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CN-116143807-B - D10 metal carbene complexes for OLED applications

CN116143807BCN 116143807 BCN116143807 BCN 116143807BCN-116143807-B

Abstract

Described herein are bidentate d10 metal carbene complexes comprising (I) Cu (I), ag (I) or Au (I), (ii) pyrazine-fused NHC ligands or pyridine-fused NHC ligands, and (iii) carbazole ligands, pyrido [2,3-b ] indole ligands or pyrido [3,4-b ] indole ligands. The radiation properties of the compounds can be controlled by thermally activating delayed fluorescence. The emission color of the complex can be adjusted by using carbazole species with different donor intensities. Methods of using the complexes are also described herein.

Inventors

  • TANG RUI
  • ZHI ZHIMING
  • CHENG GANG
  • LIN ZILONG

Assignees

  • 港大科桥有限公司
  • 香港量子人工智能实验室有限公司

Dates

Publication Date
20260512
Application Date
20221123
Priority Date
20211123

Claims (20)

  1. 1. A compound having the structure: I is a kind of Wherein: The compounds generally have neutral, negative or positive charge, M is copper, the oxidation state of which is 0, +1, +2 or +3, P' is selected from: 、 Or (b) , Wherein: Ra is independently hydrogen or isopropyl, and Rb is an isopropyl group, and is a hydroxyl group, Z has the following structure: Wherein: X 1 、X 2 、X 3 、X 4 、X 5 and X 6 are carbon, X 7 and X 8 are independently carbon or nitrogen, Rx 1 、Rx 2 、Rx 4 and Rx 5 are hydrogen, rx 3 、Rx 6 、Rx 7 and Rx 8 are independently hydrogen, halogen, cyano, unsubstituted C1-C18 alkyl, or unsubstituted C5-C26 aryl, wherein when the corresponding X 7 or X 8 is nitrogen, each Rx 7 or Rx 8 is absent, or adjacent Rxn groups together with the atoms in the ring to which they are bonded, independently form together a five-or six-membered C1-C14 alkyl substituted aryl, wherein n in the adjacent Rxn groups is a consecutive integer pair of 1 to 4 or 5 to 8.
  2. 2. The compound of claim 1, wherein Rx 3 、Rx 6 、Rx 7 and Rx 8 are independently hydrogen, halogen, methyl, cyano, t-butyl or phenyl.
  3. 3. The compound of claim 1, having the structure: VI (VI) Wherein: w is carbon or nitrogen, W is bonded to one hydrogen atom or not bonded to the hydrogen atom according to valence, V' is carbon, and is represented by the formula V, U is carbon and V is nitrogen, or U is nitrogen and V is carbon, wherein U, V and V '' are bonded to one hydrogen atom or not bonded to a hydrogen atom depending on valence, R 7 and R 8 are independently absent, hydrogen, unsubstituted C1-C18 alkyl, cyano, halogen, unsubstituted C5-C26 aryl, or adjacent R 7 groups or adjacent R 8 groups together with the atoms in the ring to which they are bonded independently form a five-or six-membered C1-C14 alkyl-substituted aryl, and N3 and n4 are independently integers between 0 and 5, R 1 and R 2 are hydrogen, or R 1 and R 2 together form the following structure: 。
  4. 4. a compound of claim 3 having the structure: VII (VII) Wherein: Rv is an unsubstituted, hydrogen or unsubstituted C1-C18 alkyl group, and R 7 and R 8 are independently hydrogen, unsubstituted C1-C18 alkyl, unsubstituted C5-C26 aryl, halogen, cyano, or Rv and R 7 together with the atoms in the ring to which they are bound form a five-or six-membered C1-C14 alkyl substituted aryl.
  5. 5. The compound of claim 3, wherein: Rv is either no or hydrogen and, R 7 and R 8 are independently hydrogen, isopropyl, tert-butyl, phenyl, fluoro or cyano, or Rv and R 7 together form 。
  6. 6. The compound of claim 1, having the structure: VIII (VIII) Wherein: (i) M=cu (I), w=n, ra=h, u=ch, v=v "=carbon, rv=h, and R 7 =R 8 =h; (ii) M=cu (I), w=n, ra=h, u=ch, v=v "=carbon, rv=h, R 7 =H;R 8 =cn; (iii) M=cu (I), w=n, ra=h, u=ch, v=v "=carbon, rv=h, R 7 =R 8 =tert-butyl; (iv) M=cu (I), w=n, ra=h, u=ch, v=v "=carbon, rv=h, R 7 =R 8 =phenyl; (v) M=cu (I), w=n, ra=h, u=ch, v=n, V "=carbon, rv=none, R 7 =R 8 =h; (vi) M=cu (I), w=u=ch, v=v "=carbon, rv=h, ra=isopropyl, R 7 =R 8 =h; (vii) M=cu (I), w=n, ra=h, u=ch, v=v "=carbon, R 8 =h, rv and R 7 together form ; (Viii) M=cu (I), w=u=ch, ra=isopropyl, v=v "=carbon, R 8 =h, rv and R 7 together form ; (Ix) M=cu (I), w=n, ra=h, u=ch, v=v "=carbon, rv=h, and R 7 =R 8 =h; (x) M=cu (I), w=n, ra=h, u=ch, v=v "=carbon, rv=h, R 7 =H;R 8 =f; (xi) M=cu (I), w=n, ra=h, u=ch, v=v "=carbon, rv=h, R 7 =R 8 =methyl; For (i), (ii), (iii), (iv), (v), (vi), (vii), (viii), the dashed line indicates no bond, and For (ix), (x) and (xi), the dashed lines indicate the presence of bonds.
  7. 7. The compound of claim 1, having the structure: Where m=cu (I).
  8. 8. A compound having the structure: I is a kind of Wherein: The compounds generally have neutral, negative or positive charge, M is gold, having an oxidation state of 0, +1, +2 or +3, P' is selected from: , Wherein: Ra is independently hydrogen or isopropyl, and Rb is an isopropyl group, and is a hydroxyl group, Z has the following structure: Wherein: X 1 、X 2 、X 3 、X 4 、X 5 and X 6 are carbon, X 7 and X 8 are independently carbon or nitrogen, Rx 1 、Rx 2 、Rx 4 and Rx 5 are hydrogen, rx 3 、Rx 6 、Rx 7 and Rx 8 are independently hydrogen, halogen, cyano, unsubstituted C1-C18 alkyl or unsubstituted C5-C26 aryl, wherein when the corresponding X 7 or X 8 is nitrogen, each Rx 7 or Rx 8 is absent, or adjacent Rxn groups together with the atoms in the ring to which they are bonded, independently form together a five-or six-membered C1-C14 alkyl substituted aryl, wherein n in the adjacent Rxn groups is a consecutive integer pair of 1 to 4 or 5 to 8.
  9. 9. The compound of claim 8, wherein Rx 3 、Rx 6 、Rx 7 and Rx 8 are independently hydrogen, halogen, methyl, cyano, t-butyl or phenyl.
  10. 10. The compound of claim 8, having the structure: VI (VI) Wherein: w is nitrogen, and the W is nitrogen, V' is carbon, and is represented by the formula V, U is carbon and V is nitrogen, or U is nitrogen and V is carbon, wherein U, V and V '' are bonded to one hydrogen atom or not bonded to a hydrogen atom depending on valence, R 7 and R 8 are independently absent, hydrogen, unsubstituted C1-C18 alkyl, cyano, halogen, or unsubstituted C5-C26 aryl, or adjacent R 7 groups or adjacent R 8 groups together with the atoms in the ring to which they are bonded independently form a five-or six-membered C1-C14 alkyl-substituted aryl, and N3 and n4 are independently integers between 0 and 5, R 1 and R 2 together form the following structure: 。
  11. 11. the compound of claim 10, having the structure: VII (VII) Wherein: Rv is an unsubstituted, hydrogen or unsubstituted C1-C18 alkyl group, and R 7 and R 8 are independently hydrogen, unsubstituted C1-C18 alkyl, unsubstituted C5-C26 aryl, halogen, cyano, or Rv and R 7 together with the atoms in the ring to which they are bound form a five-or six-membered C1-C14 alkyl substituted aryl.
  12. 12. The compound of claim 10, wherein: Rv is either no or hydrogen and, R 7 and R 8 are independently hydrogen, isopropyl, tert-butyl, phenyl, fluoro or cyano, or Rv and R 7 together form 。
  13. 13. The compound of claim 8, having the structure: VIII (VIII) Wherein: (xxi) M=au (I), w=n, u=ch, ra=h, v=v "=carbon, rv=h, R 7 =R 8 =h; (xxii) M=au (I), w=n, u=ch, ra=h, v=v "=carbon, rv=h, R 7 =R 8 =tert-butyl; The dashed line indicates the presence of a bond.
  14. 14. The compound of claim 8, having the structure: Where m=au (I).
  15. 15. A compound having the structure: I is a kind of Wherein: The compounds generally have neutral, negative or positive charge, M is gold, having an oxidation state of 0, +1, +2 or +3, P' is selected from: Or (b) Wherein: Ra is independently hydrogen or isopropyl, and Rb is an isopropyl group, and is a hydroxyl group, Z has the following structure: Wherein: X 1 、X 2 、X 3 、X 4 、X 5 and X 6 are carbon, X 7 and X 8 are independently carbon or nitrogen, Rx 1 、Rx 2 、Rx 4 and Rx 5 are hydrogen, rx 3 、Rx 7 and Rx 8 are independently hydrogen, halogen, cyano, unsubstituted C1-C18 alkyl or unsubstituted C5-C26 aryl, rx 6 is halogen, cyano, unsubstituted C1-C18 alkyl or unsubstituted C5-C26 aryl, wherein when the corresponding X 7 or X 8 is nitrogen, each Rx 7 or Rx 8 is absent, or adjacent Rxn groups together with the atoms in the ring to which they are bonded, independently together form a five-or six-membered C1-C14 alkyl-substituted aryl, wherein n in the adjacent Rxn groups is a continuous integer pair of 1 to 4 or 5 to 8.
  16. 16. The compound of claim 15, wherein Rx 3 、Rx 7 and Rx 8 are independently hydrogen, halogen, methyl, cyano, t-butyl or phenyl, and Rx 6 is halogen, methyl, cyano, t-butyl or phenyl.
  17. 17. The compound of claim 15, having the structure: VI (VI) Wherein: w is carbon or nitrogen, W is bonded to one hydrogen atom or not bonded to the hydrogen atom according to valence, V' is carbon, and is represented by the formula V, U is carbon and V is nitrogen, or U is nitrogen and V is carbon, wherein U, V and V '' are bonded to one hydrogen atom or not bonded to a hydrogen atom depending on valence, R 7 is an unsubstituted, unsubstituted C1-C18 alkyl, cyano, halogen or unsubstituted C5-C26 aryl, or adjacent R 7 groups or adjacent R 8 groups together with the atoms in the ring to which they are bonded independently form a five-or six-membered C1-C14 alkyl-substituted aryl, R 8 is independently selected from the group consisting of none, hydrogen, unsubstituted C1-C18 alkyl, cyano, halogen, and unsubstituted C5-C26 aryl, or adjacent R 7 groups or adjacent R 8 groups together with the atoms in the ring to which they are bonded independently form a five-or six-membered C1-C14 alkyl-substituted aryl, and N3 and n4 are independently integers between 0 and 5, R 1 and R 2 are hydrogen.
  18. 18. The compound of claim 17, having the structure: VII (VII) Wherein: Rv is an unsubstituted, hydrogen or unsubstituted C1-C18 alkyl group, and R 8 is hydrogen, unsubstituted C1-C18 alkyl, unsubstituted C5-C26 aryl, halogen, cyano, R 7 is unsubstituted C1-C18 alkyl, unsubstituted C5-C26 aryl, halogen, cyano, or Rv and R 7 together with the atoms in the ring to which they are bound form a five-or six-membered C1-C14 alkyl substituted aryl.
  19. 19. The compound of claim 17, wherein: Rv is either no or hydrogen and, R 8 is hydrogen, isopropyl, tert-butyl, phenyl, fluoro or cyano, R 7 is isopropyl, tert-butyl, phenyl, fluoro or cyano, or Rv and R 7 together form 。
  20. 20. The compound of claim 15, having the structure: VIII (VIII) Wherein: (xvii) M=au (I), w=n, ra=h, u=ch, v=v "=carbon, rv=h, R 7 =R 8 =cn; (xviii) M=au (I), w=n, ra=hydrogen, u=ch, v=v "=carbon, R 8 =h, rv and R 7 together form ; (Xix) M=au (I), w=u=ch, ra=isopropyl, v=v "=carbon, rv=h, R 7 =R 8 =tert-butyl; The dashed line indicates no bond.

Description

D10 metal carbene complexes for OLED applications Cross Reference to Related Applications The application claims the benefit and priority of U.S. provisional application No.63/282,496 filed 11/23 of 2021, the entire contents of which are incorporated herein by reference. Technical Field The present invention relates generally to the field of luminescent d10 metal carbene complexes, in particular d10 metal carbene complexes containing (i) pyrazine-condensed N-heterocyclic carbene ligands or pyridine-condensed N-heterocyclic carbene ligands and (ii) carbazole ligands or α -, β -, γ -or δ -carboline ligands, and the use of these complexes in Organic Light Emitting Devices (OLEDs). Background Transition metal complexes have gained great interest in commercial and academic fields as molecular probes, catalysts and luminescent materials. As a light emitting material, transition metal complexes are increasingly being investigated as potential alternatives to pure organic-based materials due to their potential for improved light emitting efficiency and device stability compared to pure organic-based materials. Currently, cyclometallated iridium (III) and platinum (II) phosphors are one of the most competitive candidate materials in commercial OLED emitters. Nevertheless, the development of metal-based or organic Thermally Activated Delayed Fluorescence (TADF) emitters is still behind, mainly because of their lower stability, which affects the lifetime of the device. For practical applications, it is necessary to improve device performance and operational stability/lifetime of metal-based OLEDs. Some studies have described d10 complexes for use as emitters in OLEDs. Including U.S. patent 9,773,986 to Thompson et al, european patent application publication 3,489,243 to Thompson et al, U.S. patent application publication 2015/0108451 to Thompson et al, and U.S. patent application publication 2019/0161504 to Thompson et al, and CN112794863. Nevertheless, these studies have not reported the results of equipment life. Other studies include complexes of Cu (I), ag (I) or Au (I), involving carbene ligands and carbazoles, such as Hamze et al, science 2019,363,601-606, shi et al, J.am.chem.Soc.2019,141,3576-3588, hamze et al, J.am.chem.Soc.2019,141,21,8616-8626, li et al, angew.chem.int.ed.2020,59,8210-8217, and Hamze et al, front.chem.2020,8:401. However, some complexes exhibit phosphorescent properties, resulting in lower radiation decay rates. For example, IPr-Cu-Cz and IMes-Cu-Cz complexes (Angew.chem.int.ed.2020, 59, 8210-8217) exhibit long-lived room temperature phosphorescence with lifetimes in the millisecond range. Therefore, there remains a need to develop improved and efficient transition metal complexes to enable higher efficiencies in products comprising OLEDs. It is therefore an object of the present invention to provide new and improved luminescent transition metal bidentate complexes containing d10 metal. Disclosure of Invention Described herein are bidentate d10 metal carbene complexes comprising (I) Cu (I), ag (I) or Au (I), (ii) pyrazine-fused N-heterocyclic carbene (NHC) ligands or pyridine-fused N-heterocyclic carbene ligands, and (iii) carbazole ligands, pyridine [2,3-b ] indole ligands or pyridine [3,4-b ] indole ligands. The radiation characteristics of these compounds can be controlled by TADF. The emission color of these compounds can also be adjusted by using carbazole, pyrido [2,3-b ] indole or pyrido [3,4-b ] indole having different donor intensities. The compounds of the present invention have the following structure: Wherein: D is carbon, and the D is carbon, T, J and W are independently carbon or nitrogen, wherein at least one of T, J and W is nitrogen, wherein when T is carbon, J is nitrogen, or when T is nitrogen, J is carbon, and T, J and W are bonded to one hydrogen atom or not bonded to a hydrogen atom depending on valence, Each Ra is independently hydrogen, unsubstituted alkyl, or substituted alkyl, Each Rb is independently unsubstituted alkyl or substituted alkyl, X and Y are nitrogen, and the nitrogen is nitrogen, L is a single bond or no bond, CY3 and CY4 are independently an unsubstituted aryl group, a substituted aryl group, an unsubstituted heteroaryl group, a substituted C 3-C20 cycloalkenyl group, an unsubstituted C 3-C20 cycloalkenyl group, or a fused combination thereof, and R 1 and R 2 are hydrogen, or R 1, J, D and R 2 together form an unsubstituted aryl, substituted aryl, unsubstituted heteroaryl or substituted heteroaryl. In some forms, the compounds of the invention have the following structure: Wherein: (i) M=cu (I), w=n, ra=h, u=ch, v=v "=carbon, rv=h, and R 7＝R8 =h; (ii) M=cu (I), w=n, ra=h, u=ch, v=v "=carbon, rv=h, R 7＝H;R8 =cn; (iii) M=cu (I), w=n, ra=h, u=ch, v=v "=carbon, rv=h, R 7＝R8 =tert-butyl; (iv) M=cu (I), w=n, ra=h, u=ch, v=v "=carbon, rv=h, R 7＝R8 =phenyl; (v) M=cu (I), w=n, ra=h, u=ch, v=n, V "=carbon, rv=none, R 7＝R8 =h; (vi) M=cu (I), w=u=ch, v=v "=carbo