EP1725541A2 - Composes reactifs misogenes a transfert de charge contenant au moins de groupements thiophere - Google Patents

Composes reactifs misogenes a transfert de charge contenant au moins de groupements thiophere

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Publication number
EP1725541A2
EP1725541A2 EP05701266A EP05701266A EP1725541A2 EP 1725541 A2 EP1725541 A2 EP 1725541A2 EP 05701266 A EP05701266 A EP 05701266A EP 05701266 A EP05701266 A EP 05701266A EP 1725541 A2 EP1725541 A2 EP 1725541A2
Authority
EP
European Patent Office
Prior art keywords
compounds
groups
thi
phe
liquid crystal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05701266A
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German (de)
English (en)
Inventor
Martin Heeney
Weimin Zhang
Steven Tierney
David 21a Castlemain Avenue SPARROWE
Maxim Shkunov
Iain 2 Goodacre Drive MCCULLOCH
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Merck Patent GmbH
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Merck Patent GmbH
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Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Priority to EP07019781A priority Critical patent/EP1876177A3/fr
Priority to EP05701266A priority patent/EP1725541A2/fr
Priority to EP07019782A priority patent/EP1903036A1/fr
Publication of EP1725541A2 publication Critical patent/EP1725541A2/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/18—Radicals substituted by singly bound hetero atoms other than halogen by sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • 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
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
    • 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
    • C09K19/38—Polymers
    • C09K19/3833—Polymers with mesogenic groups in the side chain
    • 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
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/58—Dopants or charge transfer agents
    • C09K19/582—Electrically active dopants, e.g. charge transfer agents
    • 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
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition

Definitions

  • the invention relates to new reactive mesogenic compounds with charge transport properties comprising at least two thiophene groups.
  • the invention further relates to their use as semiconductors or charge transport materials, in optical, electro-optical or electronic devices like for example liquid crystal displays, optical films, organic field effect transistors (FET or OFET) for thin film transistor liquid crystal displays and integrated circuit devices such as RFID tags, electroluminescent devices in flat panel displays, and in photovoltaic and sensor devices.
  • the invention further relates to a field effect transistor, light emitting device or ID tag comprising the reactive mesogenic charge transport compounds.
  • Organic materials have recently shown promise as the active layer in organic based thin film transistors and organic field effect transistors [see H. E. Katz, Z. Bao and S. L. Gilat, Ace. Chem. Res., 2001 , 34, 5, 359]. Such devices have potential applications in smart cards, security tags and the switching element in flat panel displays. Organic materials are envisaged to have substantial cost advantages over their silicon analogues if they can be deposited from solution, as this enables a fast, large-area fabrication route.
  • the performance of the device is principally based upon the charge carrier mobility of the semi-conducting material and the current on/off ratio, so the ideal semiconductor should have a low conductivity in the off state, combined with a high charge carrier mobility (> 1 x 10 "3 cm 2 V “1 s "1 ).
  • the semi-conducting material is relatively stable to oxidation i.e. it has a high ionisation potential, as oxidation leads to reduced device performance.
  • a known compound which has been shown to be an effective p-type semiconductor for OFETs is pentacene [see S. F. Nelson, Y. Y. Lin, D. J. Gundlach and T. N. Jackson, Appl. Phys.
  • reactive mesogenic compounds consist of a central mesogenic core comprising two or more thiophene rings, and optionally one or more phenylene rings that form a conjugated system together with the thiophene rings, said mesogenic core being linked, optionally via a spacer group, to one or more reactive groups.
  • the compounds can induce or enhance liquid crystal phases or are liquid crystalline themselves. They can be oriented in their mesophase and the polymerisable group can be polymerised or crosslinked in situ to form polymer films with a high degree of order, thus yielding improved semiconductor materials with high stability and high charge carrier mobility.
  • a further aspect of the invention relates to liquid crystal polymers, in particular liquid crystal side chain polymers obtained from the reactive mesogenic compounds according to the present invention, which are then further processed e.g. from solution as thin layers for use in semiconductor devices.
  • 'liquid crystal or mesogenic material' or 'liquid crystal or mesogenic compound' should denote materials or compounds comprising one or more rod-shaped, board-shaped or disk-shaped mesogenic groups, i.e. groups with the ability to induce liquid crystal phase behaviour.
  • Liquid crystal compounds with rod-shaped or board- shaped groups are also known in the art as 'calamitic' liquid crystals.
  • Liquid crystal compounds with a disk-shaped group are also known in the art as 'discotic' liquid crystals.
  • the compounds or materials comprising mesogenic groups do not necessarily have to exhibit a liquid crystal phase themselves. It is also possible that they show liquid crystal phase behaviour only in mixtures with other compounds, or when the mesogenic compounds or materials, or the mixtures thereof, are polymerised.
  • 'reactive group 1 or 'reactive compound' means compounds or groups that are capable of participating in a polymerisation reaction, like radicalic or ionic polymerisation from unsaturated functionality, or a polyaddition or polycondensation reaction, as well as compounds or groups that are capable of being grafted for example by a condensation or addition reaction to a reactive polymer backbone in a polymeranaloguous reaction.
  • film' includes self-supporting, i.e. free-standing, films that show more or less pronounced mechanical stability and flexibility, as well as coatings or layers on a supporting substrate or between two substrates.
  • the invention relates to compounds of formula I
  • p is a polymerisable or reactive group
  • Sp is a spacer group or a single bond
  • X is a linkage group or a single bond
  • a 1 and A 2 are independently of each other 1 ,4-phenylene or thiophene-2,5-diyl, all of which are optionally substituted with one or more groups R 1 ,
  • R 1 has one of the meanings of R
  • R° and R 00 are independently of each other H or alkyl with 1 to 12 C- atoms
  • Y 1 and Y 2 are independently of each other H, F, Cl or CN,
  • R', R" and R"' are independently of each other alkyl with 1 to 12 C- atoms
  • n 1 , 2, 3, 4 or 5
  • a 1 and A 2 denote thiophene-2,5-diyl that is optionally substituted
  • R 2 is R 1 or -C ⁇ C-R 1 and the groups R 1 have independently of each other one of the meanings of R given above, and
  • the invention also relates to the use of the compounds of formula I as semiconductors or charge transport materials, in particular in optical, electro-optical or electronic devices, like for example in field effect transistors as components of integrated circuitry, as thin film transistors in flat panel display applications or RFID tags, or in semi- conducting components for organic light emitting diode (OLED) applications such as electroluminescent displays or backlights of flat panel displays, for photovoltaic or sensor devices, or as light- modulating components for liquid crystal displays, optical films or other optical or electrooptical devices.
  • OLED organic light emitting diode
  • the invention also relates to a field effect transistor, for example as a component of integrated circuitry, as a thin film transistor in flat panel display applications, or in an RFID tag, comprising one or more compounds according to the present invention.
  • the invention also relates to a semi-conducting component, for example in OLED applications like electroluminescent displays or backlights of flat panel displays, in photovoltaic or sensor devices, comprising one or more according to the present invention.
  • a semi-conducting component for example in OLED applications like electroluminescent displays or backlights of flat panel displays, in photovoltaic or sensor devices, comprising one or more according to the present invention.
  • the inventive reactive mesogenic compounds are useful as charge transport semiconductors, in that they have.high carrier mobilities.
  • the introduction of side groups to the mesogenic core improves their solubility and therefore their solution processability.
  • the mesogenic core comprises one or more thiophene groups. They are therefore particularly useful as semiconductors or charge transport materials, as they can be processed while in the highly ordered mesophase morphology, and readily aligned by conventional techniques in a preferred direction. Both smectic and nematic mesophase ordering allows close packing of molecular pi-electron systems, which maximises intermolecular charge transfer which occurs through a hopping mechanism between adjacent molecules.
  • This ordered, and oriented microstructure can be permanently "frozen-in” by polymerising the mesogens, which can also create a structure with long range order, or "monodomain". Formation of a monodomain also maximises charge transfer by eliminating charge trap sites at grain boundaries, while the polymerisation also improves the mechanical properties of the film. Further, by cross-linking the mesogens, a highly stable structure results, which has an additional advantage of being impervious to subsequent processing solvents during device fabrication, thus allowing a wider range of solvents to be used in deposition of the next layer of the device by solution techniques. In addition, it is often observed that this cross-linking further densities the film, leading to smaller intermolecular distances and improved charge transport.
  • another aspect of the invention relates to a reactive liquid crystal mixture comprising one or more reactive mesogenic compounds of the present invention, and optionally comprising one or more further reactive compounds, which are optionally also mesogenic or liquid crystalline.
  • reactive mesogenic compounds of the present invention or mixtures comprising one or more reactive mesogenic compounds of the present invention, that exhibit a liquid crystal phase, especially a nematic and/or smectic liquid crystal phase.
  • Another aspect of invention relates to an anisotropic polymer film with charge transport properties obtainable from a reactive liquid crystal mixture as defined above that is aligned in its liquid crystal phase into macroscopically ordered orientation and polymerised or cross-linked to fix the oriented state.
  • Another aspect of the invention relates to a liquid crystal side chain polymer (SCLCP) obtained from a reactive liquid crystal material as defined above by polymerisation or polymeranaloguous reaction. Particularly preferred are SCLCPs obtained from one or more reactive mesogenic compounds or mixtures comprising them as described above.
  • SCLCP liquid crystal side chain polymer
  • Another aspect of the invention relates to an SCLCP obtained from one or more reactive mesogenic compounds or mixtures as defined above, by copolymerisation or polymeranaloguous reaction together with one or more additional mesogenic or non-mesogenic comonomers.
  • SCLCPs Side chain liquid crystal polymers or copolymers
  • the semiconducting component in which the semiconducting component is located as a pendant group, separated from a flexible backbone by an aliphatic spacer group, offer the possibility to obtain a highly ordered lamellar like morphology.
  • This structure consists of closely packed conjugated aromatic mesogens, in which very close (typically ⁇ 4 A) pi-pi stacking can occur. This stacking allows intermolecular charge transport to occur more easily, leading to high charge carrier mobilities.
  • SCLCPs are advantageous for specific applications as they can be readily synthesized before processing and then e.g. be processed from solution in ah organic solvent. If SCLCPs are used in solutions, they can orient spontaneously when coated onto an appropriate surface and when at their mesophase temperature, which can result in large area, highly ordered domains.
  • the invention also relates to the use of reactive mesogenic compounds of the present invention, or liquid crystal mixtures or polymers obtained thereof, as light-modulating component in liquid crystal displays, which may for example be switchable between two different states by an electric field, for components of liquid crystal displays, in particular optical retardation or compensation films, alignment layers or polarisers, or in other optical or electrooptical devices.
  • the invention also relates to a liquid crystal display, component of a liquid crystal display, in particular an optical retardation or compensation films, alignment layer or polariser, or an other optical or electrooptical device comprising reactive mesogenic compounds according to the present invention, or liquid crystal mixtures or polymer films obtained thereof.
  • a 1 and A 2 are unsubstituted thiophene or phenylene groups
  • R or R 1 is alkyl or alkoxy with 1 to 15 C atoms which is optionally mono-, poly- or perfluorinated,
  • X is -0-, -0-CH 2 -, -CH 2 -0- or a single bond
  • a 1 and A 2 are different from
  • R 4 is H, F or R 3 , and
  • a preferred embodiment of the present invention relates to compounds wherein -A 1 -(Z 1 -A 2 ) m - is selected of formula 111
  • ml is 2, 3 or 4
  • the groups Z independently of each other have one of the meanings of Z 1 as defined above
  • Thi is a thiophene- 2,5-diyl group
  • Phe is a 1 ,4-phenylene group, these groups being optionally substituted by one or more groups R 1 as defined above.
  • Another preferred embodiment of the present invention relates to compounds wherein -A 1 -(Z 1 -A 2 ) m - is selected of formula II2
  • m is 1 , 2, 4 or 5 and Z and Thi are as defined in formula 111.
  • Z in formulae 111 to II27 is a single bond.
  • P 1 and P 2 are identical or different groups P as defined in formula I,
  • Sp 1 and Sp 2 are identical or different groups Sp as defined in formula I,
  • X 1 and X 2 are identical or different groups X as defined in formula I,
  • R is as defined in formula I
  • R 1 to R 12 have independently of one another one of the meanings of R 1 in formula I, and are preferably H, halogen or straight-chain alkyl with 1 to 8 C-atoms that is optionally mono-, poly- or perfluorinated, and is O, 1 , 2, 3 or 4.
  • alkyl is an alkylene group with 1 to 12, preferably 2 to 8 C- atoms, t is 0 or 1 , u is 0 or 1 ,
  • R 1 to R 12 is an alkyl or alkoxy radical, i.e. where the terminal CH 2 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, octyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, or octoxy, furthermore methyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy, for example.
  • Halogen is preferably F or Cl.
  • Hetero atoms are preferably selected from N, O and S.
  • the polymerisable or reactive groups P, P 1 and P 2 are preferably
  • Oxetanes produce less shrinkage upon polymerisation (cross-linking), which results in less stress development within films, leading to higher retention of ordering and fewer defects.
  • Oxetane cross-linking also requires cationic initiator, which unlike free radical initiator is inert to oxygen.
  • Typical spacer groups are for example -(CH 2 ) P -, -(CH 2 CH 2 0) q -CH 2 CH 2 -, -CH 2 CH 2 -S-CH 2 CH 2 - or -CH 2 CH 2 -NH-CH 2 CH 2 - or -(SiR°R 00 -O) p -, with p being an integer from 2 to 12, q being an integer from 1 to 3 and R° and R 00 having the meanings given in formula I.
  • Preferred spacer groups are ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylene-thioethylene, ethylene-N-methyl- iminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene for example.
  • each of the groups P, the groups Sp, and the groups X can be identical or different.
  • SCLCPs obtained from the inventive compounds or mixtures by polymerisation or copolymerisation have a backbone that is formed by the polymerisable group P in formula I.
  • the compounds of formula I can be synthesized according to or in analogy to methods that are known to the skilled in the art and are reported in the literature. Furthermore, they can be prepared according to or in analogy to the following reaction schemes.
  • compounds of formula I can be synthesised by transition metal catalysed cross-coupling methodologies.
  • a convienent procedure is the Suzuki reaction involving aryl boronic acids, however the present compounds can also be synthesised by the transition metal catalysed coupling of organotins (Stille reaction), organozincs (Negishi coupling), organomagnesiums (Kumada coupling), organosilicon reagents or aryl lithiums.
  • the polymerisable endgroups can be incorporated before the cross-coupling step (scheme 1), or afterwards (scheme 2 or 3).
  • the reactive mesogenic compounds of formula I are particularly useful as semiconductors or charge transport materials, as they can be aligned into uniform highly ordered orientation in their liquid crystal phase by known techniques, thus exhibiting a higher degree of order that leads to particularly high charge carrier mobility.
  • the highly ordered liquid crystal state can be fixed by in situ polymerisation or crosslinking via the groups P to yield polymer films with high charge carrier mobility and high thermal, mechanical and chemical stability.
  • another aspect of the invention relates to a polymerisable liquid crystal material comprising one or more reactive mesogenic compounds of the present invention as described above and below comprising at least one polymerisable group, and optionally comprising one or more further polymerisable compounds, wherein at least one of the reactive mesogenic compounds of the present invention and/or the further polymerisable compounds is mesogenic or liquid crystalline.
  • liquid crystal materials having a nematic and/or smectic phase.
  • smectic materials are especially preferred.
  • OLED applications nematic or smectic materials are especially preferred.
  • smectic A (S A ) phases are especially preferred.
  • S A smectic A phases, furthermore highly ordered smectic phases like the S B , S E , S G and S F phase.
  • Another aspect of the invention relates to an anisotropic polymer film with charge transport properties obtainable from a polymerisable liquid crystal material as defined above that is aligned in its liquid crystal phase into macroscopically uniform orientation and polymerised or crosslinked to fix the oriented state.
  • Polymerisation is preferably carried out by in-situ polymerisation of a coated layer of the material, preferably during fabrication of the electronic or optical device comprising the inventive semiconductor material.
  • these are preferably aligned in their liquid crystal state into homeotropic orientation prior to polymerisation, where the conjugated pi-electron systems are orthogonal to the direction of charge transport. This ensures that the intermolecular distances are minimised and hence then energy required to transport charge between molecules is minimised.
  • the molecules are then polymerised or crosslinked to fix the uniform orientation of the liquid crystal state. Alignment and curing are carried out in the liquid crystal phase or mesophase of the material. This technique is known in the art and is generally described for example in D.J. Broer, et al., Angew. Makromol. Chem. 183, (1990), 45-66.
  • Alignment of the liquid crystal material can be achieved for example by treatment of the substrate onto which the material is coated, by shearing the material during or after coating, by application of a magnetic or electric field to the coated material, or by the addition of surface-active compounds to the liquid crystal material.
  • Reviews of alignment techniques are given for example by I. Sage in "Thermotropic Liquid Crystals", edited by G. W. Gray, John Wiley & Sons, 1987, pages 75-77, and by T. Uchida and H. Seki in “Liquid Crystals - Applications and Uses Vol. 3", edited by B. Bahadur, World Scientific Publishing, Singapore 1992, pages 1-63.
  • a review of alignment materials and techniques is given by J. Cognard, Mol. Cryst. Liq. CiNst. 78, Supplement 1 (1981), pages 1-77.
  • Actinic radiation means irradiation with light, like UV light, IR light or visible light, irradiation with X-rays or gamma rays or irradiation with high energy particles, such as ions or electrons.
  • Preferably polymerisation is carried out by UV irradiation at a non-absorbing wavelength.
  • a source for actinic radiation for example a single UV lamp or a set of UV lamps can be used. When using a high lamp power the curing time can be reduced.
  • Another possible source for actinic radiation is a laser, like e.g. a UV laser, an IR laser or a visible laser.
  • Polymerisation is preferably carried out in the presence of an initiator absorbing at the wavelength of the actinic radiation.
  • an initiator absorbing at the wavelength of the actinic radiation.
  • a photoinitiator can be used that decomposes under UV irradiation to produce free radicals or ions that start the polymerisation reaction.
  • a radical photoinitiator is used
  • curing polymerisable materials with vinyl, epoxide and oxetane groups preferably a cationic photoinitiator is used.
  • a polymerisation initiator that decomposes when heated to produce free radicals or ions that start the polymerisation.
  • a photoinitiator for radical polymerisation for example the commercially available Irgacure 651 , Irgacure 184, Darocure 173 or Darocure 4205 (all from Ciba Geigy AG) can be used, whereas in case of cationic photopolymerisation the commercially available UVI 6974 (Union Carbide) can be used.
  • the polymerisable material can additionally comprise one or more other suitable components such as, for example, catalysts, sensitizers, stabilizers, inhibitors, chain-transfer agents, co-reacting monomers, surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents, reactive diluents, auxiliaries, colourants, dyes or pigments.
  • suitable components such as, for example, catalysts, sensitizers, stabilizers, inhibitors, chain-transfer agents, co-reacting monomers, surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents, reactive diluents, auxiliaries, colourants, dyes or pigments.
  • Polymerisable benzodithiophenes comprising one or more groups P- Sp-X can also be copolymerised with polymerisable mesogenic compounds to induce, or, in case of mesogenic materials of formula I, enhance liquid crystal phase behaviour.
  • Polymerisable mesogenic compounds that are suitable as comonomers are known in prior art and disclosed for example in WO 93/22397; EP 0,261 ,712; DE 195,04,224; WO 95/22586 and WO 97/00600.
  • SCLCPs can be prepared from the polymerisable compounds or mixtures according to the invention by the methods described above, or by conventional polymerisation techniques which are known to those skilled in the art, including for example radicalic, cationic or anionic polymerisation from unsaturated functionality radicalic, polyaddition or polycondensation.
  • Polymerisation can be carried out for example as polymerisation in solution, without the need of coating and prior alignment, or polymerisation in situ.
  • SCLCPs by grafting compounds according to the invention with a suitable reactive group, or mixtures thereof, to presynthesized isotropic or anisotropic polymer backbones in a polymeranaloguous reaction.
  • compounds with a terminal hydroxy group can be attached to polymer backbones with lateral carboxylic acid or ester groups
  • compounds with terminal isocyanate groups can be added to backbones with free hydroxy groups
  • compounds with terminal vinyl or vinyloxy groups can be added e.g. to polysiloxane backbones with Si-H groups.
  • SCLCPs by copolymerisation or polymeranaloguous reaction from the inventive compounds together with conventional mesogenic or non mesogenic comonomers.
  • Suitable comonomers are known to those skilled in the art. In principle it is possible to use all conventional comonomers known in the art that carry a reactive or polymerisable group capable of undergoing the desired polymer-forming reaction, like for example a polymerisable or reactive group P as defined above.
  • Typical mesogenic comonomers are for example those mentioned in WO 93/22397; EP 0,261,712; DE 195,04,224; WO 95/22586 and WO 97/00600.
  • Typical non mesogenic comonomers are for example alkyl mono- or diacrylates or alkyl mono- or dimethacrylates with alkyl groups of 1 to 20 C atoms, like methyl acrylate or methyl methacrylate, trimethylpropane trimethacrylate or pentaerythritol tetraacrylate.
  • the liquid crystal material preferably comprises one or more compounds of formula I and its preferred subformulae having one or more groups P.
  • the polymer is preferably made from a liquid crystal material comprising one or more compounds of formula I and its preferred subformulae having one group P.
  • the materials of the present invention are useful as optical, electronic and semiconductor materials, in particular as charge transport materials in field effect transistors (FETs) e.g. as components of integrated circuitry, ID tags or TFT applications. Alternatively, they may be used in organic light emitting diodes (OLEDs) in electroluminescent display applications or as backlight of e.g. liquid crystal displays, as photovoltaics or sensor materials, for electrophotographic recording, and for other semiconductor applications.
  • FETs field effect transistors
  • OLEDs organic light emitting diodes
  • electroluminescent display applications or as backlight of e.g. liquid crystal displays, as photovoltaics or sensor materials, for electrophotographic recording, and for other semiconductor applications.
  • oligomers and polymers according to the invention show advantageous solubility properties which allow production processes using solutions of these compounds.
  • films, including layers and coatings may be generated by low cost production techniques e.g. spin coating.
  • Suitable solvents or solvent mixtures comprise alkanes and/ or aromatics, especially their fluorinated derivatives.
  • the materials of the present invention are useful as optical, electronic and semiconductor materials, in particular as charge transport materials in field effect transistors (FETs), as photovoltaics or sensor materials, for electrophotographic recording, and for other semiconductor applications.
  • FETs field effect transistors
  • Such FETs where an organic semiconductive material is arranged as a film between a gate- dielectric and a drain and a source electrode, are generally known e.g. from US 5,892,244, WO 00/79617, US 5,998,804, and from the references cited in the background and prior art chapter and listed below. Due to the advantages, like low cost production using the solubility properties of the compounds according to the invention and thus the processibility of large surfaces, preferred applications of these FETs are such as integrated circuitry, TFT-displays and security applications.
  • field effect transistors and other devices with semiconductive materials 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 materials according to the invention may be used in organic light emitting devices or diodes (OLEDs), e.g. in display applications or as backlight of e.g. liquid crystal displays.
  • OLEDs organic light emitting devices or diodes
  • Common OLEDs are realized using multilayer structures.
  • An emission layer is generally sandwiched between one or more electron-transport and/ or hole-transport layers.
  • 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.
  • 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 e. g. Meerholz, Synthetic Materials, 111-112, 2000, 31-34, Alcala, J. Appl. Phys., 88, 2000, 7124-7128 and the literature cited therein.
  • inventive compounds, materials or films 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 A1 or by C. Weder et al., Science, 279, 1998, 835-837.
  • the materials of the present invention are also useful for the preparation of optical films with anisotropic properties, like for example polarizers, optical retardation films, compensators, colour filters, polarization beam splitters, or polarization filters, which can be used for example as components of liquid crystal displays. Furthermore, they can be used as coatings e.g. for decorative or security use, as adhesives, or for the preparation of liquid crystal pigments.
  • a further aspect of the invention relates to both the oxidised and reduced form of the compounds and materials according to this invention. 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 or WO 96/21659.
  • the doping process typically implies treatment of the semiconductor material with an oxidating 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.
  • suitable dopants are for example halogens (e.g. I 2 , Cl 2 , Br 2 , ICI, ICI 3 , IBr and IF), Lewis acids (e.g. PF 5 , AsF 5 , SbF 5 , BF 3 , BCI 3 , SbCI 5 , BBr 3 and S0 3 ), protonic acids, organic acids, or amino acids (e.g. HF, HCI, HN0 3 , H 2 S0 4 , HCI0 4 , FS0 3 H and CIS0 3 H), transition metal compounds (e.g.
  • halogens e.g. I 2 , Cl 2 , Br 2 , ICI, ICI 3 , IBr and IF
  • Lewis acids e.g. PF 5 , AsF 5 , SbF 5 , BF 3 , BCI 3 , SbCI 5 , BBr 3 and S0 3
  • protonic acids e.g. HF, HCI,
  • FeCI 3 FeOCI, Fe(CI0 4 ) 3 , Fe(4-CH 3 C 6 H 4 S ⁇ 3)3, TiCI 4 , ZrCI 4 , HfCI 4 , NbF 5 , NbCI 5 , TaCI 5 , MoF 5 , M0CI 5 , WF 5 , WCI 6 , UF 6 and LnCI 3 (wherein Ln is a lanthanoid), anions (e.g.
  • H + Li + , Na + , K + , Rb + and Cs + ), alkali metals (e.g., Li, Na, K, Rb, and Cs), alkaline-earth metals (e.g., Ca, Sr, and Ba), 0 2 , XeOF 4 , (N0 2 + ) (SbFef), (N0 2 + ) (SbCl ⁇ -), (N0 2 + ) (BF 4 " ), AgCI0 4 , H 2 lrCI 6 , La(N0 3 ) 3 • 6H 2 0, FS0 2 OOS0 2 F, Eu, acetylcholine, R 4 N + , R 4 P + , R 6 As + , and R 3 S + (wherein R is an alkyl group).
  • alkali metals e.g., Li, Na, K, Rb, and Cs
  • alkaline-earth metals e.g., Ca, Sr, and Ba
  • 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 ot tracts in electronic applications such as printed circuit boards and condensers.
  • Step 1.1 2,5'-Bis(4-hvdroxyphenyl)bithiophene.
  • Step 1.2 6-[4-(5'-(4-r5-(1-vinyl-allyloxycarbonv ⁇ -pentylo ⁇ y]-phenyl)- r2,2'1bithiophenyl-5-vD-phenoxy1-hexanoic acid 1-vinyl-allyl ester
  • 2,5'-Bis(4-hydroxyphenyl)bithiophene (0.50 g, 1.43 mmol) is dissolved in DMF (50 ml), followed by the addition of potassium carbonate (0.59 g, 4.29 mmol), 6-bromohexanoic acid 1-vinylallyl ester (1.12 g, 4.29 mmol, see A.E.A. Contoret et al, Chem. Mater. 2002, 14, 1477) and potassium iodide (0.71 g, 4.29 mmol). This mixture is stirred overnight at 70 °C under nitrogen. After cooling, water (100ml) is added, followed by extraction with ethyl acetate (3 x 70 ml).
  • Step 2.1 5-(4-lodophenyl pentanoic acid.
  • Step 2.2 5-(4-f5'-r4-(4-Carboxy-butvn-phenvn-r2.2']bithiophenyl-5-ylV phenvD-pentanoic acid.
  • 5-(4-lodophenyl)pentanoic acid (2.64 g, 8.68 mmol) and 5,5'- di(4,4,5,5-tetramethyl[1 ,3,2Jdioxoborolan-2-yl)-2,2'-bithiophene (1.54 g, 3.69 mmol) are dissolved in anhydrous NMP (70 ml) at room temperature under nitrogen. Tetrakis(triphenylphosphine)palladium (0) (107 mg, 0.09 mmol) is added and the mixture warmed to 40°C.
  • Tetrabutylammonium hydroxide (10 mL of a 40 wt.% solution in water) is added and the mixture heated to 110°C for 16 h. The reaction is cooled to room temperature and poured into an ice-cold aqeous solution of 5% HCI (500 ml). The resulting precipitate is filtered, and triturated with water, methanol and acetone to afford 1.96 g of product. NMR showed the expected signals.
  • Step 5.3 5-
  • Step 3.1 2-Methyl-acrylic acid 6-r4-(5'-f4-r6-(2-methyl-acyloxy)- hexyloxyl-phenylH2,21bithiophenyl-5-vO-phenoxy]-hexyl ester.
  • 2,5'-Bis(4-hydroxyphenyl)bithiophene (0.50 g, 1.43 mol)
  • potassium carbonate (0.59 g, 4.29 mmol)
  • 6-chlorohexyl methacrylate (0.88 g, 4.29 mmol)
  • potassium iodide (0.71 g, 4.29 mmol)
  • Step 4.1
  • Tetrakis(triphenylphosphine)palladium(0) (0.05 g) is added to a solution of 5',5"-dibromo-[2,2';5',2"]terthiophene (0.1 Og, 0.25 mmol) in dry THF (30 ml), with stirring, under nitrogen.
  • Step 5.1
  • Tetrakis(triphenylphosphine)palladium(0) (0.01 g) is added to a solution of 4,4 ' -dibromobitphenyl (0.12 g, 0.38 mmol) in dry THF (30 ml), with stirring, under nitrogen. After 20 min, 2- ⁇ 5'-[6-(3- ethyloxyoxetan-3-ylmethoxy)hexyl]thioen-2-yl ⁇ -4,4,5,5-tetramethyl- [1 ,3,2]dioxaborolane (0.50 g, 1.22 mmol) and a solution of potassium carbonate (0.35 g, 2.5 mmol) in water (5 ml) is added.
  • Step 6.1 5-(6-chlorohexylV2,2 f -bithiophene
  • 2,2'-bithiophene 10.0 g, 60.24 mmol
  • ⁇ -butyllithium 2.5 M in hexanes, 20.0 ml, 50.0 mmol
  • 1- chloro-6-iodohexane 14.55 g, 50.0 mmol
  • Step 6.2 3-(6-r2.2 , ]bithiophenyl-5-yl-hexyloxymethvn -3-ethyl-oxetane
  • 3-Ethyl-3-oxtanemethanol (3.10 g, 26.72 mmol) is added slowly to a suspension of sodium hydride (60 % dispersion in mineral oil, 1.07 g, 26.72 mmol) in DMF (70 ml) at 0 °C, with stirring, under nitrogen. After complete addition, the ice-bath is removed and the mixture is stirred another 20 min, followed by the addition of 5-(6-chlorohexyl)-2,2 ' - bithiophene (7.61 g, 26.72 mmol). The resultant mixture is stirred overnight, then water (100 ml) is added and the mixture extracted with ethyl acetate (3 x 70 ml).
  • Step 6.3 2-(5'-f6-(3-ethyl-oxetan-3-ylmethoxy)hexyn-
  • the resultant mixture is stirred overnight at room temperature.
  • the reaction is quenched with sat. aq. NH 4 CI, and the reaction mixture is extracted with ethyl acetate (3 x 100 ml).
  • the combined organic extracts are washed with water, brine, and dried over sodium sulphate.
  • Tetrakis(triphenylphosphine)palladium(0.01g) is added to a solution of 1 ,4-dibromobenzene (0.12 g, 0.51 mmol) in dry THF (30 ml), with stirring, under nitrogen.
  • Step 7.1 3 , -Methyl-r2.2 , .5 , ,2"]terthiophene
  • Step 8.1 2-f4-r6-,Tert-butyl-dimethylsilanyloxy ⁇ hexy ⁇ -phenylV4A5,5- tetramethyl- f1 ,3,21dioxaborolane:
  • the extracts are dried (Na 2 S0 4 ) and evaporated under reduced pressure.
  • the residue is purified by column chromatography, eluting with petrol/ethyl acetate (10:0 to 4:1), to give a brown oil (13.83 g, 73 %).
  • Step 8.2 5,5 -Bis-f4-f6-(tert-butyl-dimethylsilanyloxy)hexy ⁇ -phenyl>-
  • Step 8.3 2-Methylacrylic acid 6-r4-(5'-(4-r6-(2-methylacryloyloxy)- hexynphenylH2.21bithiophenyl-5-yl)phenvnhexyl ester.
  • Step 9.2 2 4-r6-((3-ethyloxetan-3-yl)methoxy)hexynphenylV4.4.5.5- tetramethyl -H ,3,21-dioxaborolane
  • reaction is quenched with water, and the reaction mixture is extracted with ethyl acetate (3 x 50 ml). The combined organic extracts are washed with water, brine, and dried (Na 2 S0 4 ). The solvent is removed under reduced pressure and the residue is purified by column chromatography on silica, eluting with petroleum ether/ethyl acetate (9:1 to 7:3), to give a brown oil (1.60g, 71%).
  • a 20 ml microwave tube is charged with 5,5 ' -dibromothiophene (0.20 g, 0.62 mmol), tetrakis(triphenylphosphine)palladium(0) (0.05 g, 0.04 mmol), 2- ⁇ 4- [6-((3-ethyloxetan-3-yl)methoxy)-hexyl]phenyl ⁇ -4 ,4,5,5- tetramethyi-1 ,3,2-dioxaboro-nlane (0.75 g, 1.86 mmol), anhydrous THF (7 ml) and tetrabutylammonium hydroxide (20 % in water, 2 ml).
  • the tube is sealed and heated and stirred in a microwave reactor (Emrys Creator) for 1 min at 100 °C, 1 min at 120 °C and 15 min at 140 °C. After cooling, the mixture is poured into water (100 ml). The precipitate is filtrated off and washed with water and diethyl ether, to give a blue solid, which is purified by column chromatography on silica, eluting with petroleum ether/ethyl acetate (9:1 to 4:1), to give a yellow solid (0.23 g, 52%).

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Abstract

L'invention concerne des nouveaux composés mésogènes réactifs présentant des propriétés de transport de charge, qui comprennent au moins deux groupes thiofène. L'invention concerne également l'utilisation de ces composés en tant que semi-conducteurs ou que matériaux de transport de charge dans des dispositifs optiques électro-optiques ou électroniques de type affichage à cristaux liquides, films optiques, transistors à effet de champ organiques (FET ou OFET) pour des affichages à cristaux liquides à matrice active et des dispositifs à circuits intégrés de type étiquettes d'identification par radiofréquence, dispositifs électroluminescents dans des écrans plats, et dans des dispositifs photovoltaïques et de détection. L'invention concerne en outre un transistor à effet de champ, un dispositif électroluminescent ou une étiquette d'identification par radiofréquence comprenant lesdits composés mésogènes réactifs à propriétés de transport de charge.
EP05701266A 2004-02-25 2005-01-31 Composes reactifs misogenes a transfert de charge contenant au moins de groupements thiophere Withdrawn EP1725541A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP07019781A EP1876177A3 (fr) 2004-02-25 2005-01-31 Composants de transport de charge mésogènes réactifs
EP05701266A EP1725541A2 (fr) 2004-02-25 2005-01-31 Composes reactifs misogenes a transfert de charge contenant au moins de groupements thiophere
EP07019782A EP1903036A1 (fr) 2004-02-25 2005-01-31 Composants de transport de charge mésogènes réactifs

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US54706804P 2004-02-25 2004-02-25
EP04005797 2004-03-11
EP05701266A EP1725541A2 (fr) 2004-02-25 2005-01-31 Composes reactifs misogenes a transfert de charge contenant au moins de groupements thiophere
PCT/EP2005/000911 WO2005080369A2 (fr) 2004-02-25 2005-01-31 Composes mesogenes reactifs a proprietes de transport de charge

Related Child Applications (2)

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EP07019781A Division EP1876177A3 (fr) 2004-02-25 2005-01-31 Composants de transport de charge mésogènes réactifs
EP07019782A Division EP1903036A1 (fr) 2004-02-25 2005-01-31 Composants de transport de charge mésogènes réactifs

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EP1725541A2 true EP1725541A2 (fr) 2006-11-29

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EP05701266A Withdrawn EP1725541A2 (fr) 2004-02-25 2005-01-31 Composes reactifs misogenes a transfert de charge contenant au moins de groupements thiophere
EP07019781A Withdrawn EP1876177A3 (fr) 2004-02-25 2005-01-31 Composants de transport de charge mésogènes réactifs

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DE10353094A1 (de) * 2003-11-12 2005-06-09 H.C. Starck Gmbh Verfahren zur Herstellung linearer organischer Thiophen-Phenylen-Oligomere
JP5004354B2 (ja) * 2008-01-23 2012-08-22 日東電工株式会社 複屈折フィルムおよび偏光素子
WO2021233797A1 (fr) * 2020-05-18 2021-11-25 Merck Patent Gmbh Milieu cristallin liquide

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US6824706B2 (en) * 2001-07-25 2004-11-30 Merck Patent Gesellschaft Mit Beschrank Haftung Mono-, Oligo- and poly-difluorovinyl-(hetero)arylenes, their synthesis and their use as charge transport materials
EP1279689B1 (fr) * 2001-07-25 2008-10-01 MERCK PATENT GmbH Mono-, Oligo et Poly-3-(1,1-difluoroalkyl)thiophènes et leur utilisation comme matériaux de transport de charges
EP1279691A1 (fr) * 2001-07-25 2003-01-29 MERCK PATENT GmbH Mono-, oligo- et polydifluorovinyle-(hetero)arylènes, leur synthèse et utilisation comme matériau de transport de charge
EP1279690A1 (fr) * 2001-07-25 2003-01-29 MERCK PATENT GmbH Mono-, oligo, et poly-3-substitués-4-fluorothiophènes et leur utilisation comme matériaux de transport de charges
KR20030010508A (ko) * 2001-07-25 2003-02-05 메르크 파텐트 게엠베하 모노-, 올리고- 및 폴리-4-플루오로티오펜 및 전하 이동물질로서의 이들의 용도
JP2004123580A (ja) * 2002-09-30 2004-04-22 Fuji Photo Film Co Ltd チエニルアリールアセチレン化合物
EP1439590A3 (fr) * 2002-12-04 2005-03-23 MERCK PATENT GmbH Mono-, oligo- et poly(bisthienyl arylenes) et leur utilisation comme materiaux de transport de charge
US20040119049A1 (en) * 2002-12-04 2004-06-24 Martin Heeney Mono-, oligo- and poly-bis(thienyl) arylenes and their use as charge transport materials

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CN1922167B (zh) 2010-05-05
JP4901718B2 (ja) 2012-03-21
WO2005080369A2 (fr) 2005-09-01
EP1876177A2 (fr) 2008-01-09
EP1903036A1 (fr) 2008-03-26
EP1876177A3 (fr) 2008-04-02
CN1922167A (zh) 2007-02-28
JP2007533659A (ja) 2007-11-22

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