2,4,6-tris[3-(diphenylphosphinyl)phenyl]-1,3,5-triazine

CAS Number 1646906-26-4
Molecular Formula C₅₇H₄₂N₃O₃P₃
Molecular Weight 909.9 g/mol
Purity ≥99.0%
Appearance White solid

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Product Description

2,4,6-Tris(3-(diphenylphosphinyl)phenyl)-1,3,5-triazine, commonly known as PO-T2T, is a sophisticated organic compound. This highly π-conjugated molecule features a central 1,3,5-triazine core adorned with three 3-phenyl units, each bearing a diphenylphosphinyl group in the meta position. Its electron-deficient nature, stemming from the triazine core, makes it an ideal material for electron transport layers (ETL) and hole blocking layers (HBL) in organic light-emitting diodes (OLEDs). PO-T2T is particularly valued for its role in exciplex formation, which is crucial for advancing Thermally Activated Delayed Fluorescence (TADF) OLEDs. Spectroscopically, it exhibits a complex aromatic region in ¹H NMR, a downfield phosphine-oxide signal in ³¹P NMR, and strong P=O stretches in IR.

Synthesis Methods

  • Formation of Central Core: Cyanuric chloride (2,4,6-trichloro-1,3,5-triazine) is used as the starting material.

  • Nucleophilic Aromatic Substitution: Chlorine atoms are displaced by a nucleophile (e.g., Grignard reagent or aryl boronic acid) derived from a diphenylphosphine precursor.

  • Oxidation: Phosphorus atoms are oxidized from trivalent (P³⁺) to pentavalent (P⁵⁺) state using agents like hydrogen peroxide (H₂O₂) or meta-chloroperoxybenzoic acid (mCPBA).

Uses

  • Primary Application: OLEDs (Organic Light-Emitting Diodes)

    • Role: Ancillary ligand in phosphorescent OLEDs, particularly for red and green light emission.

    • Mechanism: Coordinates with lanthanide ions (e.g., Eu³⁺, Tb³⁺) to form stable complexes, shielding them from non-radiative decay pathways and acting as an "antenna" to transfer energy to the central ion.

    • Benefits: High efficiency and stability in OLED devices.

  • Other Applications:

    • Electron transport layer (ETL) and hole blocking layer (HBL) in OLEDs.

    • Exciplex formation in Thermally Activated Delayed Fluorescence (TADF) OLEDs.

    • Interface modification in perovskite light-emitting diodes (Pero-LEDs) to enhance charge injection and device performance.

Molecular Formula and Composition

  • Molecular Formula: C₅₇H₄₂N₃O₃P₃

  • Average Molar Mass: 909.8989 g/mol

  • Monoisotopic Mass: 909.243903 u

  • Elemental Mass Percent:

    • Carbon (C): 75.24%

    • Hydrogen (H): 4.65%

    • Nitrogen (N): 4.62%

    • Oxygen (O): 5.27%

    • Phosphorus (P): 10.21%

Structure and Functional Notes

  • Core: 1,3,5-triazine ring with three identical aryl substituents at the 2,4,6 positions.

  • Substituents: Each substituent is a 3-phenyl unit carrying a diphenylphosphinyl group (P=O with two phenyls attached) in the meta position on the phenyl ring.

  • Functional Groups:

    • Triazine core: Electron-deficient, contributing to its role in electron transport layers.

    • Phosphine oxide groups (P=O): High dipole moment, excellent Lewis base, and strong affinity for Lewis acids, particularly lanthanide ions.

Physical Properties

  • Appearance: White or off-white crystalline powder.

  • Solubility: Soluble in common organic solvents (CHCl₃, DCM, toluene, THF, DMF) and insoluble in water.

  • Symmetry: High C₃ symmetry.

Spectroscopic Properties

  • ¹H NMR (CDCl₃): Complex aromatic region with multiple multiplets between ~7.0–8.8 ppm; no aliphatic protons.

  • ³¹P NMR (CDCl₃): Phosphine-oxide P signal typically appears downfield (≈ +20 to +40 ppm).

  • IR: Strong P=O stretch around ~1150–1250 cm⁻¹; aromatic C–H stretches at 3000–3100 cm⁻¹.

  • UV–Vis: Strong π→π* absorption in the UV, possibly extending into the visible region.

Handling and Safety

  • Handling: Treat as an organic laboratory chemical; use gloves, eye protection, and work in a fume hood. Avoid inhalation of dust and keep away from strong reducing agents.

  • Disposal: Dispose of according to institutional or municipal regulations.

Analytical Tips

  • Identity Verification: HRMS (m/z ≈ 910.2517 for [M+H]⁺), ¹H NMR, and ³¹P NMR.

  • Elemental Analysis: Should match the percent composition within experimental error.

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