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CN-121991134-A - Spiral chiral tetradentate platinum (II) complex circularly polarized luminescent material and application thereof

CN121991134ACN 121991134 ACN121991134 ACN 121991134ACN-121991134-A

Abstract

The invention relates to the technical field of preparation of circularly polarized luminescent materials, in particular to a spiro chiral tetradentate platinum (II) complex circularly polarized luminescent material based on pyridine-carbazole-phenyl carbene and derivative structures thereof and application thereof. The provided complex molecule can autonomously induce the whole tetradentate ligand to coordinate with metal ions in a mode of small steric hindrance through a remote center chiral fragment in chiral substituted pyridine to form an optically pure spiro chiral metal complex circularly polarized light luminescent material, and the spiro chiral metal complex circularly polarized light luminescent material does not need chiral resolution, has high molecular thermodynamic stability and has important application in a circularly polarized light emitting element.

Inventors

  • LI GUIJIE
  • ZHANG CHENGYAO
  • SHE YUANBIN
  • ZHAN FENG

Assignees

  • 浙江工业大学
  • 浙江华显光电科技有限公司

Dates

Publication Date
20260508
Application Date
20241108

Claims (15)

  1. 1. A spiro chiral tetradentate platinum (II) complex circularly polarized luminescent material is characterized by having a structure shown as a general formula (I) or (I '), wherein (I) and (I') are enantiomers with each other: In formula (I) or (I'), L is O、S、CR x R y 、C＝O、SiR x R y 、GeR x R y 、NR z 、PR z 、R z P＝O、AsR z 、R z As＝O、S＝O、SO 2 、Se、Se＝O、SeO 2 、BH、BR z 、R z Bi＝O or BiR z ;R x 、R y and R z are each independently one or more of hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, deuteroalkyl, deuteroaryl, deuteroalkyl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono-or di-alkylamino, mono-or di-arylamino, ester, -CN, alkylsilyl, alkoxysilane, arylsilyl, heteroarylsilyl, aryloxysilyl; "is a carbon atom with central chirality; Y 1 、Y 2 、Y 3 is CR 3 or N, Z 1 、Z 2 、Z 3 、Z 4 、Z 5 、Z 6 、Z 7 、Z 8 is CR 4 or N; R 1 、R 2 、R 3 、R 4 each independently represents mono-, poly-or unsubstituted; r 1 、R 3 、R 4 、R a 、R b 、R m and R n are each independently one or more of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, haloalkyl, aryl, heteroaryl, haloaryl, haloheteroaryl, deuteroalkyl, deuteroalryl, deuteroalkyl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono-or di-alkylamino, mono-or di-arylamino, ester, -CN, alkylsilyl, alkoxysilane, arylsilyl, heteroarylsilyl, aryloxysilyl; R 2 is independently hydrogen, deuterium, alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted aza-aryl, substituted or unsubstituted fused ring heteroaryl, wherein when substituted, the substituents are selected from one or more of deuterium, alkyl, aryl, heteroaryl, mono or dialkylamino, mono or diarylamino, and CN.
  2. 2. The spirochiral tetradentate platinum (II) complex circularly polarized light-emitting material according to claim 1, wherein each occurrence of R 2 is independently selected from one or more of hydrogen, deuterium, -CN, F, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, deuterated t-butyl, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, substituted or unsubstituted phenyl, substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted C3-C24 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted trianilino, and when substituted, the substituent is selected from hydrogen, deuterium, F, -CN, C1-C10 alkyl, phenyl, carbazolyl, and R 2 may be linked to the substituted group to form a fused ring. .
  3. 3. The spirochiral tetradentate platinum (II) complex circularly polarized light-emitting material according to claim 1, wherein the spirochiral tetradentate platinum (II) complex circularly polarized light-emitting material has a chemical formula as shown in general formula (I-I) or (I '-I), (I-II) or (I' -II), wherein (I-I) and (I '-I), (I-II) and (I' -II) are enantiomers with each other: Wherein ,L,Y 1 -Y 3 ,Z 1 -Z 8 ,R 1 、R 3 、R 4 ,R a ,R b ,R m and R n are each as defined in claim 1; In formula (I-I) or (I' -I), X 1 、X 2 、X 3 、X 4 is each independently CR 7 or N, R 7 is each independently at each occurrence one or more of hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, deuteroalkyl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono-or di-alkylamino, mono-or di-arylamino, ester, -CN, alkylsilyl, alkoxysilane-based, arylsilyl, heteroaryl-based, aryloxy-based; R 5 、R 6 in formula (I-ii) or (I' -ii) is, independently for each occurrence, one or more of hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, deuteroalkyl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono-or di-alkylamino, mono-or di-arylamino, ester, -CN, alkylsilyl, alkoxysilane, arylsilyl, heteroarylsilyl, aryloxy-silyl, R 5 、R 6 may be fused to a ring.
  4. 4. The spirochiral tetradentate platinum (II) complex circularly polarized light-emitting material according to claim 1, wherein R a ,R b ,R m and R n are each independently one or more of hydrogen, deuterium, a fluorine atom, a substituted or unsubstituted C1-C24 alkyl group, a C3-C24 cycloalkyl group, a substituted or unsubstituted C6-C18 aryl group, a C1-C24 heteroalkyl group, a C3-C24 heterocycloalkyl group, a C6-C18 heteroaryl group, when containing a substituent, the substituent is selected from the group consisting of hydrogen, deuterium, a fluorine atom, a C1-C14 alkyl group, and R x 、R y and R z are each independently selected from the group consisting of hydrogen, deuterium, a fluorine atom, a substituted or unsubstituted C1-C24 alkyl group, a substituted or unsubstituted C6-C18 aryl group, a C1-C24 heteroalkyl group, a C6-C18 heteroaryl group, and when containing a substituent, the substituent is selected from the group consisting of hydrogen, deuterium, a fluorine atom, a C1-C14 alkyl group.
  5. 5. The spirochiral tetradentate platinum (II) complex circularly polarized light-emitting material according to claim 1, wherein each occurrence of R 1 is independently selected from hydrogen, deuterium, -CN, F, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, deuterated t-butyl, substituted or unsubstituted aryl, substituted or unsubstituted carbazolyl, wherein when substituted, the substituents are selected from hydrogen, deuterium, F, -CN, C1-C10 alkyl, and wherein when R 1 is selected from aryl, they may be linked to the substituted groups to form a fused ring.
  6. 6. The spirochiral tetradentate platinum (II) complex circularly polarized light-emitting material according to claim 1, wherein R 3 is independently selected from one or more of hydrogen, deuterium, -CN, F, substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C3-C24 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C1-C30 silyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C6-C30 indenyl, substituted or unsubstituted C6-C30 heteroindenyl, when substituted, wherein the substituents are independently selected from one or more of hydrogen, deuterium, F, -CN, C1-C10 alkyl, phenyl, carbazolyl, and wherein each occurrence of R 4 is independently selected from one or more of hydrogen, deuterium, -CN, F, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 aralkyl, substituted or unsubstituted C6-C30 indenyl, substituted or unsubstituted C6-C30 heteroindenyl, when substituted, and wherein the substituents are independently selected from one or more of hydrogen, deuterium, F, -CN, C1-C10 alkyl, phenyl, carbazolyl, and when substituted.
  7. 7. The spirochiral tetradentate platinum (II) complex circularly polarized light-emitting material according to claim 3, wherein R 7 is independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, substituted or unsubstituted aryl, substituted or unsubstituted carbazolyl, substituted or unsubstituted diphenylamino, when substituted, said substituents are selected from the group consisting of hydrogen, deuterium, fluorine atoms, methyl, ethyl, propyl, butyl, t-butyl, phenyl, biphenyl, naphthyl, carbazolyl, R 5 、R 6 is independently hydrogen, deuterium, fluorine atoms, methyl, ethyl, propyl, butyl, t-butyl, phenyl, or R 5 、R 6 may be linked to form a cyclopropane, a cyclobutane, a cyclopentane, a cyclohexane, a cycloheptane, or a cyclooctane group at each occurrence.
  8. 8. The spirochiral tetradentate platinum (II) complex circularly polarized light-emitting material according to claim 1, wherein the complex circularly polarized light-emitting material is selected from the following structures and enantiomers thereof, but is not limited thereto, wherein "D" represents deuterium:
  9. 9. use of a spiro chiral tetradentate platinum (II) complex circularly polarized light emitting material according to any one of claims 1-8 for the preparation of an electronic device.
  10. 10. The use according to claim 9, wherein the electronic device is a light emitting device, a 3D display device, a three-dimensional imaging device, an optical information encryption device, an information storage device or a bio-imaging device.
  11. 11. An organic electroluminescent device, characterized in that the organic electroluminescent device comprises a cathode, an anode and an organic functional layer therebetween, and the organic functional layer comprises the spiro chiral tetradentate platinum (II) complex circularly polarized luminescent material as claimed in any one of claims 1 to 8.
  12. 12. An organic optoelectronic device comprising a first electrode, a second electrode facing the first electrode, and a luminescent material layer disposed between the first electrode and the second electrode, wherein the luminescent material layer comprises the spiro chiral tetradentate platinum (II) complex circularly polarized luminescent material of any one of claims 1-8.
  13. 13. A display or lighting device, characterized in that it comprises the organic electroluminescent device of claim 11 and/or the organic optoelectronic device of claim 12.
  14. 14. A composition comprising a spiro chiral tetradentate platinum (II) complex circularly polarized light emitting material according to any one of claims 1-8.
  15. 15. A formulation comprising the spiro chiral tetradentate platinum (II) complex circularly polarized light emitting material of any one of claims 1-8 and at least one solvent.

Description

Spiral chiral tetradentate platinum (II) complex circularly polarized luminescent material and application thereof Technical Field The invention relates to the technical field of preparation of circularly polarized luminescent materials, in particular to a spiro chiral tetradentate platinum (II) complex circularly polarized luminescent material based on pyridine-carbazole-phenyl carbene and derivative structures thereof and application thereof. Background Circular Polarized Luminescence (CPL) is a phenomenon in which a chiral luminescent material emits left-handed or right-handed circularly polarized light after being excited, and thus design development of chiral luminescent materials is a key in this field. With the intensive research of scientific researchers, the circularly polarized luminescent material has important application in the fields of 3D display, data storage, quantum computation, optical anti-counterfeiting, biological imaging, asymmetric synthesis and the like. The phosphorescent material of the cyclometalated platinum (II) and palladium (II) complex can fully utilize all singlet excitons and triplet excitons generated by the electro-excitation due to the heavy atomic effect, so that the maximum theoretical quantum efficiency can reach 100%, and the complex is an ideal luminescent material. The two-tooth ring metal platinum (II) and palladium (II) complexes have lower rigidity, and the energy of excited state material molecules is consumed in a non-radiative mode due to the fact that the two-tooth ligands are easy to twist and vibrate, so that the luminous quantum efficiency of the two-tooth ring metal platinum (II) and palladium (II) complexes is reduced, and the luminous quantum efficiency of the three-tooth ligand-based ring metal platinum (II) and palladium (II) complexes can be improved due to the fact that the molecular rigidity of the three-tooth ligand-based ring metal platinum (II) and palladium (II) complexes is enhanced, but the chemical stability and the thermal stability of the complexes are greatly reduced due to the fact that the second single-tooth ligand (such as Cl -, phenoxy anions, alkyne anions and carbenes) is contained, and the two-tooth ligand-based ring metal complexes are difficult to sublimate and purify for preparing OLED devices, so that the luminescent materials based on the two-tooth ligand and the three-tooth ligand ring metal complexes are unfavorable for the application of the luminescent materials to the stable and efficient OLED devices. The central metal ions of the divalent ring metal platinum (II) and the palladium (II) complex are dsp 2 hybridized, so that stable and rigid planar quadrilateral configuration molecules are easily formed by coordination with tetradentate ligands, and the high molecular rigidity can inhibit non-radiative relaxation caused by molecular vibration and rotation and reduce energy loss of excited state material molecules, thereby being beneficial to improvement of the luminous quantum efficiency of the material molecules. Due to steric hindrance of two aryl groups at the tail end of the tetradentate ligand of the cyclometalated platinum (II) and palladium (II) complex, the material molecule presents a distorted quadrilateral configuration, and has the property of spiro chirality in theory, but the molecule is very easy to racemize through up-and-down vibration of the two aryl groups at the tail end of the ligand in a solution or heating sublimation process, enantiomers of the molecule cannot be separated, and the optically pure cyclometalated platinum (II) and palladium (II) complex material molecule is very difficult to obtain, so that the material molecule does not have the property of circular polarized luminescence. Therefore, how to design and develop the optical pure cyclometallated platinum (II) complex material molecule with high chemical stability and thermodynamic stability and circular polarization luminescence property has great significance and great practical value for the application of the optical pure cyclometallated platinum (II) complex material molecule in a circular polarization luminescence OLED device (CP-OLED), and is also a problem to be solved in the CP-OLED field. Disclosure of Invention The invention aims at overcoming the defects in the research and development of the current circular polarization luminescent material and provides a spiro chiral tetradentate platinum (II) complex circular polarization luminescent material and application thereof. The provided complex has pyridine-carbazole-phenyl carbene and a derivative structure thereof, and the complex molecule can autonomously induce the whole tetradentate ligand to coordinate with metal ions in a small steric hindrance manner through a remote center chiral fragment in chiral substituted pyridine to form an optically pure spiro chiral metal complex circularly polarized light luminescent material. The complex circularly polarized luminescent mat