WO2011008168A1 - Materiaux electroluminescents organiques - Google Patents

Materiaux electroluminescents organiques Download PDF

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Publication number
WO2011008168A1
WO2011008168A1 PCT/SG2009/000250 SG2009000250W WO2011008168A1 WO 2011008168 A1 WO2011008168 A1 WO 2011008168A1 SG 2009000250 W SG2009000250 W SG 2009000250W WO 2011008168 A1 WO2011008168 A1 WO 2011008168A1
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independently
compound according
optionally substituted
aryl
group
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PCT/SG2009/000250
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English (en)
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Zhikuan Chen
Ying Lin
Qinde Liu
Zhun Ma
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Agency For Science, Technology And Research
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Priority to PCT/SG2009/000250 priority Critical patent/WO2011008168A1/fr
Priority to TW099123182A priority patent/TW201127935A/zh
Publication of WO2011008168A1 publication Critical patent/WO2011008168A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • 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
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/115—Polyfluorene; Derivatives thereof
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1416—Condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
    • H10K85/146—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE poly N-vinylcarbazol; Derivatives thereof

Definitions

  • the present invention relates generally to light emitting organic materials, particularly electroluminescent organic materials, and to light emitting devices containing such compounds.
  • organic materials including organic polymers, are able to conduct charge due to inclusion of an extensive system of pi bonds in the molecule. That is, compounds with connected or conjugated pi systems, such as polyarylene compounds or
  • polyarylenevinylene compounds e.g. poly(phenylenevinylene) and polyfluorene
  • polyarylenevinylene compounds e.g. poly(phenylenevinylene) and polyfluorene
  • These extended pi molecular orbitals when unfilled or when only partially filled with electrons, provide "channels" for transport of additional electrons along the molecule when a voltage is applied to the molecule.
  • Several such extended pi orbitals can form across a conductive organic material, each having different structure and energy levels. The molecular orbital having the lowest energy level is often an effective path for transport of electrons supplied from an electrode.
  • An injected electron and hole can recombine within the emissive layer, forming a bound electron/hole pair, termed an exciton, which can emit energy when it relaxes from an excited state to a lower energy state.
  • an exciton can emit energy when it relaxes from an excited state to a lower energy state.
  • the energy may be released as ultraviolet or visible light.
  • Electroluminescent organic materials can be conjugated polymers or organic molecules.
  • Examples of polymeric electroluminescent organic materials include poly(1 ,4- phenylenevinylene)s, polyfluorenes, and their derivatives. Electroluminescent polymers are attractive because of their solution processability, which is a relatively cost effective method for manufacturing electronic devices containing electroluminescent organic materials.
  • Non-polymeric molecules represent another category of light emitting materials, for example as emitters or as charge transporting materials.
  • OLEDs organic light emitting diodes
  • organic light emitting materials typically have imbalanced charge transporting characteristics.
  • light emitting materials are able to conduct only one charge carrier, either holes or electrons, but typically not both.
  • poly(1 ,4-phenylenevinylene)s or alkoxy-substituted poly(1 ,4-phenylenevinylene)s are good hole transporters, whereas tris-(8-hydroxyquinoline) aluminum (III) (Alq3) is an electron transporter.
  • Imbalanced charge transporting in OLED devices results in low device efficiency.
  • multilayer devices with one or more of a hole injection layer, hole transport layer, electron injection layer and electron transport layer have been explored.
  • a typical construction includes a hole transport layer, an emissive layer and an electron transport layer, with possible inclusion of a hole injecting layer and/or electron injecting layer. This approach can improve device efficiency but results in increased complexity and cost.
  • Another approach to this problem is to tune the charge transporting property of the materials by incorporation of either hole transporting portions, or electron transporting portions or both into the material to try to improve the device performance. Although some materials comprising one or both of hole transporting and electron transporting portions have been developed, and the performance may be better than materials containing only one component, to date the reported device performance based on such materials is still not satisfactory.
  • blue light emitting materials which can be applied in full colour displays or solid state lighting, are the most challenging topic in OLED research because of their relative low device efficiency and short lifetime, compared to green or red light emitting materials.
  • poly(1 ,4-phenylene)s and polyfluorenes and their respective derivatives have been widely investigated and have demonstrated promising device performance for blue OLED application.
  • low luminescent efficiency and short device lifetime are the main issues for these blue light emitting materials.
  • fluorene based materials the present inventors have found that low device efficiency is mainly caused by an imbalanced charge transporting character. Poor charge injection is also a significant factor.
  • the present inventors have also noted that aggregation of the material can occur, which causes red shift of the emissive spectra.
  • most blue light emitting materials are fluorene-based polymers or small molecules and fluorene-based polymers/oligomers in particular are prone to form aggregates.
  • the undesirable red shift of the emissive spectra leads to poor colour stability and a lowering of the device efficiency.
  • the present invention provides luminescent compounds and materials, methods for their preparation, and their use in light emitting devices, including electroluminescent diodes.
  • a luminescent material having a conjugated backbone is composed of an electron donating triarylamine group in the backbone and an electron withdrawing group in a pendant side chain with a spacer portion separating the two groups.
  • the present invention provides a compound having (1 ) a backbone portion, which backbone portion includes a hole transporting portion comprising a triarylamine group; (2) a side chain portion attached to the backbone portion, which side chain portion includes an electron transporting portion comprising an electron deficient aryl group; and (3) a spacer portion located between the hole transporting portion and the electron transporting portion.
  • the present invention provides a compound comprising the structure according to formula I f A- B - C ⁇
  • -A- or -A-B- comprises a triarylamine and is optionally substituted
  • each of -B- and -C- independently comprises an arylene and is optionally substituted
  • -D is an electron deficient aryl, aryl vinylene or aryl ethynylene, and is optionally substituted with an electron withdrawing group;
  • n is independently 1 to 200.
  • the present invention provides a compound comprising the structure according to formula II:
  • each of Ar 1 , Ar 2 , Ar 4a , Ar 4bl Ar 5 , Ar 7a and Ar 7b is independently arylene, and is optionally substituted;
  • Ar 3 is independently aryl, aryl vinylene or aryl ethynylene, and is optionally substituted;
  • Ar 6 is independently an electron deficient aryl, aryl vinylene or aryl ethynylene, optionally substituted with an electron withdrawing group, and is optionally further substituted;
  • X is independently alkylene, alkenylene, -O-, -OC(O)-, -C(O)O-, -C(0)NR A -, or - NR A C(0)-, wherein each R A , if present, is independently H, alkyl or aryl and is optionally substituted;
  • e is independently 0 or 1 ;
  • each of m, s, v and w is independently 1 to 20;
  • each of I, p, r and t is independently 0 to 20;
  • z is independently 0 to 3;
  • n is independently 1 to 200;
  • the present invention provides a compound according to formula (III):
  • Ar 2 , Ar 3 , Ar 43 , Ar 4b , Ar 5 , Ar 6 , Ar 7a , Ar 7b and X are as defined above; and e, I, m, p, r, s, t, v, w, z and n are as defined above;
  • each Of Ar 8 and Ar 9 is independently aryl, aryl vinylene or aryl ethynylene and is optionally substituted.
  • the present invention provides a light emitting device comprising a compound as described herein.
  • the present invention provides an organic electroluminescent device comprising a compound as described herein.
  • the present invention provides an organic light emitting diode (OLED) comprising a compound as described herein.
  • OLED organic light emitting diode
  • a thin film comprising a compound as described herein.
  • a device comprising an anode, a cathode and a thin film as described herein, the thin film being disposed between the anode and the cathode.
  • a device comprising: an anode; an emissive layer disposed on the anode, the emissive layer comprising a compound as described herein; and a cathode disposed on the emissive layer.
  • the present invention provides a device comprising an emissive layer, wherein the emissive layer comprises a compound or thin film as described herein.
  • a device comprising: an anode; a hole transporting layer disposed on the anode; an emissive layer disposed on the hole transporting layer; an electron transporting layer disposed on the emissive layer; and a cathode disposed on the electron transporting layer; wherein at least one of the hole transporting layer, the emissive layer and the electron transporting layer comprises a compound or thin film as described herein.
  • a device comprising: an anode; a hole injecting layer disposed on the anode; a hole transporting layer disposed on the hole injecting layer; an emissive layer disposed on the hole transporting layer; an electron transporting layer disposed on the emissive layer; and a hole blocking layer disposed on the electron transporting layer; an electron injecting layer disposed on the emissive layer; a cathode disposed on the electron injecting layer; wherein at least one of the hole transporting layer, the emissive layer or the electron transporting layer comprises a compound or thin film as described herein.
  • the present invention provides a photovoltaic cell comprising an active layer wherein the active layer comprises a compound or thin film as described herein.
  • the present invention provides a chemical or bio sensor comprising a sensing layer wherein the sensing layer comprises a compound or thin film as described herein.
  • the devices referred to herein are display devices, for example a display panel.
  • a further aspect of the present invention provides a display device comprising a compound or thin film as described herein.
  • the present invention provides a method of making a compound as described herein.
  • the present invention provides a method of making a device (e.g. an OLED or a display device) as described herein. In a further aspect, the present invention provides a use of a compound as described herein in a device (e.g. an OLED or a display device) as described herein.
  • any one of the aspects may be combined with any one or more of the other aspects, optinal and preferred features associated with one aspect suitably apply to any one of the other aspects.
  • features described with reference to a method or use suitably also apply to a product (compound, device, etc) and vice versa.
  • Embodiments of compounds described herein are electroluminescent, meaning that these compounds emit light when an electrical current is passed through them.
  • these compounds are adapted for use in a charge transport layer or a light emitting layer in an organic electronic device.
  • the compounds as described herein are composed of a hole transporting portion in the backbone, an electron transporting portion in a side chain (e.g. comprising a pendant electron deficient group) and a spacer portion located between the hole and electron transporting portions. This combination of structural features not only provide the compounds with ambipolar transporting functionality but also achieve good device performance.
  • device efficiency, emissive red shift, device lifetime and driving voltage can be favourably altered (e.g. reduced or eliminated as appropriate) by adopting the particular arrangement of components described herein.
  • these compounds are solution processable, and may be readily purified to a relatively high extent.
  • the present invention provides a compound having (1 ) a backbone portion, which backbone portion includes a hole transporting portion comprising a triarylamine group; (2) a side chain portion attached to the backbone portion, which side chain portion includes an electron transporting portion comprising an electron deficient aryl group; and (3) a spacer portion located between the hole transporting portion and the electron transporting portion.
  • the light emitting compounds described herein are composed of monomer units or portions with different functionalities.
  • a first type of monomer is based on triarylamine, which can help holes to be injected from the anode and transported in the emissive layer.
  • a second type of monomer unit is composed of a pendant electron deficient structure, which can help to transport electrons in the emissive layer.
  • the hole transporting monomer unit and electron transporting monomer unit are separated from each other by a third monomer unit to reduce or prevent intramolecular interaction between the first and second monomer units. This intramolecular interaction has been found by the present inventors to be undesirable because it can lead to emissive spectrum red shift.
  • both holes and electrons can be injected into the emissive layer and transported in the emissive layer.
  • an electron deficient group as a side chain or pendant group (i.e. not part of the backbone) the present inventors have achieved a significant improvement in the problem of emissive spectrum red-shift. Specifically, the present inventors have found that placement of the electron deficient group in this way, in combination with the triarylamine portion in the backbone, significantly reduces or prevents functional interaction between the hole transporting and electron transporting portions. In this way the problem of interaction via conjugation is ameliorated.
  • the structures of both the hole transporting monomers and electron transporting monomers are bulky enough to assist in reducing or preventing
  • the design of the materials described herein suitably enhances the colour stability of light emitting materials, particularly for blue light emission applications and especially for fluorine-based light emitting materials.
  • the luminescent compounds as described herein can be used in the emissive layer of a light emitting device, or as dopant in a suitable layer in such a device. A further use is as a host material for electroluminescent light emitting diodes.
  • the compounds defined herein can be fabricated into LED devices, for example through a solution process.
  • the compounds emit blue, green, red or white light.
  • the compound is a blue-light-emitting compound.
  • the compound emits light at a wavelength in the range 400nm to 600nm.
  • the emission maximum is at less than 490nm, preferably less than 480nm and most preferably less than 470nm.
  • the compound is a green-light-emitting compound.
  • the compound is a red-light-emitting compound.
  • the compound is a white-light-emitting compound.
  • Adjustment of the emissive portions of the compound can be used to achieve a change in emission wavelength, for example any one or more of the following groups: Ar 1 , Ar 2 , Ar 43 , Ar 4b or Ar 7b .
  • the backbone can be conjugated or non-conjugated. Suitably the backbone is conjugated.
  • the compound has the structure according to formula I: f A- B - C ⁇
  • -A- or -A-B- comprises a triarylamine and is optionally substituted
  • each of -B- and -C- independently comprises an arylene and is optionally substituted
  • -D is an electron deficient aryl, aryl vinylene or aryl ethynylene, and is optionally substituted with an electron withdrawing group;
  • n is independently 1 to 200.
  • the triarylamine is incorporated into the backbone of the compound through bonding of two of the three amino aryl groups, i.e. the triarylamine is bidentate.
  • -A- or -A- B- has the structure -Ar-N(Ar)-Ar-, wherein each Ar is independently as described herein.
  • -B- whether or not it is part of the triarylamine, is a spacer between the hole transporting (triarylamine containing) portion and the electron transporting portion provided by the backbone arylene -C- and electron deficient group -D.
  • the compound comprises the structure according to formula II:
  • each Of Ar 1 , Ar 2 , Ar 4a , Ar 5 , Ar 7a and Ar 7b is independently arylene, and is optionally substituted;
  • Ar 4b is independently arylene, alkylene, bidentate ether, bidentate ester or bidentate amide and is optionally substituted;
  • Ar 3 is independently aryl, aryl vinylene or aryl ethynylene, and is optionally substituted;
  • Ar 6 is independently an electron deficient aryl, aryl vinylene or aryl ethynylene, optionally substituted with an electron withdrawing group, and is optionally further substituted;
  • X is independently alkylene, alkenylene, -O-, -OC(O)-, -C(O)O-, -C(O)NR A -, or - NR A C(O)-, wherein each R A , if present, is independently H, alkyl or aryl and is optionally substituted;
  • e is independently O or 1 ;
  • each of m, s, v and w is independently 1 to 20;
  • each of I, p, r and t is independently 0 to 20;
  • z is independently 0 to 3; and n is independently 1 to 200;
  • the hole transporting function is provided by the portion:
  • the hole transporting and electron transporting functional units are separated by one or more of the spacer groups:
  • the compound can have any suitable terminal or end-cap groups. However, aryl, aryl vinylene and aryl ethynylene groups are preferred.
  • the compound comprises the structure according to formula III:
  • Ar 1 , Ar 2 , Ar 3 , Ar 4a , Ar 4b , Ar 5 , Ar 6 , Ar 7a , Ar 7b and X are as defined above; and e, I, m, p, r, s, t, v, w, z and n are as defined above;
  • each of Ar 8 and Ar 9 is independently aryl, aryl vinylene or aryl ethynylene and is optionally substituted.
  • a compound 10 as described herein which can be an oligomer or polymer, incorporates a triarylamine portion 12 that provides a hole transporting function.
  • the compound 10 has an electron transporting portion 14, comprising the group - Ar 5 (Ar 6 )- wherein Ar 6 is electron deficient and is optionally substituted by one or more electron withdrawing groups.
  • the compound 10 includes spacer portions 16, 18, 20 and 22. Not all of these need to be present in the compound (i.e. not all of I, p, r and t must ⁇ 0), provided that there is at least one spacer portion between the hole transporting portion 12 and the electron transporting portion 14. Typically one or both of spacer portions 16 and 18 will be present. These spacer groups reduce or prevent intramolecular interaction between the hole transporting portion 12 and electron transporting portion 14.
  • aryl groups 20 and/or 22 may be present, for example to tune the emission or performance characteristics of the compound.
  • any adjustment of the conjugated building blocks in the backbone can suitably be used to affect the emission wavelength.
  • Figure 2 illustrates the backbone portion 24 of the compound.
  • each of Ar 1 , Ar 2 , Ar 43 , Ar 4b , Ar 5 , Ar 73 and Ar 7b is independently C 5-1O oarylene, preferably C 5-8 oarylene, more preferably C 5-50 arylene, more preferably C 5-40 arylene, most preferably C 5-30 arylene, and is optionally substituted.
  • each of Ar 1 , Ar 2 , Ar 4a , Ar 4b , Ar 5 , Ar 73 and Ar 7b is independently at least C 6 arylene (e.g. C 6-50 arylene).
  • each Of Ar 1 , Ar 2 , Ar 4a , Ar 4b , Ar 5 , Ar 7a and Ar 7b is independently C 6- iooarylene, preferably C 6-80 arylene, more preferably C 6 - 50 arylene, more preferably C 6-4O arylene, and most preferably C 6 - 3 oarylene, and is optionally substituted
  • each of An, Ar 2 , Ar 4a , Ar 4b , Ar 5 , Ar 73 and Ar 7b is independently carboarylene or heteroarylene.
  • each Of Ar 1 , Ar 2 , Ar 43 , Ar 4b , Ar 5 , Ar 7a and Ar 7b is independently carboarylene.
  • the heteroarylene contains one or more heteroatoms selected from O, S, N, Si and P, preferably one or more selected from O, S and N, more preferably one or more selected from O and N, and most preferably N.
  • heteroarylene contains one, two, three or four heteroatoms. Where a plurality of heteroatoms are present, they may be the same or different.
  • each Ar 1 is independently C 5-1O oarylene, preferably C 5-50 arylene, more preferably C 5-3 oarylene, more preferably C 5-15 arylene, and most preferably C 6 arylene, and is optionally substituted.
  • each Ar 1 is independently carboarylene or heteroarylene.
  • Ar 1 is carboarylene.
  • each Ar 1 is independently phenylene, fluorenylene, carbazolylene, diarylamino, spirobifluorenylene, spirosilabifluorenylene, indenocarbazolylene, indenofluorenylene, thienylene, thienothienylene or benzothiadiazolylene and is optionally substituted. In this way, if two or more Ar 1 are present, a combination of the above building blocks may be present.
  • each Ar 1 is independently phenylene and is optionally substituted.
  • Ar 1 is unsubstituted.
  • each Ar 2 is independently C 5-1 o O arylene, preferably C 5-80 arylene, more preferably C 5 . 5 oarylene, more preferably C 5-30 arylene, more preferably C 5-15 arylene, and most preferably C 6 arylene, and is optionally substituted.
  • each Ar 2 is independently carboarylene or heteroarylene.
  • Ar 2 is carboarylene.
  • each Ar 2 is independently phenylene, fluorenylene, carbazolylene, diarylamino, spirobifluorenylene, spirosilabifluorenylene, indenocarbazolylene, indenofluorenylene, thienylene, thienothienylene or benzothiadiazolylene and is optionally substituted. In this way, if two or more Ar 2 are present, a combination of the above building blocks may be present.
  • each Ar 2 is independently phenylene and is optionally substituted.
  • Ar 2 is unsubstituted.
  • Ar 2 and Ar 1 are the same.
  • Ar 2 and A ⁇ are different.
  • each Ar 43 is independently C 5-1oo arylene, preferably C 5-50 arylene, more preferably C 5-30 arylene, and most preferably C 5-15 arylene, and is optionally substituted.
  • each Ar 43 is independently carboarylene or heteroarylene.
  • Ar 43 is carboarylene.
  • each Ar 43 is independently phenylene, fluorenylene, carbazolylene,
  • each Ar 43 is independently fluorenylene and is optionally substituted, suitably as follows:
  • each Ar 43 is independently substituted fluorenylene, preferably substituted at the 9-position, suitably as follows:
  • each Ar 43 is independently substituted fluorenylene, preferably di-substituted at the 9-position, suitably as follows:
  • a particularly preferred substituent is alkyl, preferably C 2- i 5 alkyl, more preferably C 2- ioalkyl, more preferably C 3-8 alkyl, more preferably C 5-7 alkyl and most preferably C 6 alkyl, and the alkyl substituent is optionally substituted.
  • each Ar 43 is independently
  • each Ar 4b is independently C 5-1 ooarylene, preferably C 5-50 arylene, more preferably C 5- 3 0 arylene, and most preferably C 5- i 5 arylene, and is optionally substituted.
  • each Ar 4b is independently carboarylene or heteroarylene.
  • Ar 4b is carboarylene.
  • each Ar 4b is independently phenylene, fluorenylene, carbazolylene,
  • each Ar 4b is independently fluorenylene and is optionally substituted.
  • Ar 4b is the same as Ar 4a .
  • Ar 4b can be the same as Ar 7a .
  • each Ar 5 is independently C 5- ioQarylene, preferably C 5-5 oarylene, more preferably C 5-3 oarylene, and most preferably C 5-15 arylene, and is optionally substituted.
  • each Ar 5 is independently carboarylene or heteroarylene.
  • Ar 5 is carboarylene.
  • each Ar 5 is independently phenylene, fluorenylene, carbazolylene, diarylamino, spirobifluorenylene, spirosilabifluorenylene, indenocarbazolylene, indenofluorenylene, thienylene, thienothienylene or benzothiadiazolylene and is optionally substituted. In this way, if two or more Ar 5 are present, a combination of the above building blocks may be present.
  • each Ar 5 is independently fluorenylene and is optionally substituted.
  • each Ar 5 is bonded to Ar 6 at the 9-position, as follows:
  • each Ar 5 is spiro bonded to Ar 6 .
  • Ar 6 is optionally substituted fluorenyl, suitably Ar 5 (Ar 6 ) is as follows:
  • each Ar 7a is independently C 5-1O oarylene, preferably C 5 . 50 arylene, more preferably C 5-30 arylene, and most preferably C 5-15 arylene, and is optionally substituted.
  • each Ar 7a is independently carboarylene or heteroarylene.
  • Ar 7a is carboarylene.
  • each Ar 7a is independently phenylene, fluorenylene, carbazolylene,
  • each Ar 7a is independently fluorenylene and is optionally substituted, suitably as follows:
  • each Ar 7a is independently substituted fluorenylene, preferably substituted at the 9-position, suitably as follows:
  • each Ar 7a is independently substituted fluorenylene, preferably di-substituted at the 9-position, suitably as follows:
  • a particularly preferred substituent is alkyl, preferably C 2- i 5 alkyl, more preferably C 2- ioalkyl, more preferably C 3- ⁇ alkyl, more preferably C 5-7 alkyl and most preferably C 6 alkyl, and the alkyl substituent is optionally substituted.
  • each Ar 7a is independently
  • each Ar 7b is independently C 5- i O oarylene, preferably C 5-50 arylene, more preferably C 5-30 arylene, and most preferably C 5-15 arylene, and is optionally substituted.
  • each Ar 7b is independently carboarylene or heteroarylene.
  • Ar 7a is carboarylene.
  • each Ar 7b is independently phenylene, fluorenylene, carbazolylene,
  • each Ar 7b is independently fluorenylene and is optionally substituted. * ****
  • spacer groups may be the same or different.
  • Ar 4a , Ar 4b , Ar 7a and Ar 7b are the same. In other embodiments some or all of Ar 4a , Ar 4b , Ar 7a and Ar 7b are different. In embodiments Ar 43 and Ar 7a are the same. In embodiments Ar 4b and Ar 7b are the same. In embodiments Ar 43 and Ar 4b are the same. In embodiments Ar 43 and Ar 4b are the same. In embodiments Ar 7a and Ar 7b are the same. Each of Ar 4a , Ar 4b , Ar 7a and Ar 7b can be conjugated or non-conjugated with the groups to which it is attached. Preferably each Of Ar 43 , Ar 4b , Ar 7a and Ar 7b is independently conjugated with the groups to which it is attached.
  • each of the spacer groups Ar 43 , Ar 4b , Ar 73 and Ar 7b provides a conjugated link between neighbouring groups.
  • each Of Ar 43 , Ar 4b , Ar 73 and Ar 7b is independently conjugated with the hole transporting portion (-Ar 1 -N(Ar 3 J-Ar 2 -) and/or Ar 5 .
  • Ar 43 , Ar 4b , Ar 7a and Ar 7b are "neutral" in the sense that they are neither electron deficient nor electron rich. That is, suitably Ar 4a , Ar 4b , Ar 7a and Ar 7b do not provide a hole transporting or electron transporting function.
  • each Ar 3 is independently C 5- i 00 aryl, C 5-1O oaryl vinylene or C 5-1O oaryl ethynylene, preferably C 5-50 aryl, C 5-5 oaryl vinylene or C 5-50 aryl ethynylene, more preferably C 5-3 oaryl, C 5- 3 oaryl vinylene or C 5-3 oaryl ethynylene, and most preferably C 5-15 aryl, C 5-15 aryl vinylene or Cs-i 5 aryl ethynylene, and is optionally substituted.
  • each Ar 3 is independently phenylene, fluorenylene, carbazolylene, diarylamino, spirobifluorenylene, spirosilabifluorenylene, indenocarbazolylene, indenofluorenylene, thienylene, thienothienylene or benzothiadiazolylene and is optionally substituted. In this way, if two or more Ar 3 are present, a combination of the above building blocks may be present.
  • each Ar 3 is independently phenyl and is optionally substituted.
  • each Ar 3 is independently carbazoyl-substituted phenyl and is optionally substituted, suitably as follows:
  • the carbazoyl group is substituted at one or both of the 3- and 6- positions, suitably as follows:
  • the substituent at one or both of the'3- and 6-positions is carbazoyl, suitably as follows:
  • each Ar 6 is independently electron deficient C 5-1O oaryl, C 5- i O oaryl vinylene or C 5- iooaryl ethynylene, more preferably C 5-50 aryl, C 5-50 aryl vinylene or C 5-50 aryl ethynylene, more preferably C 5-3 oaryl, C 5-3 oaryl vinylene or C 5-30 aryl ethynylene, and most preferably C 5- i 5 aryl, C 5-15 aryl vinylene or C 5- i 5 aryl ethynylene, and is optionally substituted with an electron withdrawing group, and is optionally further substituted.
  • the electron deficient nature of Ar 6 may be achieved by selection of an electron deficient group per se, or by providing one or more electron withdrawing substituents. Suitable electron withdrawing groups are discussed herein.
  • each Ar 6 is conjugatedly or non-conjugatedly connected to Ar 5 .
  • Ar 6 is conjugatedly connected to Ar 5 .
  • each Ar 6 is independently one of the following structures:
  • each of R, R", R" and R 1 " is independently halo (especially -F or -Cl), -CN, -NO 2 , -CO, thionyl, sulphonyl, C 1-2 oalkyl, C 1-2 operfluoroalkyl, C 1-2 oalkoxy, C 5-50 aryl, C 5-50 arylene vinylene, or C 5-50 arylene ethynylene, and q is an integer from 0 to 6.
  • any of groups may be either monovalent or bivalent, depending on the context in which the aryl group occurs in the compound as described herein.
  • certain of the compounds are depicted with the bond that attaches the group to the remaining portion of the compound as entering into the centre of the aryl group ring, either at an atom or across a bond. It will be appreciated that such depiction is intended to represent that the particular aryl group may be attached to the remaining portion of the compound by a bond at any available position on the ring.
  • each Ar 6 is independently fluorenyl subtituted with an electron withdrawing group.
  • Ar 6 is phenyl-substituted fluorenyl, wherein the phenyl is substituted with an electron withdrawing group.
  • the fluroenyl is bonded to Ar 5 at the 9-position as follows:
  • the fluorenyl is substituted at one or both of the 2- and 7-positions, suitably with phenyl.
  • the following arrangement is preferred:
  • R EW is an electron withdrawing group.
  • each -Ar 5 (Ar 6 )- is spirobifluorenylene substituted with an electron withdrawing group.
  • the present inventors have found that the -Ar 5 (Ar 6 )- unit containing the electron deficient Ar 6 group as a pendant group can enhance electron transport in the polymer.
  • each Ar 8 is independently C 5- i O oaryl, C 5- i O oaryl vinylene or C 5-100 aryl ethynylene, preferably C 5-50 aryl, C 5-50 aryl vinylene or C 5-5 oaryl ethynylene, more preferably C5-i5ary'.
  • each Ar 8 is independently phenyl and is optionally substituted.
  • each Ar 9 is independently C 5-1O oaryl, C 5- i O oaryl vinylene or C 5-1O oaryl ethynylene, preferably C 5-50 aryl, C 5-50 aryl vinylene or C 5-50 aryl ethynylene, more preferably C 5-3 oaryl, C 5-30 aryl vinylene or Cs- 3 oaryl ethynylene, more preferably C 5- i 5 aryl, C 5 . 15 aryl vinylene or C 5- i 5 aryl ethynylene, and most preferably C 6 aryl, C 6 aryl vinylene or C 6 aryl ethynylene, and is optionally substituted.
  • each Ar 9 is independently phenyl and is optionally substituted.
  • R A if present is independently H, C 1-2 oalkyl or C 5- i 5 aryl and is optionally substituted.
  • each of m, s, v and w is independently 1 to 20.
  • each of m, s, v and w is independently 1 to 20, more preferably 1 to 10, more preferably 1 to 5, more preferably 1 to 3, and most preferably 1.
  • any one of m and s is greater than one, then the relevant Ar group (for example An for m) is chosen independently for each occurrence of that Ar group. For example, where m is 3, each of the 3 A ⁇ groups is chosen independently from the remaining 2 Ar 1 groups (and the same for Ar 2 , if present, and Ar 3 ).
  • bracketed portion e.g. [(Ar 7a ) r -(Ar 5 (Ar 6 )) s -(Ar 7b ),] in the case of w
  • the relevant groups within the bracketed portion is chosen independently for each occurrence of v or w.
  • different triarylamine hole transporting portions and/or different electron transporting portions are possible for each occurrence of m and s and/or v and w, respectively.
  • m is independently 1 to 20.
  • each m is independently 1 to 15, more preferably 1 to 10, more preferably 1 to 5, more preferably 1 to 3, and most preferably 1.
  • s is independently 1 to 20.
  • each s is independently 1 to 15, more preferably 1 to 10, more preferably 1 to 5, more preferably 1 to 3, and most preferably 1.
  • v is independently 1 to 20.
  • each v is independently 1 to 15, more preferably 1 to 10, more preferably 1 to 5, more preferably 1 to 3, and most preferably 1.
  • w is independently 1 to 20.
  • each w is independently 1 to 15, more preferably 1 to 10, more preferably 1 to 5, more preferably 1 to 3, and most preferably 1.
  • each of I, p, r and t is independently 0 to 20 but at least one of p and r ⁇ 0 and when n ⁇ 1 at least one of I and t ⁇ 0.
  • each of I, p, r and t is independently 0 to 10, more preferably 0 to 5, more preferably 0 to 3, and most preferably 0 or 1.
  • the relevant Ar group (for example Ar 43 for I) is chosen independently for each occurrence of that Ar group. For example, where I is 3, each of the 3 Ar 43 groups is chosen independently from the remaining 2 Ar 43 groups.
  • each I is independently 0 to 10 1 more preferably 0 to 5, more preferably 0 to 3, and most preferably 0 or 1.
  • each t is independently 0 to 10, more preferably 0 to 5, more preferably 0 to 3, and most preferably 0 or 1.
  • z is independently 0 to 3.
  • z is independently 0 to 1 , more preferably 0.
  • n is independently 1 to 200.
  • n is independently 1 to 100, preferably 1 to 50, more preferably 1 to 30, more preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5 and most preferably 1 to 3.
  • n 1. If n is greater than one, then the relevant groups within the bracketed portion is chosen independently for each occurrence of n. For example, each of the Ar groups and each of I, m, p, v, r, s, t and w is chosen independently for each occurrence of that Ar group or bracketed portion. Thus, for example, different triarylamine hole transporting portions and/or different electron transporting portions are possible for each occurrence of n.
  • each e is independently 0 or 1.
  • the presence Of Ar 2 is optional (for each repeating unit comprising (Ar 2 ) e ).
  • each e is independently 1.
  • the compound as described herein is an oligomer or polymer.
  • n is greater than 1 so that n defines a repeating unit in the oligomer or polymer.
  • each of v and w is independently greater than 1 so that there is a plurality of hole transporting and/or electron transporting portions.
  • any one or more of An, Ar 2 , Ar 3 , Ar 4a , Ar 4b , Ar 5 , Ar 6 , Ar 7a and Ar 7b is independently substituted.
  • Suitable substituents include one or more of branched or unbranched alkyl, branched or unbranched heteroalkyl, branched or unbranched alkenyl, branched or unbranched heteroalkenyl, branched or unbranched alkynyl, branched or unbranched heteroalkynyl, branched or unbranched alkoxy, aryl and heteroaryl.
  • each of An, Ar 2 , Ar 4a , Ar 4b , Ar 5 , Ar 6 , Ar 7a and Ar 7b is independently substituted by one or more of Ci -2 oalkyl, d -2 oalkoxy and C 5- 50 aryl, which substituents are optionally further substituted.
  • each Ar 3 is independently substituted with C 1-20 alkyl, C 1-20 alkoxy or C 5-50 aryl.
  • each Ar 3 is independently substituted phenyl, more preferably C 5-20 heteroaryl substituted phenyl, more preferably C 5-15 heteroaryl substituted phenyl, more preferably Cs- 15 N-containing heteroaryl and most preferably carbazoyl substituted phenyl.
  • Ar 3 is independently carbazoyl-phenylene and is optionally substituted.
  • Each Ar 5 is preferably independently substituted or unsubstituted phenylene, fluorenylene, spirobifluorenylene, spirosilabifluorenylene, indenofluorenylene.
  • Reference herein to the optional substitution of Ar 5 is a reference to the optional presence of a substituent in addition to Ar 6 .
  • each Ar 6 is independently substituted with an electron withdrawing group, R E w-
  • R E W is selected independently from halo (especially -F and Cl), -CN, -NO 2 , -CO, thionyl, sulphonyl and perfluoroalkyl. More preferably R E w is -CN.
  • the molecular weight Mw of the compound is in the range 1000 to 1 ,000,000 Da, more preferably 1000 to 500,000.
  • Embodiments of compounds of the present invention are luminescent, suitably
  • the present invention provides a light emitting device comprising a compound as described herein.
  • the organic electroluminescent device is or comprises an organic light emitting diode (OLED). That is, the compounds described herein are for use in organic light emitting diodes (OLEDs).
  • the present invention provides an organic electroluminescent device comprising a compound as described herein.
  • the present invention provides an organic light emitting diode (OLED) comprising a compound as described herein.
  • OLED organic light emitting diode
  • the compounds as described herein are used as an emissive layer for organic electroluminescent devices.
  • the present invention provides an organic electroluminescent device comprising an emissive layer, wherein the emissive layer comprises a compound as described herein.
  • the compound of the present invention is present in an organic layer in such organic electroluminescent devices.
  • Such embodiments may be used to form one or more of the emissive layer, a charge injection layer, a charge transport layer or a hole blocking layer.
  • the layer has the form of a thin film.
  • a thin film comprising a compound as described herein.
  • the thin film (e.g. a thin film forming the emissive layer) is typically a thin layer containing a compound as described herein, which layer may be formed to be in the order of from about 0.1 to about 1000 nm thick, preferably from about 1 to about 500 nm thick, more preferably from about 5 to about 250 nm thick, and most preferably from about 5 to about 100 nm thick.
  • the thin film may contain other components.
  • the thin film may comprise a host material such as a conductive organic chemical and a compound as described herein.
  • the host material may be for example poly(9-vinylcarbazole) (PVK), 4,4'-N 1 N'- dicarbazole-biphenyl (CBP), 4,4',4"-tri(N-carbazole)triphenylamine (TCTA), N,N'-diphenyl- N,N'-bis(3-methylphenyl)(1 ,1 '-biphenyl)-4,4'-diamine (TPD), N,N'-bis(1-naphthyl)-N,N'- diphenyl-1 ,1"-biphenyl-4,4'-diamine (NPB), 4,4',4"-tris(N,N-diphenyl-amino)
  • PVK poly(9-vinylcarbazole)
  • CBP 4,4
  • triphenylamine TDATA
  • TDAB diphenylaminobenzene
  • TDAPB TTBND
  • PPD PTDATA
  • BFA-1T PFD
  • p-dmDPS p- DPA-TDAB
  • MTBDAB MTBDAB
  • spiro-mTTB DBC
  • polyfluorene poly(styrenesulfonic acid), poly(3,4-ethylenedioxythiophene), polyacetylene
  • polypyrrole polyaniline
  • 2-(4-biphenyl)-5(4- tertbutyl-phenyl)-1 ,3,4,oxadiazole PBD
  • the ratio of the host material to the compound as described herein may be from about 100:0.01 to about 100:30.
  • the thin film may comprise a compound as described herein as a host material and may further comprise an organic dye or phosphorescent emitter, for example, dyes such as 10-(2-benzothiazolyl)-1 ,1 ,7,7-tetramethyl-2,3,6,7-tetrahydro- 1 H,5H,11 H-[l]benzo-pyrano[6,7,8-ij]quinolizin-11-one, 3-(2-benzothiazolyl)-7- (diethylamino)-2H-1-benzopyran-2-one, 4-(dicyanomethylene)-2-t-butyl-6-(1 ,1 ,7,7- tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB), rubrene, 4-(dicyanomethylene)-2-t-butyl-6- (p-diphenylaminostyryl)-4H-pyran (DCTP), 3-(dicyanomethylene)-5,5-di
  • the ratio of the compound as described herein to the dye or the phosphorescent emitter is from about 100:0.01 to about 1 :1.
  • the thin film may be formed on a suitable substrate, which may be any solid substrate, including quartz, glass, mica, a plastic substrate such as polyethylene terephthalate or polycarbonate, paper, metal, or silicon.
  • a suitable substrate which may be any solid substrate, including quartz, glass, mica, a plastic substrate such as polyethylene terephthalate or polycarbonate, paper, metal, or silicon.
  • the thin film may also be layered onto another layer when forming a multilayered device, or onto an electrode.
  • Suitable solvents include chloroform, toluene, xylene, ethyl benzoate, 1 ,1 ,2,2-tetrachloroethane, THF,
  • the thin film may be formed on a suitable surface using standard deposition or coating methods including solution coating.
  • Solution coating includes spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing, flexo printing, offset printing and inkjet printing.
  • the compounds as described herein and thin films containing such compounds may be used to construct electroluminescent devices, including single layer and multilayer devices.
  • the compounds as described herein and thin films containing such compounds may form the emissive layer in an organic light emitting diode, the active layer in an organic thin film transistor or the active layer in an organic photovoltaic cell.
  • Such devices and layers, as well as their construction, are known in the art.
  • a device comprising an anode, a cathode and a thin film as described herein, the thin film being disposed between the anode and the cathode.
  • a device comprising: an anode; an emissive layer disposed on the anode, the emissive layer comprising a compound or thin film as described herein; and a cathode disposed on the emissive layer.
  • a device comprising: an anode; a hole transporting layer disposed on the anode; an emissive layer disposed on the hole transporting layer; an electron transporting layer disposed on the emissive layer; and a cathode disposed on the electron transporting layer; wherein at least one of the hole transporting layer, the emissive layer and the electron transporting layer comprises a compound or thin film as described herein.
  • a device comprising: an anode; a hole injecting layer disposed on the anode; a hole transporting layer disposed on the hole injecting layer; an emissive layer disposed on the hole transporting layer; an electron transporting layer disposed on the emissive layer; and a hole blocking layer disposed on the electron transporting layer; an electron injecting layer disposed on the emissive layer; a cathode disposed on the electron injecting layer; wherein at least one of the hole transporting layer, the emissive layer or the electron transporting layer comprises a compound or thin film as described herein.
  • the compounds described herein are used as active layers for photovoltaic cells.
  • the present invention provides a photovoltaic cell comprising an active layer wherein the active layer comprises a compound or thin film as described herein.
  • the compounds described herein are used as a sensing layer for a chemical sensor or biosensor.
  • the present invention provides a chemical or bio sensor comprising a sensing layer wherein the sensing layer comprises a compound or thin film as described herein.
  • the devices referred to herein are display devices, for example a display panel.
  • a further aspect of the present invention provides a display device comprising a compound or thin film as described herein.
  • the present invention provides a method of making a compound as described herein.
  • the present invention provides a method of making a device (e.g. an OLED or a display device) as described herein. In a further aspect, the present invention provides a use of a compound as described herein in a device (e.g. an OLED or a display device) as described herein.
  • triarylamine as used herein pertains to a tertiary amine group NR 3 wherein each R is independently an aryl or aryl conjugatedly linked to the N.
  • each R can be independently aryl, arylalkenylene or arylalkynylene.
  • Preferred examples of the congujating linker group are vinylene and alkynylene: such that R is arylene vinylene or arylene ethynylene.
  • two of the amine substituents R are bidentate and the discussion of aryl above applies to the corresponding arylene.
  • backbone as used herein will be familiar to the skilled reader and pertains to the main chain of the compound.
  • aryl as used herein pertains to a monovalent aromatic radical derived from an aromatic compound by removal of one hydrogen atom.
  • An aromatic compound is a cyclic compound having 4n+2 pi electrons where n is an integer equal to or greater than 0.
  • the aryl group may have from 5 to 100 ring atoms, preferably 5 to 80, more preferably 5 to 50, more preferably 5 to 30 and most preferably 5 to 20 ring atoms.
  • arylene as used herein pertains to a bivalent aromatic radical derived from an aromatic compound by removal of two hydrogen atoms.
  • An aromatic compound is a cyclic compound having 4n+2 pi electrons where n is an integer equal to or greater than 0.
  • the arylene group may have from 5 to 100 ring atoms, preferably 5 to 80, more preferably 5 to 50, more preferably 5 to 30 and most preferably 5 to 20 ring atoms. Examples of arylenes in the context of substituents are set out below.
  • heteroaryl group as used herein pertains to an aryl group in which one or more of the backbone carbon atoms has been replaced with a hetero atom, for example one or more of N, O, S, Si or P.
  • heteroarylene as used herein pertains to an arylene group in which one or more of the backbone carbon atoms has been replaced with a hetero atom, for example one or more of N, O, S, Si or P.
  • the symbol "Ar” as used herein pertains generally to an aryl group, an arylene group, a heteroaryl group, a heteroarylene group, an aryl group and an adjacent vinylene group ("aryl vinylene”), an arylene group and an adjacent vinylene group (“arylene vinylene”), a heteroaryl group and an adjacent vinylene group (“heteroaryl vinylene”), a heteroarylene group and an adjacent vinylene group (“heteroarylene vinylene”), an aryl group and an adjacent ethynylene group (“aryl ethynylene”), an arylene group and an adjacent ethynylene group (“arylene ethynylene”), a heteroaryl group and an adjacent ethynylene group (“heteroaryl ethynylene”), or a heteroarylene group and an adjacent ethynylene group (“heteroarylene ethynylene”), or an aryl
  • ethynylene as used herein pertains to the bivalent radical represented by the formula -C ⁇ -.
  • alkyl as used herein pertains to a branched or unbranched monovalent hydrocarbon group, having 1 to 20 carbon atoms.
  • an "alkylene” group as used herein refers to a branched or unbranched bivalent hydrocarbon group, having 1 to 20 carbon atoms. It will be understood that alkenyl and alkenylene are the respective terms for a monovalent and bivalent hydrocarbon radical that contains one or more double bonds and that alkynyl and alkynylene are the respective terms for a monovalent and bivalent hydrocarbon radical that contains one or more triple bonds.
  • carbo refers to compounds and/or groups which have only carbon and hydrogen atoms (but see
  • hetero refers to compounds and/or groups which have at least one heteroatom, for example, multivalent heteroatoms (which are also suitable as ring heteroatoms) such as boron, silicon, nitrogen, phosphorus, oxygen, sulfur, and selenium (more commonly nitrogen, oxygen, and sulfur) and monovalent heteroatoms, such as fluorine, chlorine, bromine, and iodine.
  • heteroatom for example, multivalent heteroatoms (which are also suitable as ring heteroatoms) such as boron, silicon, nitrogen, phosphorus, oxygen, sulfur, and selenium (more commonly nitrogen, oxygen, and sulfur) and monovalent heteroatoms, such as fluorine, chlorine, bromine, and iodine.
  • saturated as used herein, pertains to compounds and/or groups which do not have any carbon-carbon double bonds or carbon-carbon triple bonds.
  • unsaturated refers to compounds and/or groups which have at least one carbon-carbon double bond or carbon-carbon triple bond.
  • Compounds and/or groups may be partially unsaturated or fully unsaturated.
  • monovalent monodentate substituents pertains to substituents which have one point of covalent attachment, via a single bond. Examples of such substituents include halo, hydroxy, and alkyl.
  • identical substituents pertains to substituents which have two points of covalent attachment, and which act as a linking group between two other moieties. Examples of such substituents include alkylene and arylene.
  • electrostatic deficient refers to a pi system that has a deficiency of valence electrons such that the pi system (e.g. aryl group) suitably exhibits an electron withdrawing effect on the group to which it is attached. That is, it has a tendency to pull electrons away from the group to which it is attached.
  • the pi system e.g. aryl group
  • electron deficient aryls include pyridyl, thiazolyl, oxadiazolyl and triazolyl, and their corresponding arylene structures.
  • neighbouring aryl group tends to make an electron-withdrawing aryl group more electron- dense than a neighbouring aryl group that is not electron-withdrawing, similar to n-type materials used in a Si semiconductor, and thus more able to transport electrons.
  • electron-withdrawing groups are groups that create a positive or delta-positive region adjacent to the backbone so as to pull electrons from the backbone toward the substituent.
  • the electron deficient pi system has one or more electron withdrawing substituents attached to it.
  • the electron deficiency of the group may be caused by the presence of the electron withdrawing substituent(s).
  • the aryl or arylene pi system is electron deficient, for example as a result of attached electron withdrawing groups.
  • electron withdrawing groups include -CN, -COOH, halo (especially -F and - Cl), -NO 2 , -CO, perfluoroalkyl, ammonio, thionyl, sulfonyl, amido linked via the oxygen, pyridinium, phosphonium, pyridyl, thiazolyl, oxadiazolyl and triazolyl.
  • Functional groups may conveniently be classified as “electron withdrawing” (-6) or “electron donating” (+ ⁇ ) groups, relative to hydrogen.
  • electron donating groups include, but are not limited to, in approximate order of decreasing strength, -O '
  • electron withdrawing groups include, but are not limited to, in approximate order of decreasing
  • substituted refers to a parent group which bears one or more substitutents.
  • substitutents refers to a chemical moiety which is covalently attached to, or if appropriate, fused to, a parent group.
  • substituents are well known, and methods for their formation and introduction into a variety of parent groups are also well known. Examples of substituents are described in more detail below.
  • alkyl refers to a monovalent moiety obtained by removing a hydrogen atom from a carbon atom of a hydrocarbon compound having from 1 to 20 carbon atoms (unless otherwise specified), which may be aliphatic or alicyclic, and which may be saturated or unsaturated (e.g., partially unsaturated, fully unsaturated).
  • alkyl includes the sub-classes alkenyl, alkynyl, cycloalkyl, cycloalkyenyl, cylcoalkynyl, etc., discussed below.
  • C 1-4 alkyl refers to an alkyl group having from 1 to 4 carbon atoms.
  • groups of alkyl groups include C 1-4 alkyl ("lower alkyl”), C 1-7 alkyl, and
  • Ci -20 alkyl Ci -20 alkyl.
  • the first prefix may vary according to other limitations; for example, for unsaturated alkyl groups, the first prefix must be at least 2; for cyclic and branched alkyl groups, the first prefix must be at least 3; etc.
  • Examples of (unsubstituted) saturated alkyl groups include, but are not limited to, methyl (C 1 ), ethyl (C 2 ), propyl (C 3 ), butyl (C 4 ), pentyl (C 5 ), hexyl (C 6 ), heptyl (C 7 ), octyl (C 8 ), nonyl (C 9 ), decyl (C 10 ), undecyl (C 11 ), dodecyl (C 12 ), tridecyl (C 13 ), tetradecyl (Ci 4 ), pentadecyl (C 15 ), and eicodecyl (C 20 ).
  • Examples of (unsubstituted) saturated linear alkyl groups include, but are not limited to, methyl (C 1 ), ethyl (C 2 ), n-propyl (C 3 ), n-butyl (C 4 ), n-pentyl (amyl) (C 5 ), n-hexyl (C 6 ), and n- heptyl (C 7 ), n-octyl (C8), n-decyl (C 10 ), n-dodecyl (C 12 ), n-tetradecyl (C 14 ), n-hexadecyl (C 16 ), n-octadecyl (C 18 ), and n-eicodecyl (C 20 ).
  • Examples of (unsubstituted) saturated branched alkyl groups include iso-propyl (C 3 ), iso-butyl (C 4 ), sec-butyl (C 4 ), tert-butyl (C 4 ), 3-pentyl, iso-pentyl (C 5 ), 3-methylbutyl, and neo-pentyl (C 5 ), 3,3-dimethylbutyl, 2-ethylbutyl, 4-methylpentyl, 2-hexyl, 2-heptyl, 2-octyl, 2-ethylhexyl, 3,7-dimethyloctyl, 2-butyloctyl, 2-hexyldecyl, 2-octyldodecyl.
  • Alkenyl As noted above, the term "alkenyl,” as used herein, pertains to an alkyl group having one or more carbon-carbon double bonds. Examples of groups of alkenyl groups include C 2-4 alkenyl, C 2-7 alkenyl, C 2 - 20 alkenyl.
  • Alkynyl As noted above, the term "alkynyl,” as used herein, pertains to an alkyl group having one or more carbon-carbon triple bonds.
  • alkynyl groups examples include C 2 - 4 alkynyl, C 2-7 alkynyl, C 2 . 2 oalkynyl.
  • (unsubstituted) unsaturated alkynyl groups include, but are not limited to, ethynyl (ethinyl, -C ⁇ CH) and 2-propynyl (propargyl, -CH 2 -C ⁇ CH).
  • Cycloalkyl refers to an alkyl group which is also a cyclyl group; that is, a monovalent moiety obtained by removing a hydrogen atom from an alicyclic ring atom of a carbocyclic ring of a carbocyclic compound, which carbocyclic ring may be saturated or unsaturated (e.g., partially unsaturated, fully unsaturated), which moiety has from 3 to 20 carbon atoms (unless otherwise specified), including from 3 to 20 ring atoms.
  • cycloalkyl includes the sub-classes cycloalkyenyl and cycloalkynyl.
  • each ring has from 3 to 7 ring atoms.
  • groups of cycloalkyl groups include C 3-2 ocycloalkyl, C 3-15 cycloalkyl, C 3-10 cycloalkyl, C 3-7 cycloalkyl.
  • cycloalkyl groups include, but are not limited to, those derived from:
  • indene C 9
  • indane e.g., 2,3-dihydro-1H-indene
  • tetraline C 9
  • alkylidene (1 ,2,3,4-tetrahydronaphthalene) (C 10 ), acenaphthene (C 12 ), fluorene (C 13 ), phenalene (C 13 ), acephenanthrene (C 15 ), aceanthrene (C 16 ), cholanthrene (C 20 ).
  • Alkylidene The term "alkylidene,” as used herein, pertains to a divalent monodentate moiety obtained by removing two hydrogen atoms from an aliphatic or alicyclic carbon atom of a hydrocarbon compound having from 1 to 20 carbon atoms (unless otherwise specified). Examples of groups of alkylidene groups include Ci -2 oalkylidene,
  • Ci -7 alkylidene Ci -4 alkylidene.
  • Alkylidyne refers to a trivalent monodentate moiety obtained by removing three hydrogen atoms from an aliphatic or alicyclic carbon atom of a hydrocarbon compound having from 1 to 20 carbon atoms (unless otherwise specified).
  • groups of alkylidyne groups include Ci -2 oalkylidyne,
  • alkylidyne groups include, but are not limited to, methylidyne ( ⁇ CH), ethylidyne ( ⁇ C-CH 3 ), and benzylidyne ( ⁇ C-Ph).
  • Carbocyclyl refers to a monovalent moiety obtained by removing a hydrogen atom from a ring atom of a carbocyclic compound, which moiety has from 3 to 20 ring atoms (unless otherwise specified). Preferably, each ring has from 3 to 7 ring atoms.
  • C 3-20 , C 3-7 , C 5-6 , etc. denote the number of ring atoms, or range of number of ring atoms.
  • C 5-6 carbocyclyl as used herein, pertains to a carbocyclyl group having 5 or 6 ring atoms.
  • groups of carbocyclyl groups include C 3-20 Ca rbocyclyl, C 3-1o carbocyclyl, C 5-10 carbocyclyl,
  • heterocyclyl refers to a monovalent moiety obtained by removing a hydrogen atom from a ring atom of a heterocyclic compound, which moiety has from 3 to 20 ring atoms (unless otherwise specified), of which from 1 to 10 are ring heteroatoms.
  • each ring has from 3 to 7 ring atoms, of which from 1 to 4 are ring heteroatoms.
  • the prefixes denote the number of ring atoms, or range of number of ring atoms, whether carbon atoms or heteroatoms.
  • the term "C 5 ⁇ heterocyclyl,” as used herein, pertains to a heterocyclyl group having 5 or 6 ring atoms. Examples of groups of heterocyclyl groups include C 3-20 heterocyclyl,
  • aryl refers to a monovalent moiety obtained by removing a hydrogen atom from an aromatic ring atom of an aromatic compound, which moiety may have from 5 to 100 ring atoms (unless otherwise specified). Preferably, each ring has from 5 to 7 ring atoms.
  • the prefixes e.g., C 5-20 , C 5-7 , C 5-6 , etc.
  • C 5-6 aryl refers to an aryl group having 5 or 6 ring atoms.
  • groups of aryl groups include C 5-20 aryl, C 5-15 aryl, C 5- i 2 aryl, C 5-1o aryl, C 5-7 aryl, C 5-6 aryl, C 5 aryl, and C 6 aryl.
  • the ring atoms may be all carbon atoms, as in "carboaryl groups.”
  • carboaryl groups include C 5- i 00 carboaryl, C 5-20 Ca rboaryl, C 5- i 5 carboaryl, C 5- i 2 carboaryl,
  • carboaryl groups include, but are not limited to, those derived from benzene (i.e., phenyl) (C 6 ), naphthalene (C 10 ), azulene (Ci 0 ), anthracene (C 14 ), phenanthrene (C 14 ), naphthacene (C 18 ), and pyrene (C 16 ).
  • aryl groups which comprise fused rings include, but are not limited to, groups derived from indane (e.g., 2,3-dihydro-1 H- indene) (C 9 ), indene (C 9 ), isoindene (C 9 ), tetraline (1 ,2,3,4-tetrahydronaphthalene (C 10 ), acenaphthene (Ci 2 ), fluorene (C13), phenalene (C 13 ), acephenanthrene (Ci 5 ), and aceanthrene (Ci 6 ).
  • indane e.g., 2,3-dihydro-1 H- indene
  • indene C 9
  • isoindene C 9
  • acenaphthene Ci 2
  • fluorene C13
  • phenalene C 13
  • acephenanthrene
  • the ring atoms may include one or more heteroatoms, as in "heteroaryl groups.”
  • heteroaryl groups include C 5-10 oheteroaryl, C 5-2 oheteroaryl,
  • monocyclic heteroaryl groups include, but are not limited to, those derived from:
  • Ni pyrrole (azole) (C 5 ), pyridine (azine) (C 6 );
  • N 1 Oi oxazole (C 5 ), isoxazole (C 5 ), isoxazine (C 6 );
  • N 1 Si thiazole (C 5 ), isothiazole (C 5 );
  • N 2 imidazole (1 ,3-diazole) (C 5 ), pyrazole (1 ,2-diazole) (C 5 ), pyridazine (1 ,2-diazine) (C 6 ), pyrimidine (1 ,3-diazine) (C 6 ) (e.g., cytosine, thymine, uracil), pyrazine (1 ,4-diazine) (C 6 ); N 3 : triazole (C 5 ), triazine (C 6 ); and,
  • heterocyclic groups (some of which are also heteroaryl groups) which comprise fused rings, include, but are not limited to:
  • Cgheterocyclic groups (with 2 fused rings) derived from benzofuran (O 1 ), isobenzofuran (O 1 ), indole (N 1 ), isoindole (Ni), indolizine (N 1 ), indoline (Ni), isoindoline (Ni), purine (N 4 ) (e.g., adenine, guanine), benzimidazole (N 2 ), indazole (N 2 ), benzoxazole (N 1 O 1 ), benzisoxazole (N 1 O 1 ), benzodioxole (O 2 ), benzofurazan (N 2 Oi), benzotriazole (N 3 ), benzothiofuran (Si), benzothiazole (N 1 S 1 ), benzothiadiazole (N 2 S);
  • C 13 heterocyclic groups (with 3 fused rings) derived from carbazole (N 1 ), dibenzofuran (O 1 ), dibenzothiophene (S 1 ), carboline (N 2 ), perimidine (N 2 ), pyridoindole (N 2 ); and, Ci 4 heterocyclic groups (with 3 fused rings) derived from acridine (Ni), xanthene (O 1 ), thioxanthene (Si), oxanthrene (O 2 ), phenoxathiin (O 1 S 1 ), phenazine (N 2 ), phenoxazine (N 1 O 1 ), phenothiazine (N 1 S 1 ), thianthrene (S 2 ), phenanthridine (N 1 ), phenanthroline (N 2 ), phenazine (N 2 ).
  • Ci 4 heterocyclic groups (with 3 fused rings) derived from acridine (Ni),
  • Heterocyclic groups which have a nitrogen ring atom in the form of an -NH- group may be N-substituted, that is, as -NR-.
  • pyrrole may be N-methyl substituted, to give N-methylpyrrole.
  • N-substitutents include, but are not limited to C 1-7 alkyl, C 3-20 heterocyclyl, C 5-2 oaryl, and acyl groups.
  • quinoline may be substituted to give quinoline N- oxide; pyridine to give pyridine N-oxide; benzofurazan to give benzofurazan N-oxide (also known as benzofuroxan).
  • Hydrogen -H. Note that if the substituent at a particular position is hydrogen, it may be convenient to refer to the compound or group as being "unsubstituted" at that position.
  • Halo -F, -Cl, -Br, and -I.
  • Ether -OR, wherein R is an ether substituent, for example, a C 1-7 alkyl group (also referred to as a C 1-7 alkoxy group, discussed below), a C 3-20 heterocyclyl group (also referred to as a C 3-20 heterocyclyloxy group), or a C 5-20 aryl group (also referred to as a Cs ⁇ oaryloxy group), preferably a C 1-7 alkyl group.
  • R is an ether substituent, for example, a C 1-7 alkyl group (also referred to as a C 1-7 alkoxy group, discussed below), a C 3-20 heterocyclyl group (also referred to as a C 3-20 heterocyclyloxy group), or a C 5-20 aryl group (also referred to as a Cs ⁇ oaryloxy group), preferably a C 1-7 alkyl group.
  • Alkoxy -OR, wherein R is an alkyl group, for example, a C 1-7 alkyl group.
  • C 1-7 alkoxy groups include, but are not limited to, -OMe (methoxy), -OEt (ethoxy), -O(nPr) (n-propoxy), -O(iPr) (isopropoxy), -O(nBu) (n-butoxy), -O(sBu) (sec-butoxy), -O(iBu) (isobutoxy), and -O(tBu) (tert-butoxy).
  • Acetal -CH(OR 1 )(OR 2 ), wherein R 1 and R 2 are independently acetal substituents, for example, a C 1-7 alkyl group, a C 3-2 oheterocyclyl group, or a C 5-2 oaryl group, preferably a Ci -7 alkyl group, or, in the case of a "cyclic" acetal group, R 1 and R 2 , taken together with the two oxygen atoms to which they are attached, and the carbon atoms to which they are attached, form a heterocyclic ring having from 4 to 8 ring atoms.
  • acetal groups include, but are not limited to, -CH(OMe) 2 , -CH(OEt) 2 , and -CH(OMe)(OEt).
  • Formyl (carbaldehyde, carboxaldehyde): -C( O)H.
  • Carboxy (carboxylic acid): -C( O)OH.
  • Thionocarboxy (thionocarboxylic acid): -C( S)OH.
  • Ester (carboxylate, carboxylic acid ester, oxycarbonyl): -C( 0)0R, wherein R is an ester substituent, for example, a C 1-7 alkyl group, a C 3-20 heterocyclyl group, or a C 5-20 aryl group, preferably a d -7 alkyl group.
  • acyloxy (reverse ester): -0C( 0)R, wherein R is an acyloxy substituent, for example, a C 1-7 alkyl group, a C 3-2 oheterocyclyl group, or a C 5-2 oaryl group, preferably a C 1-7 alkyl group.
  • R is an acyloxy substituent, for example, a C 1-7 alkyl group, a C 3-2 oheterocyclyl group, or a C 5-2 oaryl group, preferably a C 1-7 alkyl group.
  • Oxycarboyloxy: -OC( O)OR, wherein R is an ester substituent, for example, a C 1-7 alkyl group, a C 3-20 heterocyclyl group, or a C 5 . 20 aryl group, preferably a Ci -7 alkyl group.
  • ester groups include, but are not limited
  • R 1 and R 2 are independently amino substituents, for example, hydrogen, a Ci -7 alkyl group (also referred to as Ci -7 alkylamino or di-Ci -7 alkylamino), a C 3-20 heterocyclyl group, or a C 5-20 aryl group, preferably H or a Ci -7 alkyl group, or, in the case of a "cyclic" amino group, R 1 and R 2 , taken together with the nitrogen atom to which they are attached, form a heterocyclic ring having from 4 to 8 ring atoms.
  • a Ci -7 alkyl group also referred to as Ci -7 alkylamino or di-Ci -7 alkylamino
  • C 3-20 heterocyclyl group or a C 5-20 aryl group, preferably H or a Ci -7 alkyl group
  • R 1 and R 2 taken together with the nitrogen atom to which they are attached, form a heterocyclic ring having from 4 to 8 ring atoms.
  • Amino groups may be primary (-NH 2 ), secondary (-NHR 1 ), or tertiary (-NHR 1 R 2 ), and in cationic form, may be quaternary (- + NR 1 R 2 R 3 ).
  • Examples of amino groups include, but are not limited to, -NH 2 , -NHCH 3 , -NHC(CH 3 ) 2 , -N(CH 3 ) 2 , -N(CH 2 CH 3 ) 2 , and -NHPh.
  • Examples of cyclic amino groups include, but are not limited to, aziridino, azetidino, pyrrolidino, piperidino, piperazino, morpholino, and thiomorpholino.
  • amido groups include, but are not limited
  • R 1 and R 2 together with the nitrogen atom to which they are attached, form a heterocyclic structure as in, for example, piperidinocarbonyl, morpholinocarbonyl, thiomorpholinocarbonyl, and piperazinocarbonyl.
  • Thioamido (thiocarbamyl): -C( S)NR 1 R 2 , wherein R 1 and R 2 are independently amino substituents, as defined for amino groups.
  • R 1 is an amide substituent, for example, hydrogen, a C 1-7 alkyl group, a C 3-2 oheterocycIyl group, or a C 5-2 oaryl group, preferably hydrogen or a C 1-7 alkyl group
  • R 2 is an acyl substituent, for example, a Ci -7 alkyl group, a C
  • R 1 and R 2 may together form a cyclic structure, as in, for example, succinimidyl, maleimidyl, and phthalimidyl:
  • C 1-7 alkyl group a C 3-20 heterocyclyl group, or a C 5-20 aryl group, preferably hydrogen or a
  • ureido groups include, but are not limited to, -NHCONH 2 , -
  • Ci -7 alkyl group may be substituted with, for example:
  • hydroxy also referred to as a hydroxy-Ci -7 alkyl group
  • halo also referred to as a halo-Ci -7 alkyl group
  • amino also referred to as a amino-C 1-7 alkyl group
  • carboxy also referred to as a carboxy-C 1-7 alkyl group
  • C 1-7 alkoxy also referred to as a Ci -7 alkoxy-C 1-7 alkyl group
  • C 5-20 aryl also referred to as a C 5-2 oaryl-Ci -7 alkyl group.
  • a C 5-20 aryl group may be substituted with, for example:
  • hydroxy also referred to as a hydroxy-C 5-20 aryl group
  • halo also referred to as a halo-C 5-20 aryl group
  • amino also referred to as an amino-C 5 . 2 oaryl group, e.g., as in aniline
  • carboxy also referred to as an carboxy-C 5-20 aryl group, e.g., as in benzoic acid
  • C 1-7 alkyl also referred to as a Ci -7 alkyl-C 5-2 oaryl group, e.g., as in toluene
  • Ci -7 alkyl-C 5-2 oaryl group e.g., as in toluene
  • Ci -7 alkoxy also referred to as a Ci -7 alkoxy-C 5-20 aryl group, e.g., as in anisole
  • C 5-2 oaryl also referred to as a C5- 2 oaryl-C 5-2O aryl, e.g., as in biphenyl
  • hydroxy-C 1-7 alkyl The term " hydroxy-Ci -7 alkyl,” as used herein, pertains to a Ci -7 alkyl group in which at least one hydrogen atom (e.g., 1 , 2, 3) has been replaced with a hydroxy group. Examples of such groups include, but are not limited
  • Halo-Ci -7 alkyl group refers to a C 1-7 alkyl group in which at least one hydrogen atom (e.g., 1 , 2, 3) has been replaced with a halogen atom (e.g., F, Cl, Br, I). If more than one hydrogen atom has been replaced with a halogen atom, the halogen atoms may independently be the same or different.
  • Every hydrogen atom may be replaced with a halogen atom, in which case the group may conveniently be referred to as a Ci -7 perhaloalkyl group.”
  • groups include, but are not limited to, -CF 3 , -CHF 2 , -CH 2 F, -CCI 3 , -CBr 3 , -CH 2 CH 2 F, -CH 2 CHF 2 , and -CH 2 CF 3 .
  • Amino-Ci -7 alkyl refers to a C 1-7 alkyl group in which at least one hydrogen atom (e.g., 1 , 2, 3) has been replaced with an amino group. Examples of such groups include, but are not limited to, -CH 2 NH 2 , -CH 2 CH 2 NH 2 , and -CH 2 CH 2 N(CHa) 2 .
  • Carboxy-Ci -7 alkyl The term "carboxy-C 1-7 alkyl,” as used herein, pertains to a Ci -7 alkyl group in which at least one hydrogen atom (e.g., 1 , 2, 3) has been replaced with a carboxy group. Examples of such groups include, but are not limited to, -CH 2 COOH and -CH 2 CH 2 COOH.
  • C 1-7 alkoxy-C 1-7 alkyl pertains to a Ci -7 alkyl group in which at least one hydrogen atom (e.g., 1 , 2, 3) has been replaced with a
  • C ⁇ alkoxy group examples include, but are not limited
  • C 5-20 aryl-Ci -7 alkyl The term "C 5-20 aryl-C 1-7 alkyl,” as used herein, pertains to a C 1-7 alkyl group in which at least one hydrogen atom (e.g., 1 , 2, 3) has been replaced with a C 5- 20 aryl group.
  • hydroxy-C 5-2 oaryl refers to a C 5-20 aryl group in which at least one hydrogen atom (e.g., 1 , 2, 3) has been substituted with an hydroxy group.
  • groups include, but are not limited to, those derived from: phenol, naphthol, pyrocatechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol.
  • Halo-C 5-20 aryl refers to a C 5-20 aryl group in which at least one hydrogen atom (e.g., 1 , 2, 3) has been substituted with a halo (e.g., F, Cl 1 Br, I) group.
  • halo e.g., F, Cl 1 Br, I
  • groups include, but are not limited to, halophenyl (e.g., fluorophenyl, chlorophenyl, bromophenyl, or iodophenyl, whether ortho-, meta-, or para- substituted), dihalophenyl, trihalophenyl, tetrahalophenyl, and pentahalophenyl.
  • Ci -7 alkyl-C 5-2 oaryl The term "C 1-7 alkyl-C 5-20 aryl," as used herein, pertains to a C 5-2 oaryl group in which at least one hydrogen atom (e.g., 1 , 2, 3) has been substituted with a Ci -7 alkyl group.
  • Examples of such groups include, but are not limited to, tolyl (from toluene), xylyl (from xylene), mesityl (from mesitylene), and cumenyl (or cumyl, from cumene), and duryl (from durene).
  • Hydroxy-Ci -7 alkoxy -OR, wherein R is a hydroxy-C 1-7 alkyl group.
  • hydroxy-Ci -7 alkoxy groups include, but are not limited to, -OCH 2 OH, -OCH 2 CH 2 OH, and -OCH 2 CH 2 CH 2 OH.
  • Carboxy-Ci -7 alkoxy -OR, wherein R is a carboxy-C 1-7 alkyl group.
  • Examples of carboxy- C 1-7 alkoxy groups include, but are not limited to, -OCH 2 COOH, -OCH 2 CH 2 COOH, and -OCH 2 CH 2 CH 2 COOH.
  • Ci -7 alkoxy-C 1-7 alkoxy -OR, wherein R is a Ci -7 alkoxy-C 1-7 alkyl group.
  • Examples of Ci -7 alkoxy-C 1-7 alkoxy groups include, but are not limited to, -OCH 2 OCH 3 , -OCH 2 CH 2 OCH 3 , and -OCH 2 CH 2 OCH 2 CH 3 .
  • Ci -7 alkyl-C 5-2 oaryloxy -OR, wherein R is a Ci -7 alkyl-C 5-2 oaryl group.
  • examples of such groups include, but are not limited to, tolyloxy, xylyloxy, mesityloxy, cumenyloxy, and duryloxy.
  • Amino-C 1-7 alkyl-amino pertains to an amino group, -NR 1 R 2 , in which one of the substituents, R 1 or R 2 , is itself a amino-Ci -7 alkyl group (-C 1-7 alkyl-NR 3 R 4 ).
  • the amino-Ci -7 alkylamino group may be represented, for example, by the formula -NR 1 -Ci -7 alkyl-NR 3 R 4 . Examples of such groups include, but are not limited to, groups of the formula -NR 1 (CH 2 ) n NR 1 R 2 , where n is 1 to 6 (for
  • the substituent(s), often referred to herein as R are independently selected from: halo; hydroxy; ether (e.g., C 1-7 alkoxy); formyl; acyl (e.g., C 1-7 alkylacyl , C 5-20 arylacyl); acylhalide; carboxy; ester; acyloxy; amido; acylamido;
  • thioamido tetrazolyl; amino; nitro; nitroso; azido; cyano; isocyano; cyanato; isocyanato; thiocyano; isothiocyano; sulfhydryl; thioether (e.g., C 1-7 alkylthio); sulfonic acid; sulfonate; sulfone; sulfonyloxy; sulfinyloxy; sulfamino; sulfonamino; sulfinamino; sulfamyl;
  • C 1-7 alkyl including, e.g., unsubstituted Ci -7 alkyl, Ci -7 haloalkyl,
  • the substituent(s), often referred to herein as R are independently selected from: hydroxy; ether (e.g., C 1-7 alkoxy); ester; amido; amino; and, Ci -7 alkyl (including, e.g., unsubstituted C 1-7 alkyl, Ci -7 haloalkyl, Ci -7 hydroxyalkyl,
  • Figure 1 illustrates the hole transporting, electron transporting and spacer portions of the compound of formula I
  • Figure 2 illustrates the backbone portion of the compound of formula I
  • Figure 3 shows a schematic diagram of an OLED device, being an embodiment of the present invention
  • Figure 4 shows the TGA plots of PCPC4 and PTCC4
  • Figure 5 shows the DSC plots of PCPC4 and PTCC4
  • Figure 6 shows the UV-vis absorption and photoluminescence (PL) spectra of PCPC4 and PTCC4 in toluene;
  • Figure 7 shows the thin film UV-vis absorption and photoluminescence (PL) spectra of PCPC4 and PTCC4;
  • FIG. 8 shows the electroluminescence (EL) spectrum of PCPC4
  • Figure 9A and Figure 9B show the I-V-L characteristics and current efficiency of PCPC4 respectively;
  • Figure 10 shows the electroluminescence (EL) spectrum of PTCC4
  • Figure 11 A and Figure 11 B show the I-V-L characteristics and current efficiency of PTCC4 respectively.
  • Nuclear magnetic resonance (NMR) spectra were collected on a Bruker DPX 400 MHz spectrometer using chloroform-d or dichloromethane-d 2 as the solvent and
  • TMS tetramethylsilane
  • MALDI-TOF Matrix-Assisted Laser Desorption/lonization Time-Of-Flight
  • DSC Differential scanning calorimetry
  • TGA Thermal gravimetric analysis
  • TA Instrument TGA 2050 module heating rate of 20 °C/min.
  • Cyclic voltammetry (CV) experiments were performed on an Autolab potentiostat (model PGSTAT30). All CV measurements were recorded in dichloromethane with 0.1 M tetrabutylammonium hexafluorophosphate as supporting electrolyte (scan rate of 50 mV/s) using a conventional three electrode configuration consisting of a platinum wire working electrode, a gold counter electrode, and a Ag/AgCI in 3 M KCI reference electrode.
  • the absorption spectra were recorded on a Shimadzu UV-3101 PC UV-vis-NIR spectrophotometer using dichloromethane solution, except where stated otherwise, with concentration ranging from 1.8 x 10 "6 to 3.1 * 10 "6 M.
  • Example 2 Synthesis of N-(4-(9H-carbazol-9-yl)phenyl)-4-bromo-N-(4- bromophenyl)aniline (5)
  • Step 2 Synthesis of 4-[(3, 6-Di-9H-carbazol-9-yl)-9H-carbazol-9-yl]aniline (8) To a solution of 7 (3.71g, 6.0 mmol) in 250 mL of dry THF/ethanol(1 :1 ) was added
  • Step 3 Synthesis of N-(4-((3,6-Di-9H-carbazol-9-yl))phenyl)-4-bromo-N-(4- bromophenyl)aniline (9)
  • ITO/PEDOT:PSS/emissive layer/CsF/Ca/AI All devices were prepared on ITO.
  • a layer of 50nm thick polyethylenedioxythiophene-polystyrenesulfonate (PEDOT:PSS Bayer, Germany) was spin-coated onto the precleaned ITO substrates and then baked at 120 0 C for 30 minutes to extract residual water.
  • PEDOT:PSS Bayer, Germany polyethylenedioxythiophene-polystyrenesulfonate
  • a mixture of 70 wt% polymer and 30 wt% PBD, dissolved in chloroform at concentration of 1% was spin-coated at 1500 rpm onto PEDOT as the emissive layer.
  • the polymer of the emissive layer in each case is described below in Examples 13 to 21.
  • the samples were annealed at 120 0 C for 30 minutes to remove residual solvent.
  • the thickness of the emissive layer was about 80 nm.
  • a 1 nm thick CsF buffer layer and a cathode of bilayer Ca (20 nm)/AI (100 nm) were then thermally evaporated at a chamber base pressure of ⁇ 10 "4 Pa.
  • the device area was 16 mm 2 , which is determined by widths of ITO and Ca/AI electrodes.
  • the evaporated layer thicknesses were controlled using a crystal thickness monitor and a step profiler (Dektak 6M stylus profiler, Veeco) was used to determine the thickness of the spin coated films.
  • Figure 3 shows a schematic diagram of the OLED device with configuration of
  • the steady-state current-brightness-voltage characteristics were recorded using a computer-controlled source meter (Keithley 2400) with a calibrated Si photodiode.
  • the EL spectra were measured by a PR650 SpectraScan spectrophotometer. All data are obtained at room temperature.
  • Example 13 control device
  • Turn-on voltage is 3.5 V.
  • the maximum brightness is 2530 cd/m 2 (at 8.7 V); maximum current efficiency is 0.98 cd/A (at 5.1 V); current efficiency at 100 cd/m 2 is 0.91 cd/A (at 4.3 V).
  • Example 14 control device
  • Turn-on voltage is 4.7 V.
  • the maximum brightness is 2466 cd/m 2 (at 10.9 V); maximum current efficiency is 0.56 cd/A (at 8.1 V); current efficiency at 100 cd/m 2 is 0.39 cd/A (at 6.5 V).
  • Turn-on voltage is 3.7 V.
  • the maximum brightness is 3571 cd/m 2 (at 10.1 V); maximum current efficiency is 0.80 cd/A (at 6.5 V); current efficiency at 100 cd/m 2 is 0.72 cd/A (at 4.9 V).
  • Turn-on voltage is 3.2 V.
  • the maximum brightness is 5306 cd/m 2 (at 10.3 V); maximum current efficiency is 1.64 cd/A (at 5.3 V); current efficiency at 100 cd/m 2 is 1.52 cd/A (at 4.3 V).
  • Turn-on voltage is 3.1 V.
  • the maximum brightness is 6369 cd/m 2 (at 10.9 V); maximum current efficiency is 1.97 cd/A (at 5.3 V); current efficiency at 100 cd/m 2 is 1.86 cd/A (at 4.3 V).
  • Example 18 - working product C A device with the configuration of ITO/PEDOT/PCPC4b:PBD (7:3)/CsF/Ca/AI using
  • Turn-on voltage is 3.2 V.
  • the maximum brightness is 4072 cd/m 2 (at 10.3 V); maximum current efficiency is 1.16 cd/A (at 5.3 V); current efficiency at 100 cd/m 2 is 1.10 cd/A (at 4.3 V).
  • Turn-on voltage is 4.1 V.
  • the maximum brightness is 5386cd/m 2 (at 10.3 V); maximum current efficiency is 1.77 cd/A (at 6.7 V); current efficiency at 100 cd/m 2 is 1.26 cd/A (at 5.3 V).
  • Example 20 - working product E A device with the configuration of ITO/PEDOT/PTCC4:PBD (7:3)/CsF/Ca/AI using PCPC4:PBD (7:3) as the emissive layer emits greenish blue light with maximum emissive wavelength of 460 nm.
  • Turn-on voltage is 3.0 V.
  • the maximum brightness is 7257 cd/m 2 (at 7.9 V); maximum current efficiency is 1.76 cd/A (at 4.5 V); current efficiency at 100 cd/m 2 is 1.50 cd/A (at 3.8 V).
  • Turn-on voltage is 3.6 V.
  • the maximum brightness is 3157cd/m 2 (at 10.9 V); maximum current efficiency is 1.02 cd/A (at 5.3 V); current efficiency at 100 cd/m 2 is 0.97 cd/A (at 4.9 V).
  • the glass transition temperature (Tg) for PCPC4 and PTCC4 are 238 0 C and 273 0 C, respectively. This high Tg contributed to good OLED device operation.
  • UV-vis absorption and photoluminescence (PL) spectra of PCPC4 and PTCC4 in toluene are set out in Figure 6.
  • the UV-vis absorption and photoluminescence (PL) spectra of PCPC4 and PTCC4 as thin films are set out in Figure 7. (The film thickness is ⁇ 100nm.)
  • the electroluminescence (EL) spectrum of PCPC4 is shown in Figure 8.
  • the I-V-L characteristics of PCPC4 are plotted in Figure 8A.
  • the current efficiency of PCPC4 is plotted in Figure 9B.
  • the electroluminescence (EL) spectrum of PTCC4 is shown in Figure 10.
  • the I-V-L characteristics of PTCC4 are plotted in Figure 11 A.
  • the current efficiency of PTCC4 is plotted in Figure 11 B.

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Abstract

L'invention concerne un composé émetteur de lumière bleue ayant (1) une partie centrale qui comporte une partie transport de trou comprenant un groupe triarylamine; (2) une partie chaîne latérale fixée à la partie centrale; ladite partie chaîne latérale comporte une partie transport d'électrons comprenant un groupe aryle déficitaire en électrons; et (3) une partie espaceur située entre la partie transport de trou et la partie transport d'électrons.
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