WO2018095383A1 - Dérivé d'amine aromatique deutéré, procédé de préparation et utilisations associés - Google Patents

Dérivé d'amine aromatique deutéré, procédé de préparation et utilisations associés Download PDF

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WO2018095383A1
WO2018095383A1 PCT/CN2017/112704 CN2017112704W WO2018095383A1 WO 2018095383 A1 WO2018095383 A1 WO 2018095383A1 CN 2017112704 W CN2017112704 W CN 2017112704W WO 2018095383 A1 WO2018095383 A1 WO 2018095383A1
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group
atoms
substituted
ring
atom
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PCT/CN2017/112704
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Chinese (zh)
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潘君友
杨曦
黄宏
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广州华睿光电材料有限公司
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Priority to CN201780059198.2A priority Critical patent/CN109790142B/zh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
    • H01J1/54—Screens on or from which an image or pattern is formed, picked-up, converted, or stored; Luminescent coatings on vessels
    • H01J1/62—Luminescent screens; Selection of materials for luminescent coatings on vessels
    • H01J1/63—Luminescent screens; Selection of materials for luminescent coatings on vessels characterised by the luminescent material

Definitions

  • the invention relates to the field of organic electroluminescence technology, in particular to a deuterated aromatic amine derivative, a preparation method and use thereof.
  • OLEDs Organic light-emitting diodes
  • Organic electroluminescence refers to the phenomenon of converting electrical energy into light energy using organic matter.
  • An organic electroluminescence device utilizing an organic electroluminescence phenomenon generally has a structure in which a positive electrode and a negative electrode and an organic layer are contained therebetween.
  • the organic layer has a multilayer structure, and each layer contains a different organic substance. Specifically, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and the like may be included.
  • Such an organic electroluminescence device when a voltage is applied between the two electrodes, a hole is injected from the positive electrode into the organic layer, and a negative electrode is injected into the organic substance, and when the injected hole meets the electron, an exciton is formed. The excitons emit light when they transition back to the ground state.
  • Such an organic electroluminescence device has characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high responsiveness.
  • the development of a blue fluorescent material having a narrow-band emission spectrum and good stability is advantageous for obtaining a longer-life and higher-efficiency blue light device, and on the other hand, it is advantageous for the improvement of the color gamut, thereby improving the display effect.
  • the light-emitting layer of the prior art blue organic electroluminescent device adopts a host-guest doping structure.
  • the conventional blue light host material is a ruthenium-based fused ring derivative, as described in the patents CN1914293B, CN102448945B, US2015287928A1, etc.
  • these compounds have problems of insufficient luminous efficiency and brightness, and poor lifetime of the device.
  • an aryl vinylamine compound (WO 04/013073, WO 04/016575, WO 04/018587) can be used.
  • these compounds have poor thermal stability and are easily decomposed, resulting in poor lifetime of the device, which is currently the most important shortcoming in the industry.
  • the blue light-emitting materials can have deep blue light emission, and they are thermally stable, exhibit good efficiency and longevity in the organic electroluminescence element, are easy to repeat in the manufacture and operation of the device, and have simple material synthesis.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 are the same or different from each other, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 Or R 8 are each independently selected from: H, or a linear alkyl group having 1 to 20 C atoms, or an alkoxy group having 1 to 20 C atoms, or a thioalkane having 1 to 20 C atoms.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 may form a single or multiple ring to each other and/or a ring to which the group is bonded Aliphatic or aromatic ring system;
  • One or more hydrogen atoms of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 are optionally substituted by a halogen atom;
  • Ar 1 , Ar 2 , Ar 3 or Ar 4 are the same or different from each other; at least one of the Ar 1 , Ar 2 , Ar 3 or Ar 4 is a group represented by the formula (II), and the others are independently selected. a: a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms;
  • one or more of the groups Ar 1 , Ar 2 , Ar 3 or Ar 4 may form a polycyclic aliphatic or aromatic ring system with each other and/or a ring bonded to the group;
  • At least one hydrogen atom of Ar 1 , Ar 2 , Ar 3 or Ar 4 is substituted by a halogen atom;
  • X represents an oxygen atom or a sulfur atom
  • R 9 to R 16 is a single bond to the N atom of the formula (I), and the balance is selected from: H, or a linear alkyl group having 1 to 20 C atoms, or 1 to 20 a C atom alkoxy group, or a thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms, or having 3 to 20 C atoms An alkoxy group, or a thioalkoxy group having 3 to 20 C atoms, or a substituted or unsubstituted silyl group, or a substituted ketone group having 1 to 20 C atoms, or 2 to 20 Alkoxycarbonyl group of C atom, or aryloxycarbonyl group having 7 to 20 C atoms, cyano group, carbamoyl group, haloformyl group, formyl group, isocyano group, isocyanate, thiocyanate or isothio
  • One or more groups in R 9 -R 16 may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded;
  • At least one hydrogen atom in R 9 - R 16 is substituted by a deuterium atom.
  • a high polymer comprising at least one repeating unit selected from the above-described deuterated aromatic amine derivatives.
  • a mixture comprising the above-described deuterated aromatic amine derivative or a high polymer as described above, and at least one organic functional material selected from the group consisting of: a hole (also called a hole) injection or transport material (HIM) /HTM), hole blocking material (HBM), electron injecting or transporting material (EIM/ETM), electron blocking material (EBM), organic matrix material (Host), singlet illuminant (fluorescent illuminant), triplet Luminescent body (phosphorescent emitter), thermally excited delayed fluorescent material (TADF material), and organic dye.
  • a hole also called a hole injection or transport material (HIM) /HTM
  • HBM hole blocking material
  • EIM/ETM electron injecting or transporting material
  • EBM electron blocking material
  • organic matrix material Host
  • singlet illuminant fluorescent illuminant
  • triplet Luminescent body phosphorescent emitter
  • TADF material thermally excited delayed fluorescent material
  • a composition comprising the above-described deuterated aromatic amine derivative or the above-mentioned high polymer or a mixture thereof, and at least one organic solvent.
  • An organic electronic device comprising the above-described deuterated aromatic amine derivative or the above-mentioned high polymer or a mixture thereof or the above composition.
  • the above-mentioned deuterated aromatic amine derivative has a fluorescence emission having an emission wavelength at a short wavelength, and its emission spectrum exhibits a narrow half-peak width, so that the substance has a deep blue fluorescence emission and has high luminous efficiency.
  • the organic electroluminescent device prepared from the above aromatic amine derivative has dark blue color coordinates, high luminous efficiency, and long device life.
  • 1 is a schematic diagram of an electronic device of an embodiment.
  • the host material In the present invention, the host material, the matrix material, the Host material, and the Matrix material have the same meaning and are interchangeable.
  • metal organic complexes metal organic complexes, metal organic complexes, and organometallic complexes have the same meaning and are interchangeable.
  • composition printing ink, ink, and ink have the same meaning and are interchangeable.
  • H has the same meaning as a hydrogen atom
  • D has the same meaning as a ruthenium atom
  • substitution of an atom by a deuterium atom means that one or more hydrogen atoms in Ar 6 may or may not be substituted by a deuterium atom.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 are the same or different from each other, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 Or R 8 are each independently selected from: H, or a linear alkyl group having 1 to 20 C atoms, or an alkoxy group having 1 to 20 C atoms, or a thioalkane having 1 to 20 C atoms.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 may form a single or multiple ring to each other and/or a ring to which the group is bonded Aliphatic or aromatic ring system.
  • One or more hydrogen atoms of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 are optionally substituted by a halogen atom; the Ar 1 , Ar 2 , Ar 3 Or at least one hydrogen atom in Ar 4 is replaced by a deuterium atom.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 are the same or different from each other; and R 1 , R 2 , R 3 , R 4 , R 5 , R 6, R 7 or R 8 are each independently selected from: H, or straight-chain alkyl group having 1 to 10 C atoms, or an alkoxy group having 1 to 10 C atoms, or having from 1 to 10 a thioalkoxy group of a C atom, or a branched or cyclic alkyl group having 3 to 10 C atoms, or an alkoxy group having 3 to 10 C atoms, or sulfur having 3 to 10 C atoms Alkoxy, or a substituted or unsubstituted silyl group, or a substituted keto group having 1 to 10 C atoms, or an alkoxycarbonyl group having 2 to 10 C atoms, or 7 to 10 An aryloxycarbonyl group of a C atom,
  • Ar 1 , Ar 2 , Ar 3 or Ar 4 are the same or different from each other; at least one of the Ar 1 , Ar 2 , Ar 3 or Ar 4 is a group represented by the formula (II), and the others are independently selected.
  • the moieties may form a polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • One or more hydrogen atoms of the Ar 1 , Ar 2 , Ar 3 or Ar 4 are optionally further substituted with a halogen atom.
  • Ar 1 , Ar 2 , Ar 3 or Ar 4 are the same or different from each other; at least one of the Ar 1 , Ar 2 , Ar 3 or Ar 4 is a group represented by the formula (II) And the other each independently selected from: a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 30 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 30 ring atoms; One or more of the groups may form a polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • One or more hydrogen atoms of the Ar 1 , Ar 2 , Ar 3 or Ar 4 are optionally substituted by a deuterium atom.
  • Ar 1 , Ar 2 , Ar 3 or Ar 4 are the same or different from each other; at least one of the Ar 1 , Ar 2 , Ar 3 or Ar 4 is a group represented by the formula (II) Others are each independently selected from: a substituted or unsubstituted aromatic or heteroaromatic ring system having 10 to 25 ring atoms, or an aryloxy or heteroaryloxy group having 10 to 25 ring atoms; One or more of the groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded. One or more hydrogen atoms of the Ar 1 , Ar 2 , Ar 3 or Ar 4 are optionally substituted by a deuterium atom.
  • the aromatic ring system in the substituted or unsubstituted aryl group has from 5 to 15 carbon atoms in the parent core structure (ring system); in one embodiment, a substituted or unsubstituted aryl or hetero group
  • the aromatic ring system in the aryl group contains 5 to 10 carbon atoms in the parent core structure (ring system).
  • the total number of carbon atoms and heteroatoms of the parent core structure of the heteroaromatic ring system in the substituted or unsubstituted heteroaryl group is at least 4.
  • the heteronuclear structure (ring system) of the heteroaromatic ring system in the substituted or unsubstituted heteroaryl group contains 2 to 15 carbon atoms, and at least one hetero atom; in one embodiment, the substitution or The heteronuclear structure (ring system) of the heteroaromatic ring system in the unsubstituted heteroaryl group contains 2 to 10 carbon atoms, and at least one hetero atom.
  • the hetero atom may be Si, N, P, O, S and/or Ge; in one embodiment, the hetero atom is selected from the group consisting of Si, N, P, O and/or S; in one embodiment, the hetero atom Selected from N, O or S.
  • the above aromatic ring system or aromatic group means a hydrocarbon group containing at least one aromatic ring, and includes a monocyclic group and a polycyclic ring system.
  • the heteroaromatic ring or heteroaromatic group described above refers to a hydrocarbon group (containing a hetero atom) containing at least one heteroaromatic ring, and includes a monocyclic group and a polycyclic ring system.
  • These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, a fused ring. At least one of these rings of the polycyclic ring is aromatic or heteroaromatic.
  • the aromatic or heteroaromatic ring system includes not only an aromatic or heteroaromatic system, but also a plurality of aryl or heteroaryl groups may be interrupted by short non-aromatic units ( ⁇ 10% of non-H atoms). Preferably, less than 5% of a non-H atom, such as a C, N or O atom). Therefore, a system such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine or diaryl ether is also considered to be an aromatic ring system.
  • the aromatic group is selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzopyrene, triphenylene, anthracene, anthracene, spiro and their derivatives.
  • the heteroaromatic group is selected from the group consisting of furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, and evil.
  • One or more groups in R 9 -R 16 may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or a ring bonded to the group; at least one hydrogen of R 9 -R 16 The atom is replaced by a deuterium atom.
  • Ar 1 -Ar 4 may be further selected to comprise the following structural groups:
  • a 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 respectively represent CR 3 or N;
  • Ar 1 -Ar 4 may be further selected to comprise a structure wherein H on the ring may be optionally substituted:
  • the deuterated aromatic amine derivative has the structure shown in the formula (III):
  • R 2 , R 6 , Ar 2 , Ar 4 , R 9 - R 16 and X are the same as defined in the formula (II).
  • the structure represented by the general formula (III) contains at least one D; in one embodiment, the structure represented by the general formula (III) contains at least two D; in one embodiment, The structure represented by the formula (III) contains at least three D; in one embodiment, the structure represented by the formula (III) contains at least four or more Ds.
  • the D atom contained in the formula (III) is at a position where R 9 - R 16 are.
  • the D atom contained in the formula (III) is at a position where R 9 and R 16 are located.
  • the D atom contained in the formula (III) is at a position where R 9 and R 16 are located and Ar 2 and Ar 4 .
  • the D atom contained in the formula (III) is at a position where R 9 , R 16 , R 2 , and R 6 are located, and Ar 2 and Ar 4 .
  • the D atom By deuterating the different positions of the structure represented by the general formula (III), the D atom has the most beneficial effect at the position where R 9 and R 16 are located. Such a beneficial effect is relative to a structure that does not contain a D atom, or a structure in which the D atom is at the position of R 10 - R 15 , and which exhibits a significant improvement in material and device stability.
  • the deuterated aromatic amine derivative has the structure represented by the general formula (IV)
  • X represents an oxygen atom or a sulfur atom
  • Ar 2 and Ar 4 are the same or different, and each of Ar 2 and Ar 4 is independently selected from: substituted or unsubstituted substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 40 ring atoms. Or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, deuterated or undeuterated; one or more of the groups of Ar 2 and Ar 4 may be each other and/or The ring-bonded ring forms a monocyclic or polycyclic aliphatic or aromatic ring system; one or more hydrogen atoms in the Ar 2 or Ar 4 are optionally substituted with a deuterium atom.
  • Ar 2 and Ar 4 are the same or different, and each of Ar 2 and Ar 4 is independently selected from: substituted or unsubstituted substituted or unsubstituted aromatic having 5 to 20 ring atoms. Or a heteroaromatic ring system, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms, deuterated or undeuterated; one or more of the groups of Ar 2 and Ar 4 may be The rings bonded to each other and/or to the group form a polycyclic aliphatic or aromatic ring system; one or more hydrogen atoms in the Ar 2 or Ar 4 are optionally substituted with a deuterium atom.
  • Ar 2 and Ar 4 are the same or different, and each of Ar 2 and Ar 4 is independently selected from: substituted or unsubstituted substituted or unsubstituted aromatic having 5 to 15 ring atoms. Or a heteroaromatic ring system, or an aryloxy or heteroaryloxy group having 5 to 15 ring atoms, deuterated or undeuterated; one or more of the groups of Ar 2 and Ar 4 may be The rings bonded to each other and/or to the group form a polycyclic aliphatic or aromatic ring system; one or more hydrogen atoms in the Ar 2 or Ar 4 are optionally substituted with a deuterium atom.
  • the Ar 2 , Ar 4 is or has a substituted or unsubstituted aryl or heteroaryl group having the following structure:
  • Z is CR 21 or N, but no two adjacent Zs are N at the same time;
  • R 21 -R 23 are each independently selected from H, or a linear alkyl group having 1 to 20 C atoms, or an alkoxy group having 1 to 20 C atoms, or a thio group having 1 to 20 C atoms.
  • P is a saturated cycloalkane or heterocycloalkane having 3 to 10 ring atoms
  • P is a saturated cycloalkane or heterocycloalkane having from 3 to 8 ring atoms
  • P is a saturated cycloalkane or heterocycloalkane having from 5 to 6 ring atoms.
  • the dotted line indicates a single bond in which the group is bonded to the N atom of the aromatic amine.
  • the Ar 2 and Ar 4 are selected from aryl or heteroaryl groups shown below:
  • R 2 and R 6 are the same or different, and each of R 2 or R 6 is independently selected from H, or a linear alkyl group having 1 to 20 C atoms, or an alkoxy group having 1 to 20 C atoms, Or a thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms, or an alkoxy group having 3 to 20 C atoms, or having 3 to a thioalkoxy group of 20 C atoms, or a substituted or unsubstituted alkylsilyl group having 3 to 30 C atoms, or an arylsilyl group having 8 to 30 C atoms, or having 5 to a substituted or unsubstituted aromatic or heteroaromatic ring system of 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms; one or more of said R 2 and R 6 One hydrogen atom is optionally substituted by
  • R 2 and R 6 are the same or different, and each of R 2 and R 6 is independently selected from: H, or a linear alkyl group having 1 to 10 C atoms, or 1 to 10 An alkoxy group of a C atom, or a thioalkoxy group having 1 to 10 C atoms, or a branched or cyclic alkyl group having 3 to 10 C atoms, or an alkane having 3 to 10 C atoms An oxy group, or a thioalkoxy group having 3 to 10 C atoms, or a substituted or unsubstituted alkylsilyl group having 3 to 15 C atoms, or an aryl group having 8 to 15 C atoms a silane group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 20 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms.
  • One or more hydrogen atoms of R 2 and R 6
  • R 2 and R 6 may be the same or different, and each of R 2 and R 6 is independently selected from a linear or branched alkane or a cycloalkane of 3 to 6 C atoms;
  • R 2 and R 6 may be the same or different, and each of R 2 and R 6 is independently selected from a linear or branched alkane or a cycloalkane of 3-5 C atoms;
  • R 2 and R 6 may be the same or different, and each of R 2 and R 6 is independently selected from a linear or branched alkane or a cycloalkane of 3-4 C atoms.
  • R 2 , R 6 may be the same or different, and each of R 2 and R 6 is independently selected from an aromatic or heteroaromatic group having 5 to 20 ring atoms;
  • R 2 , R 6 may be the same or different, and each of R 2 and R 6 is independently selected from an aromatic or heteroaromatic group having 5 to 12 ring atoms;
  • R 2 and R 6 may be the same or different, and each of R 2 and R 6 is independently selected from an aromatic or heteroaromatic group having 5 to 12 ring atoms, and the group has 5
  • the aromatic or heteroaromatic group of -12 ring atoms also contains at least one D atom.
  • the R 2 and R 6 are each independently selected from the group consisting of: H, D, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl , cyclobutyl, methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, ethylhexyl, trifluoro Methyl, pentafluoroethyl, trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cyclohep
  • W is CR 31 or N, but no two adjacent Ws are N at the same time;
  • R 31 may be H, or a linear alkyl group having 1 to 10 C atoms, or an alkoxy group having 1 to 10 C atoms, or a thio group having 1 to 10 C atoms.
  • R 2 , R 6 are substituted or unsubstituted aryl or heteroaryl having the following structure:
  • the R 2 and R 6 are each a hydrogen atom; in one embodiment, the R 2 and R 6 are both deuterium atoms; in one embodiment, the R 2 and R 6 is an isopropyl group; in one embodiment, the R 2 and R 6 are both isobutyl; in one embodiment, the R 2 and R 6 are both t-butyl groups; in one embodiment And R 2 and R 6 are each a tetramethylsilane; in one embodiment, the R 2 and R 6 are both benzene; in one embodiment, the R 2 and R 6 are both diphenyl In one embodiment, both R 2 and R 6 are benzene or diphenyl having at least one D atom.
  • R 10 - R 15 are each independently selected from: H, or a linear alkyl group having 1 to 20 C atoms, or an alkoxy group having 1 to 20 C atoms, or sulfur having 1 to 20 C atoms.
  • one or more of the R 10 -R 15 groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or a ring bonded to the group
  • R 10 -R 15 are each independently selected from: H, or a linear alkyl group having 1 to 10 C atoms, or an alkoxy group having 1 to 10 C atoms, or having 1 to 10 C atom thioalkoxy groups, or a branched or cyclic alkyl group having 3 to 10 C atoms, or an alkoxy group having 3 to 10 C atoms, or having 3 to 10 C atoms a thioalkoxy group, either a substituted or unsubstituted silyl group, a cyano group (-CN), or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 20 ring atoms, or An aryloxy or heteroaryloxy group of 5 to 20 ring atoms in which one or more groups may form a monocyclic or polycyclic aliphatic or aromatic group with each other and/or a ring bonded to said group.
  • Family ring system One or more of the various groups described
  • R 10 -R 15 are each independently selected from H; in one embodiment, R 10 -R 15 are each independently selected from D.
  • the deuterated aromatic amine derivative has the structure represented by the general formula (V)
  • the Ar 2 and Ar 4 are identical to each other, and the Ar 2 and Ar 4 are selected from the structures shown below:
  • the R 2 and R 6 are the same as each other, and the R 2 and R 6 are selected from a hydrogen atom, an isopropyl group or an isobutyl group.
  • the deuterated aromatic amine derivative is selected from the group consisting of the following structures:
  • active materials comprise at least one leaving group, for example, bromine, iodine, boric acid or a boronic ester.
  • Suitable reactions to form C-C linkages are well known to those skilled in the art and are described in the literature. Particularly suitable and preferred coupling reactions are SUZUKI, STILLE and HECK coupling reactions.
  • a high polymer comprising at least one repeating unit selected from the above-described deuterated aromatic amine derivatives.
  • the high polymer is a non-conjugated high polymer wherein the deuterated aromatic amine derivative is attached to a side chain.
  • the high polymer is a conjugated high polymer.
  • a composition comprising the above-described deuterated aromatic amine derivative or the above-mentioned high polymer, and at least one organic solvent.
  • a mixture comprising the above-described deuterated aromatic amine derivative or a high polymer as described above, and at least one organic functional material selected from the group consisting of: a hole (also called a hole) injection or transport material (HIM/ HTM), hole blocking material (HBM), electron injecting or transporting material (EIM/ETM), electron blocking material (EBM), organic matrix material (Host), singlet illuminant (fluorescent illuminant), triplet luminescence Body (phosphorescent emitter), thermally excited delayed fluorescent material (TADF material) and organic dye.
  • a hole also called a hole injection or transport material
  • HBM hole blocking material
  • EIM/ETM electron injecting or transporting material
  • EBM electron blocking material
  • organic matrix material Host
  • singlet illuminant fluorescent illuminant
  • triplet luminescence Body phosphorescent emitter
  • TADF material thermally excited delayed fluorescent material
  • the mixture comprises the above-described deuterated aromatic amine derivative or the above-described high polymer, and a fluorescent host material (or a singlet matrix material).
  • the above deuterated aromatic amine derivative or the above-mentioned high polymer may be used as a guest, and the weight percentage thereof is ⁇ 15% by weight;
  • the above-mentioned deuterated aromatic amine derivative or the above-mentioned high polymer is ⁇ 12% by weight;
  • the above-mentioned deuterated aromatic amine derivative or the above-mentioned high polymer is ⁇ 9 wt% by weight
  • the above-mentioned deuterated aromatic amine derivative or the above polymer has a weight percentage of ⁇ 8 wt%
  • the above-described deuterated aromatic amine derivative or the above-mentioned high polymer has a weight percentage of ⁇ 7 wt%.
  • the mixture is a deuterated aromatic amine derivative or a high polymer of the above, another fluorescent emitter (or singlet emitter), and a fluorescent host material.
  • the above-mentioned deuterated aromatic amine derivative or the above-mentioned high polymer can be used as an auxiliary luminescent material, and its weight ratio with another fluorescent illuminant is from 1:2 to 2:1.
  • the mixture is a deuterated aromatic amine derivative or a high polymer as described above, and a TADF material.
  • the mixture comprises the above-described deuterated aromatic amine derivative or the above-described high polymer, and HTM material.
  • HTM singlet matrix materials
  • singlet emitters singlet emitters
  • Suitable organic HIM/HTM materials may optionally comprise compounds having the following structural units: phthalocyanine, porphyrin, amine, aromatic amine, biphenyl triarylamine, thiophene, thiophene such as dithienothiophene and thiophene, pyrrole, aniline , carbazole, azide and azepine and their derivatives.
  • suitable HIMs also include self-assembling monomers such as compounds containing phosphonic acid and sliane derivatives; metal complexes and crosslinking compounds and the like.
  • An electron blocking layer is used to block electrons from adjacent functional layers, particularly the luminescent layer.
  • the electron blocking material (EBM) of the electron blocking layer (EBL) requires a higher LUMO than an adjacent functional layer such as a light emitting layer.
  • the HBM has a larger excited state level than the adjacent luminescent layer, such as a singlet or triplet, depending on the illuminant, while the EBM has a hole transport function.
  • HIM/HTM materials that typically have high LUMO levels can be used as EBMs.
  • cyclic aromatic amine-derived compounds useful as HIM, HTM or EBM include, but are not limited to, the following general structures:
  • Each of Ar 1 to Ar 9 may be independently selected from the group consisting of a cyclic aromatic hydrocarbon compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalrene, phenanthrene, anthracene, anthracene, fluorene, anthracene, anthracene; Heterocyclic compounds such as dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, oxazole, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, evil Triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, acesulfazine, oxadiazine, hydrazine
  • Ar 1 to Ar 9 may be independently selected from the group consisting of:
  • n is an integer from 1 to 20; X 1 to X 8 are CH or N; and Ar 1 is as defined above.
  • metal complexes that can be used as HTM or HIM include, but are not limited to, the following general structures:
  • M is a metal having an atomic weight greater than 40
  • (Y 1 -Y 2 ) is a two-dentate ligand, Y 1 and Y 2 are independently selected from C, N, O, P and S; L is an ancillary ligand; m is an integer from 1 to The maximum coordination number of this metal; m+n is the maximum coordination number of this metal.
  • (Y 1 -Y 2 ) is a 2-phenylpyridine derivative.
  • (Y 1 -Y 2 ) is a carbene ligand.
  • M is selected from Ir, Pt, Os, and Zn.
  • the HOMO of the metal complex is greater than -5.5 eV (relative to the vacuum level).
  • the example of the singlet host material is not particularly limited, and any organic compound may be used as the host as long as its singlet energy is higher than that of the illuminant, particularly the singlet illuminant or the luminescent illuminant.
  • Examples of the organic compound used as the singlet host material may be selected from the group consisting of a cyclic aromatic compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, anthracene, phenanthrene, anthracene, anthracene, fluorene, fluorene, fluorene, An aromatic heterocyclic compound such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, oxazole, carbazole, pyridine Anthraquinone, pyrrole dipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrim
  • the singlet host material can be selected from compounds comprising at least one of the following groups:
  • R 1 may be independently selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl;
  • Ar 1 is an aryl group Or a heteroaryl group, which has the same meaning as Ar 1 defined in the above HTM;
  • n is an integer from 0 to 20;
  • X 1 -X 8 is selected from CH or N;
  • X 9 and X 10 are selected from CR 1 R 2 Or NR 1 .
  • Singlet emitters tend to have longer conjugated pi-electron systems.
  • styrylamine and its derivatives disclosed in JP 2913116 B and WO 2001021729 A1
  • indenoindenes and derivatives thereof disclosed in WO 2008/006449 and WO 2007/140847.
  • the singlet emitter may be selected from the group consisting of monostyrylamine, dibasic styrylamine, ternary styrylamine, quaternary styrylamine, styrene phosphine, styrene ether and arylamine.
  • a monostyrylamine refers to a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine.
  • a dibasic styrylamine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a ternary styrylamine refers to a compound comprising three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a quaternary styrylamine refers to a compound comprising four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a preferred styrene is stilbene, which may be further substituted.
  • the corresponding phosphines and ethers are defined similarly to amines.
  • An arylamine or an aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic ring or heterocyclic systems directly bonded to a nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably selected from the fused ring system and preferably has at least 14 aromatic ring atoms.
  • Preferred examples thereof are aromatic decylamine, aromatic quinone diamine, aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine.
  • An aromatic amide refers to a compound in which a diaryl arylamine group is attached directly to the oxime, preferably at the position of 9.
  • An aromatic quinone diamine refers to a compound, Two of the diarylamine groups are attached directly to the oxime, preferably at the 9,10 position.
  • the definitions of aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine are similar, wherein the diaryl aryl group is preferably bonded to the 1 or 1,6 position of hydrazine.
  • Examples of singlet emitters based on vinylamines and arylamines are also preferred examples and can be found in the following patent documents: WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007 /115610, US 7250532 B2, DE 102005058557 A1, CN 1583691 A, JP 08053397 A, US 6251531 B1, US 2006/210830 A, EP 1957606 A1 and US 2008/0113101 A1, the entire contents of which are hereby incorporated by reference. This article is incorporated herein by reference.
  • Further preferred singlet emitters can be selected from indenoindole-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, benzoindoloindole-amines and benzoindenoindole-diamines , as disclosed in WO 2008/006449, dibenzoindolo-amine and dibenzoindeno-diamine, as disclosed in WO 2007/140847.
  • polycyclic aromatic hydrocarbon compounds in particular derivatives of the following compounds: for example, 9,10-bis(2-naphthoquinone), naphthalene, tetraphenyl, xanthene, phenanthrene , ⁇ (such as 2,5,8,11-tetra-t-butyl fluorene), anthracene, phenylene such as (4,4'-bis(9-ethyl-3-carbazolevinyl)-1 , 1 '-biphenyl), indenyl hydrazine, decacycloolefin, hexacene benzene, anthracene, spirobifluorene, aryl hydrazine (such as US20060222886), arylene vinyl (such as US5121029, US5130603), cyclopentane Alkene such as tetraphenylcyclopentadiene, rub
  • the thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials.
  • Such materials generally have a small singlet-triplet energy level difference ( ⁇ Est), and triplet excitons can be converted into singlet exciton luminescence by anti-intersystem crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation.
  • the quantum efficiency in the device can reach 100%.
  • the material structure is controllable, the property is stable, the price is cheap, no precious metal is needed, and the application prospect in the OLED field is broad.
  • the TADF material needs to have a small singlet-triplet energy level difference, preferably ⁇ Est ⁇ 0.3 eV, and secondly ⁇ Est ⁇ 0.2 eV, preferably ⁇ Est ⁇ 0.1 eV.
  • the TADF material has a relatively small ⁇ Est, and in another preferred embodiment, the TADF has a better fluorescence quantum efficiency.
  • TADF luminescent materials can be found in the following patent documents: CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1), WO2013154064( A1), Adachi, et.al. Adv. Mater., 21, 2009, 4802, Adachi, et. al. Appl. Phys. Lett., 98, 2011, 083302, Adachi, et. al. Appl. Phys. Lett ., 101, 2012, 093306, Adachi, et. al. Chem.
  • TADF luminescent materials are listed in the table below:
  • a composition comprising the above-described deuterated aromatic amine derivative or a high polymer thereof or a mixture thereof, and an organic solvent.
  • the deuterated aromatic amine derivative is used as a singlet emitter material.
  • composition comprising a host material and the above aromatic amine derivative or a high polymer thereof or a mixture thereof.
  • composition comprising at least two host materials and the above-described deuterated aromatic amine derivative or a high polymer thereof or a mixture thereof.
  • composition comprising a host material, a thermally activated delayed fluorescent material and the above-described deuterated aromatic amine derivative or a high polymer thereof or a mixture thereof.
  • composition comprising a hole transporting material (HTM) and a deuterated aromatic amine derivative or a high polymer thereof or a mixture thereof;
  • HTM hole transporting material
  • a composition comprising a hole transporting material (HTM) comprising a crosslinkable group And a deuterated aromatic amine derivative or a high polymer thereof or a mixture thereof.
  • HTM hole transporting material
  • the above composition is a solution.
  • the above composition is a suspension.
  • the composition comprises 0.01% by weight to 20% by weight of the above-mentioned deuterated aromatic amine derivative or a high polymer thereof or a mixture thereof;
  • the composition comprises 0.1% by weight to 15% by weight of the above-mentioned deuterated aromatic amine derivative or a high polymer thereof or a mixture thereof;
  • the composition comprises from 0.2% by weight to 10% by weight of the above-mentioned deuterated aromatic amine derivative or a high polymer thereof or a mixture thereof;
  • the composition comprises from 0.25 wt% to 5 wt% of the above deuterated aromatic amine derivative or a high polymer thereof or a mixture thereof.
  • a composition the solvent used in the composition is selected from the group consisting of: an aromatic or heteroaromatic, an ester, an aromatic ketone or an aromatic ether, an aliphatic ketone or an aliphatic ether, an alicyclic or An olefinic compound, or an inorganic ester compound such as a boronic acid ester or a phosphate ester, or a mixture of two or more solvents.
  • composition comprising at least 50% by weight of an aromatic or heteroaromatic solvent
  • composition comprising at least 80% by weight of an aromatic or heteroaromatic solvent
  • composition comprising at least 90% by weight of an aromatic or heteroaromatic solvent.
  • examples based on aromatic or heteroaromatic solvents are, but are not limited to, 1-tetralone, 3-phenoxytoluene, acetophenone, 1-methoxynaphthalene, p-diiso Propylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, o-diethylbenzene , m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecane Benzobenzene, 1-methylnaphthalene, 1,2,4-trich
  • suitable and preferred solvents are aliphatic, cycloaliphatic or aromatic hydrocarbons, amines, thiols, amides, nitriles, esters, ethers, polyethers, alcohols, glycols or polyols.
  • the alcohol represents a suitable class of solvent.
  • Preferred alcohols include alkylcyclohexanols, especially methylated aliphatic alcohols, naphthols and the like.
  • the solvent may be a cycloalkane such as decalin.
  • the solvent may be used singly or as a mixture of two or more organic solvents.
  • the above composition comprises a deuterated aromatic amine derivative or a high polymer thereof, and at least one organic solvent, and may further comprise another organic solvent, and another organic solvent.
  • organic solvent examples include, but are not limited to, methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene , m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1,1,1-trichloro Ethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decal
  • the organic solvent in the above composition is a solvent having a Hansen solubility parameter in the following range:
  • ⁇ d (dispersion force) is in the range of 17.0 to 23.2 MPa 1/2 , especially in the range of 18.5 to 21.0 MPa 1/2 ;
  • ⁇ p polar forces in the range of 0.2 ⁇ 12.5MPa 1/2, especially in the 2.0 ⁇ 6.0MPa 1/2;
  • the boiling point parameter should be considered when selecting the organic solvent in the above composition.
  • the organic solvent has a boiling point ⁇ 150 ° C; in one embodiment, the organic solvent has a boiling point ⁇ 180 ° C; in one embodiment, the organic solvent has a boiling point ⁇ 200 ° C In one embodiment, the organic solvent has a boiling point ⁇ 250 ° C; in an embodiment, The organic solvent has a boiling point of ⁇ 275 ° C; in one embodiment, the organic solvent has a boiling point of ⁇ 300 ° C.
  • the boiling points within these ranges are beneficial for preventing nozzle clogging of the inkjet printhead.
  • the organic solvent can be evaporated from the solvent system to form a film comprising the functional material.
  • a composition the viscosity of the selected solvent, has a surface tension as follows:
  • the surface tension parameter should be considered when selecting the organic solvent in the above composition. Suitable ink surface tension parameters are suitable for a particular substrate and a particular printing method. For example, for inkjet printing, in one embodiment, the surface tension of the organic solvent at 25 ° C is in the range of about 19 dyne / cm to 50 dyne / cm; the surface tension of the organic solvent at 25 ° C is about 22 dyne The range of /cm to 35dyne/cm; the surface tension of the organic solvent at 25 ° C is in the range of about 25 dyne / cm to 33 dyne / cm.
  • the surface tension of the ink at 25 ° C is in the range of from about 19 dyne / cm to 50 dyne / cm; in one embodiment, the surface tension of the ink at 25 ° C is in the range of from about 22 dyne / cm to 35 dyne / cm; In one embodiment, the ink has a surface tension at 25 ° C ranging from about 25 dyne/cm to 33 dyne/cm.
  • the viscosity parameter of the ink should be considered when selecting the organic solvent in the composition.
  • the viscosity can be adjusted by different methods, such as by the selection of a suitable organic solvent and the concentration of the functional material in the ink.
  • the organic solvent has a viscosity of less than 100 cps; in one embodiment, the organic solvent has a viscosity of less than 50 cps; in one embodiment, the organic solvent has a viscosity of 1.5 to 20cps.
  • the viscosity herein refers to the viscosity at ambient temperature at the time of printing, and is usually 15 to 30 ° C, preferably 18 to 28 ° C, more preferably 20 to 25 ° C, and most preferably 23 to 25 ° C. Compositions so formulated will be particularly suitable for ink jet printing.
  • a composition has a viscosity at 25 ° C in the range of from about 1 cps to about 100 cps; in one embodiment, a composition having a viscosity at 25 ° C in the range of from about 1 cps to about 50 cps; In one embodiment, a composition has a viscosity at 25 ° C in the range of from about 1.5 cps to about 20 cps.
  • the ink obtained by the organic solvent satisfying the above boiling point and surface tension parameters and viscosity parameters can form a functional material film having uniform thickness and composition properties.
  • deuterated aromatic amine derivatives and their high polymers and compositions are used in organic electronic devices.
  • the organic electronic device can be selected from an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic laser, and an organic spintronic device.
  • OLED organic light emitting diode
  • OCV organic photovoltaic cell
  • OEEC organic light emitting cell
  • OFET organic field effect transistor
  • OLED organic light emitting field effect transistor
  • a functional layer on a substrate by evaporation or a co-evaporation method together with at least one other organic functional material on a substrate Forming a functional layer thereon, or coating the above composition onto a substrate by printing or coating to form a functional layer
  • the printing or coating method may be selected from, but not limited to, inkjet printing, spraying Nozzle Printing, Typography, Screen Printing, Dip Coating, Spin Coating, Blade Coating, Roller Printing, Twist Roll Printing, Lithography, Flexo Printing, Rotary Printing, Spraying, Brushing or Pad Printing, Slit type extrusion coating, etc.
  • the above composition is used as a printing ink for the preparation of an organic electronic device.
  • the above-described organic electronic device is prepared by a printing or coating preparation method.
  • suitable printing or coating techniques include, but are not limited to, inkjet printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, twist roll printing, lithography, flexography Printing, rotary printing, spraying, brushing or pad printing, slit-type extrusion coating, etc.
  • Preferred are gravure, screen printing and inkjet printing. Gravure printing, ink jet printing will be applied in embodiments of the invention.
  • the solution or suspension may additionally comprise one or more components such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, binders and the like for adjusting viscosity, film forming properties, adhesion, and the like.
  • the functional layer formed by the above described preparation method has a thickness of from 5 nm to 1000 nm.
  • An organic electronic device comprising at least one of the above-described deuterated aromatic amine derivatives or a high polymer thereof, or at least a functional layer prepared by using the above composition.
  • an organic electronic device includes: a cathode, an anode, and a functional layer between the cathode and the anode, wherein the functional layer contains at least one aromatic amine derivative as described above or a high thereof Polymer or composition thereof.
  • the organic electronic device described above is an electroluminescent device, particularly an OLED (shown in FIG. 1), including a substrate 101, an anode 102, at least one luminescent layer 104, and a cathode 106. .
  • the substrate 101 can be opaque or transparent.
  • a transparent substrate can be used to make a transparent light-emitting component. See, for example, Bulovic et al. Nature 1996, 380, p29, and Gu et al, Appl. Phys. Lett. 1996, 68, p2606.
  • the substrate can be rigid or elastic.
  • the substrate can be plastic, metal, semiconductor wafer or glass.
  • the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice.
  • the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150 ° C or higher, preferably more than 200 ° C, more preferably more than 250 ° C, preferably More than 300 ° C. Examples of suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).
  • PET poly(ethylene terephthalate)
  • PEN polyethylene glycol (2,6-n
  • the anode 102 can comprise a conductive metal or metal oxide, or a conductive polymer.
  • the anode can easily inject holes into a hole injection layer (HIL) or a hole transport layer (HTL) or a light-emitting layer.
  • HIL hole injection layer
  • HTL hole transport layer
  • the absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV.
  • anode material examples include, but are not limited to, Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like.
  • suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art.
  • the anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices in accordance with the present invention.
  • Cathode 106 can include a conductive metal or metal oxide.
  • the cathode can easily inject electrons into the EIL or ETL or directly into the luminescent layer.
  • the work function of the cathode and the LUMO level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) in the luminescent layer or
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the absolute value of the difference in conduction band energy levels is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV.
  • all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention.
  • cathode material examples include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like.
  • the cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • the OLED may further include other functional layers such as a hole injection layer (HIL) or a hole transport layer (HTL) 103, an electron blocking layer (EBL), an electron injection layer (EIL) or an electron transport layer (ETL) 105, and a hole. Barrier layer (HBL).
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL Barrier layer
  • the light-emitting layer 104 in the light-emitting device is vacuum-deposited, and the evaporation source thereof contains the above aromatic amine derivative or a high polymer thereof or a combination thereof or a mixture thereof.
  • the luminescent layer 104 in the light emitting device is prepared by printing the above aromatic amine derivative of the present invention or a high polymer thereof or a composition thereof or a mixture thereof.
  • the electroluminescent device has an emission wavelength between 300 and 1000 nm; in one embodiment, the electroluminescent device has an emission wavelength between 350 and 900 nm; in one embodiment, the electroluminescent device The illuminating wavelength is between 400 and 800 nm.
  • organic electronic devices are used in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, and the like.
  • the electronic device of the above organic electronic device includes, but is not limited to, a display device, a lighting device, a light source, a sensor, and the like.
  • the present invention does not indicate a reagent or instrument of a specific source, and is a conventional reagent or instrument purchased from the market.
  • 1,6-dibromoindole (6.5 g, 18 mmol), N-[1,1'-biphenyl]-2-yl-2', 3', 4',5',6'-d 5 )dibenzofuran-6-d-4-amine (12.3 g, 36 mmol), Pd(dba) 2 (620 mg, 1.08 mmol), NaOtBu (10.4 g, 108 mmol) (tBu) 3 P (650 mg, 3.24 mmol) and anhydrous toluene (200 mL), and stirred at 100 ° C overnight. After completion of the reaction, the precipitated solid was filtered, washed with toluene and methanol to give a pale yellow solid powder (11.9 g, 75%).
  • N-([1,1'-biphenyl]-3-yl-2',3',4',5',6'-d 5 )- N-(6-bromoindol-1-yl)dibenzofuran-6-d-4-amine (11.2 g, 18 mmol), N-[1,1'-biphenyl]-2-yl-2', 3 ', 4', 5 ' , 6'-d 5) dibenzofuran -6-d-4- amine (6.2g, 18mmol), Pd ( dba) 2 (310mg, 0.54mmol), NaOtBu (5.2g , 54 mmol), (tBu) 3 P (325 mg, 1.6 mmol) and anhydrous toluene (200 mL), and stirred at 100 ° C overnight. After completion of the reaction, the precipitated solid was filtered, washed with to
  • 1,6-dibromoindole (5.7 g, 16 mmol), N-([1,1';3',1"-terphenyl]-4'- Base-2,2',3,3',4,4',5,5',6,6"-d 10 )dibenzofuran-6-d-4-amine (13.5 g, 32 mmol), Pd (dba) 2 (550 mg, 0.96 mmol), NaOtBu (5.76 g, 96 mmol), (tBu) 3 P (580 mg, 2.9 mmol) and anhydrous toluene 200 mL, and stirred at 100 ° C overnight. After completion of the reaction, the precipitated solid was filtered, washed with toluene and methanol to give a pale yellow solid powder (12.3 g, 74%).
  • 1,6-dibromoindole (3.6 g, 10 mmol), N-([1,1'-biphenyl]-2-yl)dibenzofuran- 4-amine (6.7 g, 20 mmol), Pd(dba) 2 (345 mg, 0.6 mmol), NaOtBu (5.76 g, 60 mmol), (tBu) 3 P (360 mg, 1.8 mmol) and anhydrous toluene 100 mL, stirred at 100 ° C overnight. After completion of the reaction, the precipitated solid was filtered, washed with toluene and methanol to give a pale yellow solid powder (6.1 g, 72%).
  • HIL a triarylamine derivative
  • HTL a triarylamine derivative
  • a, cleaning of the conductive glass substrate when used for the first time, can be washed with a variety of solvents, such as chloroform, ketone, isopropyl alcohol, and then UV ozone plasma treatment;
  • HIL 50 nm
  • HTL 35 nm
  • EML 25 nm
  • ETL 28 nm
  • cathode LiQ / Al (1nm / 150nm) in a high vacuum (1 ⁇ 10 -6 mbar) in the thermal evaporation;
  • the device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.
  • the current-voltage (J-V) characteristics of each OLED device are characterized by characterization equipment while recording important parameters such as efficiency, lifetime and external quantum efficiency. It has been found that the color coordinates of the blue light device prepared by using Compound 1 - Compound 10 as the EML layer illuminant are better than that of Comparative Compound 1, for example, the color coordinates of the device prepared by Compound 2 are (0.149, 0.083); The luminous efficiency of the blue light device prepared by using Compound 10 as the EML layer illuminant is in the range of 6-8 cd/A, which has more excellent luminous efficiency than Comparative Compound 1, and in the life of the device, Compound 1 - Compound 10 is used as the EML layer. The lifetime of the blue light device prepared by the illuminant is better than that of the comparative compound. For example, the device prepared by the compound 2 has a T95 of more than 1500 hours at 1000 nits.
  • the deuterated aromatic amine derivative provided by the present invention has a significantly improved device lifetime relative to the aromatic amine derivative without deuteration, and the device lifetime of Compound 1 is 1521h, while the life of Comparative Compound 2 was 756h.
  • the deuterated aromatic amine derivative provided by the present invention has a significantly improved device lifetime relative to the aromatic amine derivative without deuteration, and the device lifetime of compound 2 is 1530h, while the life of the comparative compound was 756h.
  • a device containing a deuterated aromatic amine derivative (compound 1) in which R 9 (or R 16 ) in the formula II is a halogen atom contains R 11 (or The device of R 14 ) is a deuterated aromatic amine derivative of fluorene atom (Comparative Compound 3) has a high lifetime. It can be seen that the deuterated position is preferably in the dibenzofuran unit, more preferably in R 9 or R 16 . For example, the lifetime of the device prepared for Compound 1 was 1521 h, while the lifetime of Comparative Compound 3 was 1007 h.

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Abstract

La présente invention concerne un dérivé d'amine aromatique deutéré représenté par la formule générale (I). Le dérivé d'amine aromatique deutéré possède une émission de fluorescence à une courte longueur d'onde d'émission de lumière, et le spectre d'émission de lumière du dérivé d'amine aromatique deutéré a une largeur étroite de demi-pic, et par conséquent, le matériau a une émission de fluorescence bleu foncé et a une efficacité d'émission de lumière élevée. Un composant électroluminescent organique préparé en utilisant le dérivé d'amine aromatique possède des coordonnées de couleur bleu foncé, une efficacité d'émission de lumière élevée et une longue durée de vie de composant.
PCT/CN2017/112704 2016-11-23 2017-11-23 Dérivé d'amine aromatique deutéré, procédé de préparation et utilisations associés WO2018095383A1 (fr)

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