil bath and refiuxed overnight After the solution was cooled to room temperature, the solvent was remov ed by roto-ev aporation to afford caide product The crude product was re-dissolv ed into methy lene choloπde and water mixture (1 1. 50 mL) The organic and aqueous lav er was separated The organic layer was w ashed w ith water (10 mL x2) and brine (10 mLx l ) The mixture was concentrated and loaded onto an AIO2 basic sample cartridge The sample was eluled out using THF with 2% methanol using combi-flash s\ slem The fractions w as concentrated and chilled in a refrigerator ov ernight, this collected 0 1 136 g of the

I S product ¹H NMR (CDCIi. δ) 9 46 (s. 4H). 8 62 (d. 4H). 7 90 (d. 2H). 7 64 (d. 2H) 7 54 (b. 2H), 7 49 (d, 4H). 7 45 (dd, 6H). 2 48 (s, 6H), 2 10 (m, 4H). 1 15 (m. 12H). 0 81 (tm, 10H) Maldi (M+ = 849 12)

EXAMPLE 2 Sy nthesis of compound 10

[0043| A solution of 9.9-dιhex\ lfluorene-2.7-bιs-boronιc acid (2 9 g. 6 9 mmol) and ethy lene gh col ( 1 7 g, 27 5 mmol) in chloroform (20 ml) was heated at reflux for 1 hour The cooled mixture was diluted with saturated sodium chloπde and the organic layer was passed through a cone of anhvdrous CaSθ₄ (Diieπle) Evaporation of soh ent afforded 3 g of a solid mass that was recr\ siallιzed from acetonitπle to afford 2 34 g (72%) of the product as a white solid ¹H NMR (CD₂CI₂) δ 7 8 (m. 6. ArH). 4 48 (s. 8. OCH₂). 2 05 (01.4.Ar₂CCH_JiCsHi,). I I (m. l 2.alιphatic CH₂). 0 75 (1.6.CH₂CH,) and 0 60 ppm (m.4.penullimate CH₂)

EXAMPLE 3 S> nthesis of compound 2

[0044| 4-Bromo-3-meth\ 1 phen\ 1 diaza-carbazole (compound 9. 0 3486 g. 1 03 1 mmol) and 0.3422 g (0 5028 mmol) of 2^".7^"-di-t-but\ l spιrofluorene-2.7-diboronic acid bιs(neopent\ I diol) ester (compound 1 1 ) were placed into a 50 mL of three neck flask 10 mL of dioxane and I O mL of K₂CO; (2N aqueous solution) were added to the flask The mixture was e\ acuated and filled with argon three times and then a \ ery small pinch of Pd(PPIu)₄ was added The mixture was stirred and e\ acuated and filled w ith argon three times The flask was immersed in an oil bath and refluxed o\ ernight After the solution was cooled to room temperature, the soKent was renxned b> rolo- evaporation to afford crude product The crude product was re-dιssol\ ed into methylene choloride and water mixture ( 1 1. 50 mL) The organic and aqueous

was separated The organic layer was washed with water (I O mL x2) and brine ( IO mL x 1 ) The mixture was concentrated and loaded onto an AIO₂ basic sample cartridge. The sample was eluted out using THF with 2% methanol using combi-flash system. The fractions was concentrated and chilled in a refrigerator overnight, this collected 0.10 g of product.

EXAMPLE 4: Synthesis of compound 1 1

[0045| A solution of 2.7-dibromo-2\7^'-di-tert-butylspirofluorene (5.86 g. 10 mmol) in anhydrous diethylether (100 ml) was cooled to -78°C and treated dropwise with a solution of n-butyllithium ( 1.6 M in hexane, 20.8 mmol). The stirred mixture was allowed to warm to ambient temperature and stirring was continued for an additional hour. The resulting slurry was re-cooled to -78 ⁰C and treated with isopropoxypinacol borate (4.65 g, 25 mmol). The mixture was again allowed to warm to ambient temperature and was stirred an additional 3 hours. The mixture was quenched by- addition of water (25 ml) and toluene (50 ml) was added. Combined organic washings

9 were dried (CaSO.0 and solvent was removed under vacuum to afford a while solid that was recrystallized from toluene to afford 3.7 g (55%) of the bis borate. ¹H NMR (CD₂Cl₂) δ 7.9-6.6 (m, 12,ArH), 1.30 (s.24,bprate CH3 s) and 1.20 ppm (s, 1 H.tBu).

EXAMPLE 5: Synthesis of compound 3

[0046| N-(3-methyl-4-bromo phenyl) diaza carbazole (compound 9, 1.314 g, 3.88 mmol) and |9.9-bis|4-(hexyloxy)phenyl |-fluorene-2.7-diyi|bis- 1.3,2-dioxaborolane (compound 12. 1.2793 g. 1.94 mmol) were weighed out into a 100 mL of three neck round bottom flask. To this flask, 40 mL of dioxane and 40 mL of K₂CO-, (2N) were added. The mixture was degassed using argon for 30 minutes. Then a pinch of Pd(PPh_?)α was added. The reaction was heated under reflux for overnight. The entire mixture was evaporated to dryness using roto-evaporation. The residue was re- dissolved in a 200 mL of CH₂CI₂ and 100 mL of water mixture. The organic layer and aqueous layer was separated. The organic layer was washed with water ( 100 mL\2) and brine (100 mLxl ). After dried over Na₂SOa. the solvent was removed and the crude product was separated using alumina basic column with THF/hexanes as the eluting solvent. ().% g of product was obtained. ¹H NMR (CDCb₅ δ) 9.46 (s. 4H), 8.62 (d, 4H), 7.94 (d. 2H). 7.55 (d, 2H). 7.49 (s, 2H), 7. 47 (dd. 2H). 7.45 (s. 2H), 7.43(s+d, 4H), 7.39 (d, 2H), 7.24 9d. 2H), 3.91 (t. 4H). 2.40 (s, 6H), 1.76 (m. 4H). 1.44 (b. 4H), 1.33 (m. 8H), 0.90 (s, 6H). Maldi (M+ 1033.6000)

EXAMPLE 6: Synthesis of compound 4

[0047] 4-bromo-3-methyl phenyl diaza-carbazole (compound 9, 0.6216 g, 1.83 mmol) and 0.2377 g (0.5743 mmol) of l,3,5-benz.ene triboronic acid bis(neopentyl diol) ester (compound 13) were placed into a 50 mL of three neck flask. 25 ml_ of dioxane and 10 mL of K₂COj (2N aqueous solution) were added to the flask. The mixture was evacuated and filled with argon three times and then a very small pinch of Pd(PPIh)₄ was added. The mixture was stirred and evacuated and filled with argon three times. The flask was immersed in an oil bath and refluxed overnight After the solution was cooled to room temperature, the product was precipitated out. The solid product was collected by centrifuge and washed with water acetone couple of times. Maldi (M+850.6234), ¹H NMR (CDCI₅, δ) 9.49 (s, 6H), 8.65 (d. 6H), 7.70 (d, 3H), 7.59 (s. 3H). 7.53 (m, 3H), 7.49 (dd, 3H), 7.44 (d. 6H)_.. 2.27 (s. 9H).

EXAMPLE 7: Synthesis of compound 13

[0048| Step 1. A flame dried 100 ml flask equipped with an overhead stirrer was charged with small Mg turnings (3.65 g, 150 g-atom). chlorolrimethylsilane ( 16 g. 140 mmol). 1 ,2-dibromoelhane ( 100 mg) and anhydrous THF (40 ml). To the stirred mixture was added over I hour 1.3,5-tribromobenzene ( 12.5 g. 39.7 mmol). The reaction mixture began to reflux almost immediately on addition of the aryl bromide. When the exothermic reaction subsided the mixture was heated at reflux for 16 hours. On cooling, the mixture solidified to a hard cake. The liquid phase was decanted from the solid MgBr₂ and the solids were washed repeatedly with ether. Combined ether extracts were washed with water and brine then stripped to afford 1 1.4 g of a dark oil. The oil was chromatographed on ~ 100 g of silica gel eluted with hexane.

[0049] Step 2. A flame-dried 10 ml flask was charged with purified tris- trimethylsilylbenzene prepared as described in step I , (395 mg₇ 1.34 mmol). To this was added BBr₅ (700 μl, 1.85 g, 7 4 mmol). The resulting mixture was heated at reflux (~ 90^°C) for 35 hour. The mixture was cooled to room temperature and excess BBr-, was removed by vacuum distillation. The residue was diluted with hexane and allowed to stand at room temperature overnight. Water was added cautiously followed by a mixture of methanol and neopentyl glycol. The mixture was stripped to near dryness and the residue was stirred with methanol to dissolve excess neopentyl glycol and deposit the product as a white solid (84%). ¹H NMR (CH₂CI₂) δ 8.35 (sJ.ArH). 3.80 (s.12.borate OCH₂) and I O ppm (s. l 8.borate CH_:/s)

EXAMPLE 8 Synthesis of compound 5

[0050| N-(3,5-dimethy!-4-bromo phenyl) diaza carbaκole (compound 14. 1.21 g. 3.4 mmol) and [9,9-bis|4-(hexyloxy)phenyl|-fluorene-2.7-diyl|bis- l ,3.2-dioxaborolane (compound 12, 0.7539 g. 1. 14 mmol) were weighed out into a 500 mL of three neck round bottom flask. To this flask. 34 mg of Pd(OAc)₂ and 220 mg of 2- dicyclohexylphosphino-2 \6^"-dimethoxybiphenyl were added, followed by 200 mL of toluene. The solution was degassed using a stream of argon. In a separate flask. 3.7 g of water and 3.7 g of tetraethylamonium hydroxide were combined and degassed using a stream of argon for 15 minuntes. The base solution was added to the toluene solution in a drop wise fashion. The toluene solution was brought to 80 ⁰C under argon and stirred overnight. The second day, upon cooling, the solution was filtered and evaporated to dryness. The residue was separated using alumina basic column with THF as the eluting solvent. 0.6 g of product was obtained. ¹H NMR (CDCl₃, δ) 9.49 (s, 4H), 8.65 (d, 4H). 7.98 (d, 2H), 7.45(d. 4H), 7.33 (s, 2H), 7.31 (dd. 2H). 7.27(s. 4H), 7.22(d, 4H), 3.92 (t. 4H), 2. 16 (s. 12H), 1.76 (m. 4H), 1.44 (b. 4H), 1.33 (m, 8H), 0.90.(s, 6H). Maldi (M+ = 1061.7932)

EXAMPLE 9: Synthesis of compound 14

{00511 N-(3,5-dimethyl phenyl) diaza carbazole (compound 15, 1.3 g, 4.7 mmol) was gradually added to 5 mL of concentrated H₂SO4, which was chilled in ice water. 0.485 mL of bromine was added over H) minutes. The mixture was gradually warmed up to room temperature and refluxed for 24 hours. The reaction mixture was poured into 40 mL of ice water and diluted by THF (20 mL). After the solution was neutralized by Na₂CO.; (8.8 g), the organic layer was separated and removed. The residue was extracted with 30 mL of THF and 2 mL of methanol mixture. The insoluble material was discarded. THF and methanol mixture was concentrated to afford crude product as a mixture of two isomers. After crystallization from acetonitrile, only desired symmetrical mixture was collected. ¹H NMR (CDCI₃, δ) 9.47 (s, 2H), 8.62 (d, 2H), 7. 34 (dd, 2H), 7.25 (s, 2H)_: 2.56(s. 6H).

EXAMPLE 10: Synthesis of compound 15 NH₂

\\ //

Pd(dba),, NaOCjH₉I <\ J

[00521 To 9 38 mL of l ,2-dιmetho\> ethane (DME). Pd(dba)₂ (0 495 g. 0 0X735 mmol) and ITF (041 Ig, 0 08735 mmol) were added and the mixture was stirred at 45 °C for 20 minutes To this mixture, dimethv I aniline (3 53 g, 0 029 mol). compound 16 (6 47 g. O 03 mol). tBuONa (7 18 g. 0 0745 mol). and DME (84 mL) were added This mixture was reflαxed overnight The next da> . the solution was cooled at 50 ⁰C Saturated NaCl aqueous solution (36 mL) was added, the insoluble solid was sepaiated by nidation, then the residue was washed with THF (50 mL) The υiganic laver of filtrate was separated, the solvent was removed under reduced pressure The first crop of product was obtained b\ extracting the solid using eth\ lacetate A second crop of product was collected b> adding hexane into ethv I acetate solution Combined to gne 85% of v ield

EXAMPLE l I Synthesis of compound 16

H

BN POCI₃

N ^y cf V

N AJ₂O, Cl

16

[0053| 2.2^"-Dιh\ dro\> -5.5^"-bιp> πdine (92 67 g 0 14 mmol) was added to 8 5 mL of phosphorus ox\ -chloride and was refluxed for an hour Then excess amount of phosphorus oxv -chloride was removed under reduced pressure The residue was diluted b> toluene (7 7 mL). and was slo\vl\ added ice water within 60 ⁰C for an hour To this mixture, 42 mL of eth> 1 acetate was added The mixture was neutralized using K₂CO^ until the PH was basic The precipitate was removed b> filtration and the filtrate was separated Organic lav er was combined and washed w ith equal amount of water and saturated brine solution The soh ent was removed and the solids were redissohed into eth> I acetate/toluene ( 1/4) mixture and 18 g of Al₂O-, was added The mixture was stirred for 40 minutes, then AbO- was filtered and soh ent was removed The crude product was re-cr> stallized from hexanes to obtain I 7 g of desired product

EXAMPLE 12 Preparation of compound 6

[0054] A degassed mixture of compound 17 (385 mg. 1 0 mmol). compound 18 (367 mg. 0 5 mmol). Pd(OAc)₂ (4 5 mg. 0 02 mmol). tπ-o-toK lphosphine (21 4 mg. 0 07 mmol). letraelh\ lammonium hs droxide (7 4 g of a 10% aqueous solution) and toluene (20 ml) was heated under nitrogen for 18 hours at 70 C The cooled mixture was diluted w ith toluene, filtered through Celite and transferred to a separator) funnel The organic phase was washed with water (2 x 50 ml) and saturated NaCI ( 1 x 50 ml) Removal of solvent afforded a residue that was chromatographed on silica gel eluted w ith a methanol/meth\ lene chloride gradient The product, compound 6. was obtained as a colorless foam

EXAMPLE 13 Preparation of compound 7

[0055) A degassed mixture of compound 1 7 (385 mg. 1 0 mmol). compound 19 (367 mg. 0 5 mmol). Pd(OAc)₂ (4 5 mg. 0 02 mmol). tπ-o-tol> lphosphine (21 4 mg. 0 07 mmol). tetraethylammonium hydroxide (7.4 g of a 10% aqueous solution) and toluene (20 ml) was heated under nitrogen for 18 hours at 70 C. The cooled mixture was diluted with toluene, filtered through Celite and transferred to a separatory funnel. The organic phase was washed with water (2 x 50 ml) and saturated NaCl ( 1 x 50 ml). Removal of solvent afforded a residue that was chromatographed on silica gel eluted with a methanol/methylene chloride gradient. The product, compound 7, was obtained as a colorless foam.

Example 14: Preparation of compound 17

[0056| A degassed solution of compound 9 (3.98 g, 1 1.76 mmol), bis- pinacolatodiborane (4.48 g. 17.6 mmol), potassium acetate (5. 19 g. 52.9 mmol) and Pd(OAc)₂ (0.26 g, 1. 176 mmol) in N-melhylpyrrolidinone ( 100 ml) was heated under nitrogen at 128 C for 16 hours. The cooled mixture was filtered through silica gel. The filtrate was diluted with ethyl acetate (150 ml) and transferred to a separatory funnel. The solution was washed with cold IN HCl (3 x 150 ml), water ( 1 x 150 ml) and saturated NaCI (I x 100 ml). Removal of solvent afforded a residue that was chromatographed on silica gel eluted with 50-100% ethyl acetate-hexane to afford 1.4 g (30%) of the desired product.

Example 15: Synthesis of compound 18

[0057] A 250 ml flask fitted with a magnetic stirrer and a distillation head was charged with 2.7-dibromo-9_:9-bis-4-hydroxyphenyIfiuorene (5.08 g, 10 mmol) and toluene ( 130 ml). The flask and solids were azeolropically dried by distillative removal of approximately 100 ml of toluene. The flask was then charged with DMF (150 ml), K₂CO_? (5.80 g. 42 mmol) and N-2-chloroethylmorpholine (3.91 g. 21 mmol). This mixture was healed at 90 C for 4 days. The cooled mixture was poured into 400 g of ice water and the residue was extracted with 3 x 200 ml of ethyl ether. The combined ether washes were washed with water (3 x 150 ml) and brine ( I \ 100 ml), then stπpped to afford an oil that was triturated with cold ether to afford 8 g of a fluffy white powder that w as chromatographed on 80 g of neutral alumina to afford the product as a white solid. ¹H NMR (CD₂Cl₂) δ 7.7-7.4 (mAfluorene-H^'s). 4.08 0.4.ArOCH₂). 3.68 (t.8,morpholine-OCH₂). 2.78 (t_;4.N-CH₂CH₂Oar) and 2.58 ppm (t_;8. morpholine-N-CHys)

Example 16: Synthesis of compound 19

[0058| Step 1. Preparation of 2,7-dibromo-9.9-bis-(4-hydroxy-3- carbomethoxy)phenylfluorene. A mixture of 2.7-dibromofluorenone ( 16 g, 4.76 mmol). methyl salicylate (76 g. 500 mmol), methanesulfonic acid ( 100 ml) and an ion exchange resin having bound mercapto groups (6.0 g) was stirred mechanically at 70 C for 16 hours The cooled mixture was poured inlo I liter of ice water, diluted w ith ~ 650 ml of eth\ l acetate, then filtered to remov e the ion exchange resin The aqueous phase was discarded and the organic phase was washed with water (2 \ 300 ml) and brine (I \ 300 ml), then passed through a cone of anrrs drous CaSO, Remov al of solv ent under v acuum afforded a residue that was diluted with hexane and chilled to deposit a white solid that was recrs stalhzed from toluene to afford 17 4 g (60%) of the product as a white solid ¹H NMR (CH₂CI₂) δ 10 8 (s.2.ΛrOH). 8 0-6 9 (m.12.ArH). and 3 90 (s.6. ArCO₂CH-.)

[0059| Step 2 A solution of 2.7-dιbromo-9.9-bis- (4-h\ dro\> -3- carbometho\\ )phen\ lfluorene (4 68 g. 7 5 mmol). n-he\\ lbromιde (3 2 g. 19 mmol). K₂CO^, (4 0 g. 28 9 mmol) and tetrabutv lammonium bromide (50 mg) in N. N- dimethylfoimanude (125 ml) was healed and stiπed at 100 C Aflei 21 hours an additional 0 5 g of n-hew lbromide and 0 5 g of K₂CO-, w as added and healing was continued for an additional 5 hours The cooled mixture was poured into 400 ml of cold HCl (0 5 N) The acidified mixture was extracted with 2 \ 200 ml of eth\ I acetate and the combined organic extracts were washed with water (3 x 300 ml) and brine ( 1 x 200 ml) The dried extracts (using CaSO.») were stπpped to dn ness under v acuum and the residue, a light amber oil. was crx stallιzed from methanol to afford 1 6 g (27%) of ihe product as a white solid Additional product was obtained from (he mother liquors ¹H NMR (CH₂Cl₂) δ 7 75-6 80 (m, 12.ArH). 4 05 (t.4. ArOCH₂), 3 80 (s.6. ArCO₂CHO- 1 80 (m.4.ArOCH₂CH₂). 1 60- 1 35 (m.12.

ArOCH₂CH₂CH₂CH₂CH₂CH-,) and 0 98 ppm (t.6 ArOCH₂CH₂CH₂CH₂CH₂CHj)

[0060] While onlv certain features of the invention hav e been illustrated and described herein, mam modifications and changes will occur to those skilled in the art Il is therefore. Io be understood that the appended claims are intended to cov er all such modifications and changes as fall within the true spirit of the invention

Claims

CLAIMS:

1. An optoelectronic device comprising:

a cathode:

an electron-transporting layer comprising a compound of formula I:

a light emitling-layer; and

an anode;

v, herein

R¹ and R* are independently at each occurrence, hydrogen, a C₁-C₂₀ aliphatic radical, a C₃-C₂₀ aromatic radical, or a C₃-C₂₀ cycloaliphatic radical;

R* is H or alU-1;

a and b are, independently at each occurrence O, or an integer ranging from 1 to 3:

n is 2 or 3; and

Ar is an aryl.

2. ^'Hie optoelectronic device of claim 1. wherein the compound of formula 1 is

3. The optoelectronic device of claim L wherein Ar is

wherein R⁴ and R* are independently a OCw aliphatic radical, a OCw aromatic radical, a CyC^ cycloaliphatic radical, or R⁴ and R\ taken together, form a 10- to 13- membered bicyclic or tiicyclic aromatic or heteroaromalic ring system.

4. The oploeleclronic device of claim I , wherein Ar is

wherein R⁴ and R^s are independently a CVCM aliphatic radical, a C>C;><) aromatic radical, a Cs-Cw cycloaliphatic radical, or R¹ and R*. taken together, form a 10- to 13- membered bicyclic or tricyclic aromatic or heteroaromatic ring system.

5. Tlie optoelectronic device of claim 1. wherein the compound of formula J is

6. The optoelectronic device of claim 1. wherein Ar is

wherein R⁶ and R⁷ are independently a C1-C20 aliphatic radical, a C₃-C₂₀ aromatic radical, or a C₃-C₂₀ cycloaliphatic radical.

7. The optoelectronic device of el aim 1 , wherein Ar is

and R⁸ is independently at each occurrence a direct bond or an aikyl and c is an integer ranging from 2 to 6.

8. Tiie optoelectronic device of claim 1 , wherein Ar is selected from

9. The optoelectronic device of claim 1 , wherein Ar is selected from

The optoelectronic device of claim 1, wherein R³ is methyl. , The optoelectronic device of claim 1, wherein the compound is of formula

12. Tlie optoelectronic device of claim 1. wherein the compound is of formula

13. A compound of formula I:

wherein

R¹ and R² are independently at each occurrence, hydrogen, a C₁-C₂₀ aliphatic radical, a C₃-C₂₀ aromatic radical, or a C₃-C₂₀ cycloaliphatic radical;

R³ is H or alkyl;

a and b are, independently at each occurrence 0, or an integer ranging from 1 to 3;

n is 2 or 3: ami

Ar is an aryl.

14. The compound of claim 13, wherein Ar is

wherein R¹ and R^? are independently a C₆-C₂₀ aliphatic radical, a C₆-C₂₀ aromatic radical, a C₆-C₂₀ cycloaliphatic radical, or R⁴ and R⁵, taken together, form a 10- to 13-membered bicyclic or tricyclic aromatic or heleroaromatic ring system.

15. The compound of claim 13, being of formula

16. The compound of claim 13, wherein Ar is

, wherein R⁶ and R⁷ are independently a C₁-C₂₀ aliphatic radical, a CrCso aromatic radical, or a C₃-C₂₀ cydoaliphatic radical.

17. The compound of claim 1, wherein Ar is

wherein R* is independently at each occurrence a direct bond or an αlkyl and c is an integer ranging from 2 to 6.

18. The compound of claim 13, wherein Ar is selected from

19. The compound of claim 13, wherein R³ is methyl.

20. The compound of claim 13, being of formula