GB2424881A - 2,7-Di(halophenyl)-9,9-bisalkylfluorene derivatives for liquid crystal compositions & organic electroluminescent display devices - Google Patents

2,7-Di(halophenyl)-9,9-bisalkylfluorene derivatives for liquid crystal compositions & organic electroluminescent display devices Download PDF

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GB2424881A
GB2424881A GB0606551A GB0606551A GB2424881A GB 2424881 A GB2424881 A GB 2424881A GB 0606551 A GB0606551 A GB 0606551A GB 0606551 A GB0606551 A GB 0606551A GB 2424881 A GB2424881 A GB 2424881A
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Mark John Goulding
Warren Duffy
Cecile Schott
Peer Kirsch
Alexander Hahn
Masayoshi Suzuki
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Merck Patent GmbH
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C07C25/22—Polycyclic aromatic halogenated hydrocarbons with condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/02—Monocyclic aromatic halogenated hydrocarbons
    • C07C25/13—Monocyclic aromatic halogenated hydrocarbons containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes

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  • Organic Chemistry (AREA)
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Abstract

The invention relates to 2,7-di(halophenyl)-9,9bisalkylfluorene derivatives of formula I and liquid crystal compositions comprising them, and their use in liquid crystal displays and organic electroluminescent display devices (inter alia). <EMI ID=1.1 HE=34 WI=132 LX=396 LY=721 TI=CF> <PC>[wherein R<3> and R<4> are independently of each other straight-chain or branched alkyl with 8 to 20 C atoms that is optionally mono- or polyfluorinated, and in which one or more non-adjacent CH2 groups are optionally replaced by -O-, -CY<1>=CY<2>- or -C=C-, <DL TSIZE=3> <DT>Y<1><DD>and Y<2> are independently of each other H, F, CI or CN, <DT>X<DD>is F or CI <DT>s<DD>is independently of one another 1, 2, 3 or 4, <DT>t<DD>is independently of one another 0,1, 2 or 3 and </DL> the remaining substituents, m and n are as defined herein.

Description

P05044 EB.doc Halopheflyl Derivatives of BisalkylfluOrefle
Field of the Invention
The invention relates to 2,7-di(halopheflYl)-9,9bisalkylflUOrefle derivatives, liquid crystal (LC) compositions comprising them, and their use in LC displays and organic electroluminescent display devices.
Background and Prior Art
Organic materials containing a fluorene moiety are known in prior art, and various types of these materials have been reported. For example, poly(dioctyl)flUOrene (PFO) is a solution processable main chain polymer which exhibits LC phases at high temperature and can be processed into macroscOPicallY aligned thin films which produce polarised electroluminescence, as reported by Grell et al., J. Kor.
Phys. Soc. (2000), 36(6), 331 -336. Further dialkylflUorefle containing main chain polymers, especially for use in OLED displays, are disclosed in Bernius et al., J. Mat. Sci. (2000), 11(2), 111-116; Chun et al., Polymer Preprints (2002), 43(1), 81-82 and Kameshima et al., J. Pol. Sd., Part A: Polymer Chemistry (2001), 39(18), 3143-31 50).
Low molar mass LC compounds containing a dialkylfluorefle moiety have been reported by Contoret et al., Mol. Cryst. Liq. Cryst., Science and Technology Section A, (2001), 368, 271-278 and Eastwood et al., Synt. Met. (2001), 121 (1-3), 1659-1660.
In the compounds disclosed in the above-mentioned documents the dialkyiflUOrene moiety is chemically bonded either to other dialkylflUOrene moieties, as in the case of PFO, or to other aromatic rings or conjugated moieties, usually in arrangements that are symmetrical in their substitution about the dialkylfluOrefle moiety.
WO 02/055463 Al discloses LC compounds comprising a fluorinated fluorene moiety and one further ring.
P05044 EB doc Further compounds containing diaflcylfluorene moieties in conjunction with halo-substituted phenyl rings are disclosed in Shah et al., Pol.
Mat. Sci. & Eng. (1999), 80, 199; US 2003/0141 809 Al and JP 2002- 317033 A2. However, in these cases the halogen atom is not added for the purpose of modifying the thermal behaviour.
Polymerisable mesogenic compounds (reactive mesogens) with a dialkyifluorene group and polymer films prepared thereof are disclosed in Kelly et al., Chem. Mater. (2004), 16, 4928 and US 2003-0203128 Al,furthermore in US 2003-119936 Al, US 2003- 0018097 Al, US 2003-099862 Al, US 2003-0027017 Al, US 2003- 099785 Al and US 2003-0021913 Al.
It is an aim of the present invention to provide fluorene compounds which have advantageous properties, in particular broad nematic LC phases and low melting points. Another aim of the invention is to provide advantageous uses for the new compounds, in particular as components of optical, electrooptical and electronic devices. Other aims of the invention are immediately evident to those skilled in the
art from the following description.
The above aims can be achieved by providing compounds as described in the present invention. Therein, dialkylfluorefle and fluorophenyl are combined as molecular moieties in molecular structures to produce materials which possess nematic LC phases at temperatures that are low enough to make their incorporation into multi-component LC mixtures possible.
Summary of the Invention
The invention relates to compounds of formula I P05044 EB.doc X) R3 R4 X)
I
wherein R1 and R2 are independently of each other F, Cl, CN, NCS, SF5, or an unpolymerisable straight-chain or branched alkyl group with I to 20 Catoms that is optionally mono- or polysubstituted by F, Cl or CN, and in which one or more non-adjacent CH2 groups are optionally replaced, in each case independently from one another, by -0-, -S-, -NH-, -NR -, -SiR R -, -GO-, -COO-, -OCO-, -OCO-O-, -S-GO-, -CO-S-, -CY1CY2- or -CEC- in such a manner that 0 and/or S atoms are not linked directly to one another, R3 and R4 are independently of each other straight-chain or branched alkyl with 8 to 20 C atoms that is optionally mono- or polyfluorinated, and in which one or more non- adjacent CH2 groups are optionally replaced by -0-, -CY1CY2- or -CC-, R5 and R6 independently of each other have one of the meanings of R1, R and R are independently of each other H or alkyl with I to 12 C-atoms, Y' and Y2 are independently of each other H, F, Cl or CN, A1 and A2 are independently of each other an aromatic or alicyclic ring or a group comprising two or more fused aromatic or alicyclic rings, wherein these rings optionally contain one P05044 EB doc or more hetero atoms selected from N, 0 and S, and are optionally mono- or polysubstituted by L, L has one of the meanings of R1, Z1 and Z2 are independently of each other -0-, -8-, -GO-, -COO-, -OCO-, -S-GO-, -GO-S-, -0-COO-, -CO-NR -, -NR -GO-, -OCH2-, -GH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SGF2-, -CH2CH2-, -GF2GH2-, -GH2GF2-, -GF2CF2-, -CH=N-, -N=CH-, -N=N-, -GH=GR -, -GY1CY2-, -CC-, -GHGH-GOO-, -OCO-GHCH- or a single bond, X isForGi, s is in case of multiple occurrence independently of one another 1,2,3 or4, t is in case of multiple occurrence independently of one another0,1,20r3, m and n are independently of each other 0, 1, 2 or 3.
The invention further relates to an LC composition comprising one or more compounds of formula I. The invention further relates to a semiconducting, charge transport or light-emitting material comprising at least one compound or composition as described above and below.
The invention further relates to the use of a compound, composition, semiconductor material, charge transport material or lightemitting material as described above and below in electrooptiCal displays, liquid crystal displays (LCDs), eLCDs, optical films, polariserS, compensatOrS, beam splitters, reflective films, alignment layers, colour filters, holographic elements, hot stamping foils, coloured P05044 EB doe images, decorative or security markings e.g. for consumer objects or documents of value, LC pigments, adhesives, synthetic resins with anisotropic mechanical properties, cosmetics, pharmaceutics diagnostics, nonlinear optics, optical information storage, electronic devices, OFET5, integrated circuits (IC), thin film transistors (TFT), flat panel display applications, Radio Frequency Identification (REID) tags, organic light emitting diodes (OLED), electroluminescent displays, backlights of LCDs, photovoltaic or sensor devices, electrode materials for batteries, photocondUctOr5 electro- photographic uses, electrophOtOgraphic recording, or as chiral dopants.
The invention further relates to a serniconducting or light-emitting component comprising one or more compounds or compositions as described above and below, especially for use in OLEDS, ICs, OFET5, TFTs, LCDs, photovoltaic or sensor devices, electrode materials, photocOndUctors and electrophotOg raphic applications.
The invention further relates to an optical, electrooptical or electronic device, in particular an alignment layer or a device selected from LCD5, OLEDs, OFET5, ICs and TFTs, comprising one or more compounds, compositions or components as described above and below.
The invention further relates to a TFT array for flat panel displays, REID tag, electroluminescent display or backlight comprising one or more compounds, compositions, polymers, components or devices as described above and below.
The invention further relates to a security marking or security device comprising one or more compounds, compositions, components or devices as described above and below.
Brief Description of the Drawinci
P05044 EB doc Figure IA and 2A show excitation and emission spectra of compounds according to example I and 2.
Figure 1 B and 2B show fluorescence spectra of compounds according to example I and 2.
Detailed Description of the Invention
The compounds according to the present invention exhibit high stability, low melting points and nematic phases, and do also have a good solubility in nematic LC host mixtures, enabling their use in LC and emissive display applications.
Especially unsymmetrical compounds of formula I, wherein the two groups attached to the fuorene core are different from each other, are especially advantageous because they have lower melting points than symmetrical ones. Compounds of formula I with few or no oxygen atoms are advantageous due to their higher stability.
Compounds of formula I with alkyl or fluoroalkyl substitution instead of alkoxy substitution, especially the oxygen free, unsymmetrical compounds, are advantageous due to their higher stability and solubility in TFT-LC host mixtures.
The compounds according to the present invention are especially suitable for use as components of LC compositions forming a Blue Phase. They are also effective for broadening the temperature range of the Blue Phase.
Especially preferred are compounds of formula I wherein - R3 and R4 are unpolymeriSable groups, i.e. groups that have low or no reactivity in a polymerisation or polymeraflalOgOUS reactions, - R3 and R4 do not contain a terminal C=C double bond, - one or more groups Z1 and Z2, preferably all groups Z1 and Z2 denote a single bond, - one or more groups Z' and Z2 denote -CF2O- or -OCF2-, p05044 EB doc - m is I and Z1 is a single bond and/or n is I and Z2 is a single bond, - A1 or A2 denote I,4-phenylefle that is optionally substituted by one or more groups L, in particular I,4-phenylefle substituted by one or two fluorine atoms.
- R' and R2 are selected from F, Cl, CN, C1-C20-alkyl that is optionally substituted with one or more fluorine atoms, C1-C2o- alkenyl, C 1C20-alkynyl, C1-C20-alkOXY, C1C20-thioalkYl, C1-C20-silYl, C1- C20-ester, C1-C20-amiflo, 1C20fluoroalkyl, (CH2CH2O)m with m being an integer from I to 6, very preferably F, C1-C20-alkyl C1-C20- alkoxy, C1 C20-thioalkYl or C1C20fluorOalkYl, - one or both of R' and R2 are alkyl or alkoxy with I to 12 C atoms, preferably I to 8 C atoms, - one or both of R1 and R2 are F, Cl, OCF3, CF3, OCHF2 or CN, - R3 and R4 are selected from straight-chain alkyl, alkenyl and alkoxy with 8 to 20, preferably 11 to 20 C atoms, mandnarel, - mis1andnisOo1, - mand nare2, - sislor2.
- tisO, - one or both of t are I or 2 and R5 and/or R6 is halogen, preferably F. Further preferred are compounds of formula I wherein Rh11)m is different from A' and A2 are independently of each other an aromatic or alicyclic ring, preferably a 5-, 6- or 7-membered ring, or a group comprising two or more, preferably two or three, fused aromatic or alicyclic rings, wherein these rings optionally contain one or more hetero atoms P05044 EB doc selected from N, 0 and S, and are optionally mono- or L is preferably F, Cl, CN, CH3, C2H5, OCH3, 0C2H5, COCH3, COC2H5, COOCH3, COOC2H5, CE3, OCF3, OCHF2 or 0C2F5, in particular F, Cl, CN, CH3, C2H5, OCH3, COCH3 or OCF3, most preferably F, Cl, CH3, OCH3 or COCH3.
Preferred groups A1 and A2 are for example furan, pyrrol, thiophene, oxazoe, thiazole, thiadiazole, imidazole, phenylene, cyclohexylene, cyclohexenylene, pyridine, pyrimidine, pyrazine, azulene, indane, naphthalene, tetrahyd ronaphthalene, anthracene and phenanthrene.
Particularly preferably A" and A2 are selected from furane-2,5-diyl, thiophene-2,5-diyl, thienothiophene-2,5-diyl, dithienothiophene-2,6- diyl, pyrrol-2, 5-diyl, I,4-phenylene, azulene-2,6-diyl, pyridine-2,5- diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, I,2,3,4-tetrahydronaphthalene-2,6-diyl, indane-2, 5-diyl, or I,4-cyclohexylene wherein one or two non-adjacent CH2 groups are optionally replaced by 0 and/or S, wherein these groups are unsubstituted, mono- or Preferably the groups (A" -Z" )m and (Z2-A2) contain only unfused rings A"2. Very preferably the groups (A"-Z1)m and (Z2-A2) comprise one or two 5- or 6-membered rings.
The groups (AZ')m and (Z2-A2) can be identical or different. In a preferred embodiment of the present invention the groups (AZ")m and (Z2A2) are mirror images of each other. In another preferred embodiment of the present invention the groups (A"-Z")m and (Z2-A2) are different.
Preferably (A"Z")m and (Z2-A2) are selected from the following formulae P05044 EB doe (L) ----z- ha lIb (L)r (L)r I Ic (L)r lid (L)r lie (L) (L) hf (L) (L) hg (L) cooz- hlh P05044 EB doc *.10- (L) coo Iii (L)r Ilk z- II m II n 110 lip llq
N
-iii3---- P05044 EB.doc - 11 - us lit -i-\-- \=)__Z\ Ilu wherein Z has one of the meanings of Z1 in formula I, L has one of the meanings of formula I and is preferably F, and r is 0, 1, 2, 3 or 4, preferably 0,1 or2.
(L) (L) The groups and preferably denote or -j5- with L having each independently one of the meanings given above.
Especially preferred are the following compounds Ia R' lb R" R" P05044 EB doc Ic Id F I e wherein R and R' have independently of each other one of the meanings of R1 in formula I, and are preferably F, Cl, CN or optionally fluorinated straight-chain alkyl or alkoxy with I to 12 Catoms or alkenyl, alkenyloxy or alkynyl with 2 to 12 C- atoms, R" and R" have independently of each other one of the meanings of R3 in formula I and are preferably straight chain alkyl, alkoxy, thioalkyl or fluorinated alkyl with 8 to 20 C-atoms.
If one of R1 is an alkyl or alkoxy group, i.e. where the terminal CH2 group is replaced by -0-, this may be straight-chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6, 7 or 8 carbon atoms and accordingly is preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyt, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, or octoxy, furthermore methyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, P05044 EB doc pentadecyl, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy, for example.
Oxaalkyl, i.e. where one CH2 group is replaced by -0-, is preferably straight-chain 2-oxapropyl (=methoxymethyl), 2- (=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl), 2-, 3-, or 4-oxapentyl, 2-, 3-, 4-, or 5oxahexyl, 2-, 3-, 4-, 5-, or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl or 2-, 3-, 4-, 5-, 6-,7-, 8- or 9- oxadecyl, for example.
If one of R14 is an alkyl group wherein one or more CH2 groups are replaced by -CH=CH-, this may be straight-chain or branched. It is preferably straight-chain, has 2 to 10 C atoms and accordingly is preferably vinyl, prop-I-, or prop-2-enyl, but-I-, 2- or but-3-enyl, pent1-, 2-, 3- or pent-4-enyl, hex-I-, 2-, 3-, 4- or hex-5-enyl, hept-I-, 2-, 3-, 4-, 5- or hept-6-enyl, oct-I-, 2-, 3-, 4-, 5-, 6- or oct-7-enyl, nonI-, 2-, 3-, 4-, 5-, 6-, 7- or non-8-enyl, dec-I-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or dec-9-enyl.
Especially preferred alkenyl groups are C2-C7-I E-alkenyl, C4-C7-3Ealkenyl, C5-C7-4-alkenyl, C6-C7-5-alkenyl and C7-6-alkenyl, in particular C2-C7-1 E-alkenyl, C4-C7-3E-alkenyl and C5-C7-4-alkenyl.
Examples for particularly preferred alkenyl groups are vinyl, I Epropenyl, I E-butenyl, I E-pentenyl, I E-hexenyl, I E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 C atoms are generally preferred.
If one of R14 is an alkyl or alkenyl group that is monosubstituted by CN or CF3, it is preferably straight-chain. The substitution by CN or CF3 can be in any desired position.
If one of R1 is an alkyl or alkenyl group that is at least monosubstituted by halogen, it is preferably straight-chain. Halogen is preferably F or Cl, in case of multiple substitution preferably F. The resulting groups include also perfluorinated groups. In case of P05044 EB doe monosubstitution the F or Cl substituent can be in any desired position, but is preferably in co-position. Examples for especially preferred straight-chain groups with a terminal F substituent are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl and 7-fluoroheptyl. Other positions of F are, however, not excluded.
Halogen is preferably F or Cl.
R1 can be an achiral or a chiral group. In case of a chiral group it is preferably selected of formula Ill: -Q1 -CH-Q
III
wherein Q' is alkylene or alkylene-oxy with I to 9 C atoms, arylene or heteroarylene as defined above, or a single bond, Q2 is alkyl or alkoxy with I to 10 C atoms which may be unsubstituted, mono- or polysubstituted by F, Cl, Br or CN, it being also possible for one or more non-adjacent CH2 groups to be replaced, in each case independently from one another, by -CC-, -0-, -S-, -NH-, -N(CH3)-, -GO-, -COO-, -OCO-, -OGO-O-, -S-GO- or -CO-S- in such a manner that oxygen atoms are not linked directly to one another, or aryl or heteroaryl as defined above, being different from Q1 or Q3, Q3 is F, Cl, Br, CN or alkyl, alkoxy, aryl or heteroaryl as defined for Q2 but being different from Q2 or Q1, n case Q1 in formula Ill is an alkylene-oxy group, the 0 atom is preferably adjacent to the chiral C atom.
p5O44 EB doc Preferred chira groups of formU'a fl are 2-aWy, 2-akO, ZmethY' 2methY0 2f uoroayi 2flUOr0a0I 2-(2- ethifl)aW01 I,1,itrifiU0r02 and pacUaY preferred chira grouPS are 2-bUtY (1methyPt0P 2- methytV 2rflethY1PeI 3-methVP' 2-ethy' 2- proPylPeVt1 in partiCU 2-n1ethV, 2thyut0XV, 2- methylPentoXVl 3thylpt0XV,thythex0XV1 1 methYlhexoXVI 2\OctV X, 2oxa3methy' Soxa4methylpeT 4methVhI 2-heXY, 2-octy, 2-fl0nY, 2-decy dOdeCy1 6meth0XY0Ct0XVI 6- methYloCtOXVI SrnethyP y0 rb0rW, 2methybYl0XVI 3methYtva00XVI 4methyth00XV12 chOrPr0Pb00XV1 2chloro3metlb oXy, 2ch1Or04- methY0XVI 2chloro3met eryOX 2methy30XapeI 1 methoXYPr0PY 2-0XY IethOXyPr0Py2OXVI I butoXVpropy2OXV1 2fluorooc0XV,2.
fluorodecY0XV1 1,1,1 t uoro2o0XV1 1,1,1 triflUoro201 2- fluoromethyo0XV for examP'e. Ve preferred are 2-heXV 2-oc, 2oC0XV1 1,1,itru0r02' 1,1,1triflU0ro20 and 1,1,1- trflUOro20(0 n additi0fl, comP0U5 containing an achiral branched groUP R1 may 0casiony be of impOrtance for examP' due to a reduction in the tendency towards crystaU%zatb0 Branched groups of this type generah'Y do not contain more than one chain branch. Preferred achiral branched groUPS are isopr0Pyi isobut (=methyPr0PY)1 tert- buty, isoPentyl (3methybI isopropoXV 2thypr0POXV and 3thybUt0XV.
The 0pound5 according to the present invention can be synthe according to or in na09y to methods whiCh are known per se and whiCh are deSCrib in standard works of organic chemistry such as, for eXamP' l-louben' MethOde der organischen Chemie, Thieme' ag, 5tuttga Some specific and preferred methods are described in the reaction schemes in the examP P05044 EB doc The LC compositions according to the present invention preferably contain at least one compound of formula I and a nematic host mixture comprising one or more nematic or nematogenic compounds.
Preferably the LC compositions are mixtures consisting of 2 to 25, preferably 3 to 15 compounds, at least one of which is a compound of formula I. The other compounds forming the nematic host mixture are preferably low molecular weight liquid crystal compounds selected from nematic or nematogenic substances, for example from the known classes of the azoxybenzenes, benzylidene-anilines7 biphenyls, terphenyls, phenyl or cyclohexyl benzoates, phenyl or cyclohexyl esters of cyclohehexanecarboxyliC acid, phenyl or cyclohexyl esters of cyclohexylbenzoic acid, phenyl or cyclohexyl esters of cyclohexylcyclohexanecarbOxyliC acid, cyclohexylphenyl esters of benzoic acid, of cyclohexanecarboxylic acid and of cyclohexylcyclohexanecarboxyliC acid, phenylcyclohexanes, cyclohexylbiphenyls, phenylcyclohexylcycloheXaneS, cyclohexyl-cyclohexanes, cyclohexylcyclohexeneS, cyclohexylcyclohexylcyClo-hexefles, I,4-biscyclohexylbenzenes, 4,4'-bis-cyclohexylbipheflylS, phenyl- or cyclohexylpyrimidines, phenyl- or cyclohexylpyridines, phenyl- or cyclohexylpyridazines, phenyl- or cyclohexyldioxanes, phenyl- or cyclohexyl-1, 3-dithianes, I,2-diphenyl-ethanes, I,2-dicyclohexylethaneS, 1 -phenyl-2-cyclohexylethanes, I cyclohexyl2-(4-phenylcyclohexyl)- ethanes, I -cyclohexyl-2-biphenyl-ethanes, I -phenyl-2-cyclohexyl- phenylethanes, optionally halogenated stilbenes, benzyl phenyl ether, tolanes, substituted cinnamic acids and further classes of nematic or nematogenic substances. The I,4-phenylene groups in these compounds may also be laterally mono- or difluorinated.
The most important compounds that are possible as components of these LC mixtures can be characterized by the following formula IV RaLaGERb iv P05044 EB doe wherein L and E, which may be identical or different, are in each case, independently from one another, a bivalent radical from the group formed by -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, - Pyr-, -Dio-, -B-Phe- and -B-Cyc- and their mirror images, where Phe is unsubstituted or fluorine-substituted I,4-phenylene, Cyc is transI,4-cyclohexylene or 1,4-cyclohexenylene, Pyr is pyrimidine-2,5-diyl or pyridine-2,5-diyl, Dio is I,3-dioxane-2,5-diyl and B is 2-(trans-1,4cyclohexyl)ethyl, pyrimidine-2,5-diyl, pyridine-2, 5-diyl or I,3-dioxane2,5-diyl.
G in these compounds is selected from the following bivalent groups -CH=CH-, -N(O)N-, -CH=CY-, -CH=N(O)-, -CC-, -CH-CH-, -CO-O-, -CH-O-, -CO-S-, -CH-S-, -CH=N-, -COO-Phe-COO- or a single bond, with Y being halogen, preferably chlorine, or -CN.
R and Rb are, in each case, independently of one another, alkyl, alkenyl, alkoxy, alkenyloxy, alkanoyloxy, alkoxycarbonyl or alkoxycarbonyloxy with I to 18, preferably 3 to 12 C atoms, or alternatively one of R and Rb is F, CF3, OCF3, Cl, NCS or CN.
In most of these compounds R and Rb are, in each case, independently of each another, alkyl, alkenyl or alkoxy with different chain length, wherein the sum of C atoms in nematic media generally is between 2 and 9, preferably between 2 and 7.
Many of these compounds or compositions thereof are commercially available. All of these compounds are either known or can be prepared by methods which are known per se, as described in the literature (for example in the standard works such as Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), to be precise under reaction conditions which are known and suitable for said reactions. Use may also be made here of variants which are known per Se, but are not mentioned here.
P05044 EBdoc A further aspect of the invention relates to both the oxidised and reduced form of compounds of formula I or compositions comprising them. Either loss or gain of electrons results in formation of a highly delocalised ionic form, which is of high conductivity. This can occur on exposure to common dopants. Suitable dopants and methods of doping are known to those skilled in the art, e.g., from EP 0 528 662, US 5,198,153 orWO 96/21659.
The doping process typically implies treatment of the semiconductor material with an oxidising or reducing agent in a redox reaction to form delocalised ionic centres in the material, with the corresponding counterions derived from the applied dopants. Suitable doping methods comprise for example exposure to a doping vapor in the atmospheric pressure or at a reduced pressure, electrochemical doping in a solution containing a dopant, bringing a dopant into contact with the semiconductor material to be thermally diffused, and ion-implantantion of the dopant into the semiconductor material.
When electrons are used as carriers, suitable dopants are for example halogens (e.g., 12, Cl2, Br2, Id, Id3, lBr and IF), Lewis acids (e.g., PF5, AsF5, SbF5, BF3, BCI3, SbCl5, BBr3 and SO3), protonic acids, organic acids, or amino acids (e.g., HF, HCI, HNO3, H2S04, HCIO4, FSO3H and CISO3H), transition metal compounds (e.g., FeCI3, FeOCI, Fe(C104)3, Fe(4-CH3C6H4SO3)3, TiCI4, ZrCI4, HfC4, NbF5, NbCI5, TaCl5, MoF5, MoCI5, WF5, WCI5, UF6 and LnCl3 (wherein Ln is a lanthanoid), anions (e.g., Cr, B, r, l3, HS04, SO42, N03, C104, BF, PF6, AsF6, SbF6, FeCI4, Fe(CN)63, and anions of various sulfonic acids, such as aryl-S03). When holes are used as carriers, examples of dopants are cations (e.g., H, Lit, Na, K, Rb and Cs), alkali metals (e.g., Li, Na, K, Rb, and Cs), alkaline-earth metals (e.g., Ca, Sr, and Ba), 02, XeOF4, (NO2) (SbF6), (NO2) (SbCI6), (NO2) (BF4), AgCIO4, H2lrCl6, La(N03)3 6H20, FSO200SO2F, Eu, acetylcholine, R4N, (R is an alkyl group), R4P (R is an alkyl group), R6As (R is an alkyl group), and R3S (R is an alkyl group).
P05044 EB.doc The conducting form of the compounds and materials of the present invention can be used as an organic "metal" in applications, for example, but not limited to, charge injection layers and ITO planarising layers in organic light emitting diode applications, films for flat panel displays and touch screens, antistatic films, printed conductive substrates, patterns or tracts in electronic applications such as printed circuit boards and condensers.
The compounds and materials of the present invention are useful as optical, electronic, semiconductor or light-emitting materials, in particular as charge transport materials in OFETs as components of ICs, RFID tags or TFTs, and as light-emitting materials for OLEDs in electroluminescent display applications or as backlight of for example LCDs. Alternatively, they may be used as photovoltaics or sensor materials, for electrophotographic recording, and for other semiconductor applications.
The compounds and materials according to the invention are especially useful as charge transport or semiconductor materials, or as components thereof, which have high carrier mobilities.
Particularly preferred are materials of formula I wherein R3'4 are selected from long alkyl, alkoxy, thioalkyl or fluoroalkyl groups. The introduction of long lateral chains R3'4 into the fluorene group improves their solubility and therefore their solution processibility.
Furthermore, the presence of such side chains also renders these materials effective as n-type semiconductors. The electron- withdrawing nature of fluoroalkyl substituents will also lower the HOMO further and result in a more stable material, which is less susceptible to oxidation.
Semiconductor devices like OFETs, where an organic semiconductive material is arranged as a film between a gate- dielectric and a drain and a source electrode, are generally known in prior art and described for example in US 5,892,244, WO 00/79617, US 5, 998,804. Due to the advantages, like low cost production using the solubility properties of the compounds according to the invention P05044 EB doe and thus the processibility of large surfaces, preferred applications of these FETs are such as integrated circuitry, TFT-displays and security applications.
In security applications, OFETs and other devices with semiconductive materials, like transistors or diodes, may be used for ID tags or security markings to authenticate and prevent counterfeiting of documents of value like banknotes, credit cards or ID cards, national ID documents, licenses or any product with money value, like stamps, tickets, shares, cheques etc..
The compounds and materials according to the invention may also be used as a means to produce macroscopically aligned electroluminescent layers, for example in organic light emitting devices or diodes (OLEDs). Such OLEDs can be used as emitters of linear or circular polarised light, suitable in display applications or as backlight of liquid crystal displays, security elements, antiglare lighting elements, horticultural lighting elements etc..
Common OLEDs are typically realized using multilayer structures. An emission layer is generally sandwiched between one or more electrontransport and! or hole-transport layers. By applying a voltage, electrons and holes as charge carriers move towards the emission layer where their recombination leads to the excitation and hence luminescence of the lumophor units contained in the emission layer. The inventive compounds, materials and films may be employed in one or more of the charge transport layers and! or in the emission layer, corresponding to their electrical and/ or optical properties. Furthermore their use within the emission layer is especially advantageous, if the compounds, materials and films according to the invention show electroluminescent properties themselves or comprise electroluminescent groups or compounds. The selection, characterization as well as the processing of suitable
monomeric, oligomeric and polymeric compounds or materials for the use in OLEDs is generally known by a person skilled in the art, see, P05044 EB doc e.g., Meerholz, Synthetic Materials, 111-112, 2000, 31-34, Alcala, J. AppI. Phys., 88, 2000, 7124-7128 and the literature cited therein.
According to another use, the inventive compounds or materials, especially those which show photoluminescent properties, may be employed as materials of light sources, e.g., of display devices such as described in EP 0 889 350 Al or by C. Weder et al., Science, 279, 1998, 835-837.
According to another use, the inventive compounds or materials can be used alone or together with other materials in or as alignment layers in LCD or OLED devices, as described for example in US 2003/0021913. The use of charge transport compounds according to the present invention can increase the electrical conductivity of the alignment layer. When used in an LCD, this increased electrical conductivity can reduce adverse residual dc effects in the switchable LCD cell and suppress image sticking or, for example in ferroelectric LCDs, reduce the residual charge produced by the switching of the spontaneous polarisation charge of the ferroelectric LCs. When used in an OLED device comprising a light emitting material provided onto the alignment layer, this increased electrical conductivity can enhance the electroluminescence of the light emitting material. The compounds or materials according to the present invention having mesogenic or LC properties can form oriented anisotropic films as described above, which are especially useful as alignment layers to induce or enhance alignment in an LC medium provided onto said anisotropic film. The materials according to the present invention may also be combined with photoisomerisable compounds and/or chromophores for use in or as photoalignment layers, as described in US 2003/0021913.
The examples below serve to illustrate the invention without limiting it. In the foregoing and the following, all temperatures are given in degrees Celsius, and all percentages are by weight, unless stated otherwise. The following abbreviations are used to illustrate the liquid crystalline phase behaviour of the compounds: G = glassy state; K = P05044 EB doc - 22 - crystalline; N = nematic; S = smectic; N*, Ch = chiral nematic or cholesteric; I = isotropic. The numbers between the symbols indicate the phase transition temperatures in C. T (N-I) is the temperature of the nematic/isotropic phase transition (in C), Tg is the glass transition temperature.
Example I
Compound (1) (2,7-Bis-(2-fluoro-4'-propyl-biPheflYl-4-Yl)-9,9-dioctyl9H-fluorene) is prepared as follows.
2,7-dibromo-9, 9-dioctyifluorene (5g, 9mmoles), 2'-Fluoro 4-n-propylbiphenyl-4'-bOrofliC acid (5.05g, 20mmoles), 1,1 Bis diphenylphosphiflo ferrocene di chloro palladium (II) (0.2g, 0.245mmoles) and I,4-dioxane (20m1) are combined under a nitrogen atmosphere and heated at 103 C for 18 hours. TLC indicates complete consumption of the starting materials, and the reaction mixture is added to water. The reaction mixture is worked up with water and DCM and then dried with magnesium sulphate before being concentrated under vacuo. This gives 9.62g of an orange oil.
The crude product is purified by column chromatography over silica P05044 EB doc - 23 - gel, eluting with petrol and ethyl acetate. 2.55g or colourless crystals are isolated, which are further purified by recrystallistion from ethanol, to yield a pure product. Proton NMR spectroscopy and GC- MS confirm the structure.
The pure compound (1) exhibits the following mesophase behaviour K 105 N 111 I and the following extrapolated properties when measured as a 10% wlw solution in Merck ZLI-4792.
I (N-I) 52 C Lfl 0.2823 e 1.8276 n0: 1.5452 & -1.17 11: 2.225 c: 3.391
Example 2
Compound (2) (2,7-Bis-(2-fluoro-4-octyloxy-phenYl)-9,9-dioCtYl-9Hfluorene) is prepared as follows. ::
P05044 EB doc 2,7-dibromo-9,9-dioctylfluorene (5g, gmmoles), 3-fluoro-1 octyloxyphenyl-4'-boronic acid (5.37g, 21 mmoles), tetrakis palladium triphenylphosphine (0) (0.lg, 0.9mmoles), potassium phosphate monohydrate (5.8g, 27mmoles) and I,4-dioxane (2Oml) are combined under a nitrogen atmosphere and heated at 103 C for 18 hours. TLC indicates complete consumption of the starting materials, and the reaction mixture is added to water. The reaction mixture is worked up with water and DCM and then dried with magnesium sulphate before being concentrated under vacuo. The crude product is purified by column chromatography over silica gel, eluting with petrol and ethyl acetate. I.84g of colourless crystals are isolated, which are further purified by recrystallistion from ethanol, to yield a pure product. Proton NMR spectroscopy and GC-MS confirm the structure.
The pure compound (2) exhibits the following mesophase behaviour K 55 I and the following extrapolated properties when measured as a 10% w/w solution in Merck ZLI-4792 T(N-l) -124 C Lfl 0.319 e 1.8345 n0: 1.51 52 -4.56: 1.036: 5.594
Example 3
Compound (3) (2-(4-Ethoxy-2, 3-difluoro-phenyl)-7-(3-fl uoro-4'-propylbiphenyl-4-yl)-9,9-dioctyl-9H-fluorefle) is prepared as follows.
P05044 EB.doc
F
- yB(0H)2 BrQJO + HC " (3b) (3a) 73 i ( ) 178 817 Br (3e) H17C8 C8H17 H7CHccHF L (3) 17 8 8 17 F (3c): A mixture of 56.4 g (230 mmol) of (3a), 59.3 g (230 mmol) of (3b), 51 g of sodium metaborate octahydrate, 3.5 g of Pd(PPh3)2Cl2, 2.5 ml hydrazine hydrate, 1.5 I of THF and 230 ml of H20 is refluxed for 6 h. The work-up is done in the usual manner. The crude product is purified by chromatography (toluene; silica gel) and crystallization from toluene. Yield 59.1 g (67%) of (3c) as colourless crystals, m.p. 203 C, nematic.
(3d): A solution of 53.5 g (141 mmol) of(3c) in 2.8 I of THF is treated at -78 C with 90 ml (143 mmol) of n-BuLl (15% solution in hexane).
After 30 mm, ioo ml (141 mmol) of bromooctane are added and the P05044 EB doc temperature is allowed to rise to room temp. After 1 h, the mixture is cooled again to -78 C and treated again with 90 ml (143 mmol) of n- BuLi (15% solution in hexane). After 30 mm, again 100 ml (141 mmol) of bromooctane are added, and the temperature is allowed to rise to room temp. The mixture is hydrolized with 500 ml of water, and the work-up is done as usual. The crude product is purified by chromatography (heptane/CH2CI2 9:1, silica gel). Yield 65 g (65%) of (3d) as colourless crystals, m.p. 55 C.
(3e): A solution of 52 g (85 mmol) of (3d) in 500 ml of CH2CI2 is treated dropwise at room temp. with 44 ml (85 mmol) of bromine.
The work-up is done as usual, and the crude product is purified by chromatography (heptane/CH2CI2 9:1, silicagel) and crystallization from ethanol/heptane 3:1. Yield 45.1 g (64%) of (3e) as colourless crystals.
(3): A mixture of 9.3 g (13.6 mmol) of (3e), 2.9 g (14.4 mmol) of 2,3difluoro-4-ethoxybenzene boronic acid, 3 g of sodium metaborate octahydrate, 300 mg of Pd(PPh3)2C12, 0.2 ml hydrazine hydrate, 60 ml of THF and 15 ml of H20 is refluxed for 6 h. The work-up is done in the usual manner. The crude product is purified by chromatography (heptane/MTBE 9:1; silica gel) and crystallization from heptane. Yield: 5. 6 g (54%) of (3) as colourless crystals, m.p. 73 C.
Compound (3) exhibits the following extrapolated properties when measured as a 10% w/w solution in Merck ZLI-4792 I (N-I) -20.3 C An 0.217 -1.3
Example 4
P05044 EB.doc - 27 - Compound (4) (2-{4-[1, I -difluoro-1 -(3,4, 5-trifluoro-phenoxy)-methyl]3,5difluoro-phenyl}-7-(3-fluoro-4'-propyl-biPheflYl-4-Yl)-9,9-dioctyl9H-fluorene) is prepared as follows. Br
(a) 178 817 F Br-(k (4b) F H7cHccHo (4a): A solution of 27.3 g (40 mmol) of (3e) in 250 ml of THF is treated at -78 C with 26 ml (41 mmol) of n-BuLi (15% in hexane).
After I h, 5 ml (44 mmol) of trimethyl borate are added, and the mixture is allowed to warm up to 0 C. 50 ml 2 N HCI are added, and the mixture is worked up as usual. The crude boronic acid (24.6 g, contains 75% product) is used for the further reactions.
(4): A mixture of 6 g (7 mmol, contains 75% product) of (4a), 2.7 g (6.9 mmol) of (4b), 1.5 g of sodium metaborate octahydrate, 150 mg of Pd(PPh3)2C12, 0.1 ml hydrazine hydrate, 50 ml of THF and 7 ml of H20 is refluxed for 6 h. The work-up is done in the usual manner.
The crude product is purified by chromatography (heptane/MTBE 9:1; silica gel) and subsequent preparative HPLC. Yield: 4 g (63%) of (4) as colourless crystals, m.p. 82 C.
P05044 EB doc Compound (4) exhibits the following extrapolated properties when measured as a 10% w/w solution in Merck ZLI-4792 T (N-I) -1 9.2 C n 0.217 15.2
Example 5
Compound (5) (3Fluoro4'-propyl-biPheflYl-4-Yl)-9,9-diOctYI7(3,4,5trifluoro-phenyl)-9H-flUorefle) ) is prepared as follows.
H7ccO1Hcc (5): A mixture of 11 g (12.8 mmol) of (4a), 2.8 g (13.3 mmol, contains 75% product) of 3,4,5-trifluorobromobeflZefle, 2.8 g of sodium metaborate octahydrate, 300 mg of Pd(PPh3)2C12, 0.2 ml hydrazine hydrate, 50 ml of THF and 12 ml of H20 is refluxed for 6 h. The work- up is done in the usual manner. The crude product is purified by chromatography (heptane/MTBE 9:1; silica gel) and subsequent preparative H PLC. Yield: 1.5 g of (5) as colourless crystals.
Compound (5) exhibits the following extrapolated properties when measured as a 10% w/w solution in Merck ZLI-4792 G-5K79 I Lfl 0.1840 ne: 1.7312 n0: 1.5472 6.0 c: 10.4 4.4 P05044 EB doc
Example 6
Solid state fluorescence data from thin films of compounds (1) and (2) are obtained as follows. Iwt% toluene solutions of (I) and (2), respectively, are spin-coated speed at I,500r.p.m onto clean Quartz substrates, followed by heating at 100 C for 3mm on a hot plate.
The ionization potential (identical to the absolute HOMO level IQ measured from the vacuum level (=0eV)) is measured using AC-2.
Figures IA and 2A show the excitation spectrum (curve b) and emission spectrum (curve a) for compound (I) and (2), respectively.
The HOMO-LUMO gap is calculated from the band edge of the absorption and fluorescence spectra. For this HOMO-LUMO gap calculation, the intersection point of the excitation spectrum (curve b) and fluorescence spectrum (curve a) is used as the band edge energy (BEE). The results are as follows: Compound (1): BEE = 3.14eV at 395nm Compound (2): BEE = 3. 33eV at 372nm Fluorescence spectra of compounds (I) and (2) are measured using a fluorimeter and an excitation wavelengh of 220nm. The results are shown in Figure I B and 2B, respectively. Compound (1) and (2) are fluorescent, showing maximum fluorescence around 4IOnm. From this, it can be inferred that the materials show electroluminescence at similar wavelengths of emission.

Claims (26)

  1. P05044 EB.doc - 30 - Patent Claims 1. A compound of formula I X) R3 R4 X)
    I
    wherein R1 and R2 are independently of each other F, Cl, CN, NGS, SF5, or an unpolymerisable straight-chain or branched alkyl group with I to 20 Catoms that is optionally mono- or polysubstituted by F, Cl or CN, and in which one or more non-adjacent CH2 groups are optionally replaced, in each case independently from one another, by -0-, -S-, -NH-, -NR -, - S1R R -, -CO-, -COO-, -OCO-, -OCO-0-, -S-GO-, -CO-S-, -CY1=CY2- or -CEC- in such a manner that 0 and/or S atoms are not linked directly to one another, R3 and R4 are independently of each other straight-chain or branched alkyl with 8 to 20 C atoms that is optionally mono- or polyfluorinated, and in which one or more non-adjacent CH2 groups are optionally replaced by -0-, -CY1GY2- or -cC-, R5 and R6 independently of each other have one of the meanings of R1, R and R are independently of each other H or alkyl with I to 12 C-atoms, Y' and Y2are independently of each other H, F, CI or CN, P05044 EB.doc A1 and A2 are independently of each other an aromatic or alicyclic ring or a group comprising two or more fused aromatic or alicyclic rings, wherein these rings optionally contain one or more hetero atoms selected from N, 0 and S, and are optionally mono- or L has one of the meanings of R, I Q' Z' and Z2 are independently of each other - 0-, -S-, -Go-, -COO-, -OCO-, -S-CO-, -CO-S-, -0-COO-, -CO-NR -, -NR -CO-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2CH2-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR -, -CY'=CY2-, -CC-, -CH=CH-COO-, -OCO-CHCH- or a single bond, X isForCl, s is in case of multiple occurrence independently of one another 1,2,3 or4, t is in case of multiple occurrence independently of one anotherO,1,2or3and m and n are independently of each other 0, 1, 2 or 3.
  2. 2. A compound according to claim 1, characterized in that R1 and R2 are selected from F, Cl, CN, C1-C20-alkyt that is optionally substituted with one or more fluorine atoms, C1-C20-alkenyl, C1- C20-alkynyl, C1-C20-alkoxy, C1-C20-thioalkyl, C1-C20-silyl, C1-C20- ester, C1-C20-amino, C1-C20-fluoroalkyl or (CH2CH2O)m with m being an integer from I to 6.
    P05044 EB.doc
  3. 3. A compound according to claim I or 2, characterized in that R3 and/or R4 are selected from straight-chain alkyl, alkenyt or alkoXy with 8 to 20 C-atomS.
  4. 4. A compound according to claim 3, characteriZed in that one of R3 and R4 is straight-chain ailcyl, alkenyl or alkoxy with 8 to 20 C- atoms and the other is F.
  5. 5. A compound according to at least one of claims I to 4, cnaracterized in that one or more groupS Z' and Z2 are a single bond.
  6. 6. A compound according to at least one of claims I to 5, characterized in that A and A2 are selected from furane-2,S- diyl, thiophene-2,5-diYl1 thienothiOPhene2,S.thYhi dithienothiOPhefle2,6- diyl, pyrrol-2,5-diyl, I,4phenylefle, azutene-2,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalefle-2,6-diyl, 1,2,3 indane-2,5-diYt, or I,4cycloheXYlefle wherein one or two non- adjacent CH2 groups are optionally replaced by 0 and/or S and wherein the above groups are unsubstitUted, mono- or polysubstituted by L as defined in claim 1.
  7. 7. A compound according to at least one of claims I to 6, craracter1zed in that A' and A2 are I,4-pheflylene that is optionally substituted by one or more groups L as defined in claim 1.
  8. 8. A compound according to at least one of claims I to 7, characterized in that A' and A2 are selected from I,4phenyler%e 2- or 3-fluoro-1,4-phenylene1 2,3diflUOr01,4-pheflylene and 3,5-difluorO-1,4phenylene.
  9. 9. A compound according to at least one of claims 1 to 8, characterized in that m is I and n is 0 or 1.
    P05044 EB doc
  10. 10. A compound according to at least one of claims I to 9, selected from the formulae lb R" R1" Ic R" R'" F Id R" It F Rt" le R" wherein R and R' have independently of each other one of the meanings of R1 in claim 1, R" and R" have independently of each other one of the meanings of R3 in claim 1.
  11. 11. An LC composition comprising one or more compounds according to at least one of claims I to 10.
  12. 12. A semiconducting, charge transport or light-emitting material comprising at least one compound or composition according to at least one of claims I to 11.
  13. 13. Use of a compound, composition, semiconductor material, charge transport material or light-emitting material according to at least one of claims I to 12 in an electrooptical display, liquid crystal display (LCD), eLCD, optical film, polariser, compensator, beam splitter, reflective film, alignment layer, colour filter, holographic element, hot stamping foil, coloured image, decorative or security marking, e.g. for consumer objects or documents of value, LC pigment, adhesive, synthetic resin with anisotropic mechanical properties, cosmetic, pharmaceutic, diagnostic, nonlinear optic, optical information storage, electronic device, OFET, integrated circuit (IC), thin film transistor (TFT), flat panel display application, Radio Frequency Identification (RFID) tag, organic light emitting diode (OLED), electroluminescent display, backlight for an LCD, photovoltaic or sensor device, electrode material for batteries, photoconductor, electro-photographic use, clectro- photographic recording, or a chiral dopant.
  14. 14. A semiconducting or light-emitting component, characterized in that it comprises one or more compounds or a composition according to at least one of claims I to 12.
  15. 15. An optical, elcctrooptical or electronic device, alignment layer, or device selected from LCDs, OLEDs, OFETs, ICs and TFTs, characterized in 35 - that it comprises one or more compounds, compositions or components according to at least one of claims Ito 12 and 14.
  16. 16. A TIFT array for a flat panel display, an REID tag, an electroluminescent display or a backlight, characterised in that it comprises one or more compounds, compositions, components or devices according to at least one of claims Ito 12 and 14.
  17. 17. A security marking or security device, characterised in that it comprises one or more compounds, compositions, components or devices according to at least one of claims I to 12 and 14.
  18. 18. An electrooptical display, liquid crystal display (LCD), eLCD, optical film, polariser, compensator, beam splitter, reflective film, alignment layer, colour filter, holographic element, hot stamping foil, coloured image, decorative or security marking, e.g. for consumer objects or documents of value, LC pigment, adhesive, synthetic resin with anisotropic mechanical properties, cosmetic, pharmaceutic, diagnostic, nonlinear optic, optical information storage, electronic device, OFET, integrated circuit (IC), thin film transistor (TFT), flat panel display application, Radio Frequency Identification (RFID) tag, organic light emitting diode (OLED), electroluminescent display, backlight for an LCD, photovoltaic or sensor device, electrode material for batteries, photoconductor, clectrophotographic use, electro-photographic recording, or a chiral dopant, comprising a compound, composition, semiconductor material, charge transport material or light emitting material as claimed in any of claims 1 to 12 and 14.
  19. 19. A compound substantially as herein described as being in accordance with the invention.
    - 36 -
  20. 20. An LC composition substantially as herein described as being in accordance with the invention.
  21. 21. A semiconducting, charge transport or light-emitting material substantially as herein described as being in accordance with the invention.
  22. 22. An electrooptical display, liquid crystal display (LCD), eLCD, optical film, polariser, compensator, beam splitter, reflective film, alignment layer, colour filter, holographic element, hot stamping foil, coloured image, decorative or security marking, e.g. for consumer objects or documents of value, LC pigment, adhesive, synthetic resin with anisotropic mechanical properties, cosmetic, pharmaceutic, diagnostic, nonlinear optic, optical information storage, electronic device, OFET, integrated circuit (IC), thin film transistor (TFT), fiat panel display application, Radio Frequency Identification (RFID) tag, organic light emitting diode (OLED), electroluminescent display, backhght for an LCD, photovoltaic or sensor device, electrode material for batteries, photoconductor, electrophotographic use, electro-photographic recording, or a chiral dopant, comprising a compound, composition, semiconductor material, charge transport material or light emitting material substantially as herein described as being in accordance with the invention.
  23. 23. A semiconducting or light-emitting component substantially as herein described as being in accordance with the invention.
  24. 24. An optical, electrooptical or electronic device, alignment layer, or device selected from LCDs, OLEDs, OFETs, ICs and TFTs, substantially as herein described as being in accordance with the invention.
  25. 25. A TFT array for a flat panel display, an REID tag, an electroluminescent display or a backlight-, substantially as herein described as being in accordance with the invention.
    - 37 -
  26. 26. A security marking or security device substantially as herein described as being in accordance with the invention.
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US9951089B2 (en) 2010-02-03 2018-04-24 Infinity Pharmaceuticals, Inc. Methods of treating a fatty acid amide hydrolase-mediated condition
CN103872263A (en) * 2012-12-07 2014-06-18 乐金显示有限公司 Organic light emitting diode device and liquid crystal type emitting material for the same
US20140160398A1 (en) * 2012-12-07 2014-06-12 Lg Display Co., Ltd. Organic light emitting diode device and liquid crystal type emitting material for the same
US9371484B2 (en) * 2012-12-07 2016-06-21 Lg Display Co., Ltd. Organic light emitting diode device and liquid crystal type emitting material for the same
CN103872263B (en) * 2012-12-07 2016-12-28 乐金显示有限公司 Oled device and for its liquid crystal type luminescent material
CN103896853A (en) * 2012-12-27 2014-07-02 海洋王照明科技股份有限公司 Pyrimidinyl electron transport material and preparation method thereof, and organic electroluminescent device
US9917260B2 (en) 2013-08-23 2018-03-13 Basf Se Compounds with terminal heteroarylcyanovinylene groups and their use in organic solar cells
GB2525245A (en) * 2014-04-17 2015-10-21 Lomox Ltd Fluoroalkylfluorene derivatives
US10084137B2 (en) 2014-04-17 2018-09-25 Lomox Limited Fluoroalkylfluorene derivatives
US10923662B2 (en) 2014-04-17 2021-02-16 Lomox Limited Fluoroalkylfluorene derivatives
US11107992B2 (en) 2015-10-16 2021-08-31 Lomox Limited Cross-linkable charge transport materials
CN106083538A (en) * 2016-06-07 2016-11-09 阜阳欣奕华材料科技有限公司 A kind of compound, liquid-crystal composition and liquid crystal display
CN106083538B (en) * 2016-06-07 2019-05-28 阜阳欣奕华材料科技有限公司 A kind of compound, liquid-crystal composition and liquid crystal display
CN109251136A (en) * 2017-07-14 2019-01-22 阜阳欣奕华材料科技有限公司 A kind of compound, liquid-crystal composition and display device
CN109251136B (en) * 2017-07-14 2022-01-18 阜阳欣奕华材料科技有限公司 Compound, liquid crystal composition and display device
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US12049466B2 (en) 2018-05-17 2024-07-30 Forma Therapeutics, Inc. Fused bicyclic compounds useful as ubiquitin-specific peptidase 30 inhibitors
US11535618B2 (en) 2018-10-05 2022-12-27 Forma Therapeutics, Inc. Fused pyrrolines which act as ubiquitin-specific protease 30 (USP30) inhibitors
US11814386B2 (en) 2018-10-05 2023-11-14 Forma Therapeutics, Inc. Fused pyrrolines which act as ubiquitin-specific protease 30 (USP30) inhibitors
CN112175627A (en) * 2020-09-24 2021-01-05 北京科技大学 Preparation method of blue phase liquid crystal composite material containing fluorene core bending type compound

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