Spiro-Cyclometalated Iridium Emitters for Stable [4+2] OLED Emission

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Solution Overview

Problem

Existing iridium (III) phosphors face issues with geometrical isomerization under drastic conditions, leading to vulnerabilities in thermal and chemical stability, which are not adequately addressed by tridentate ligands, and there is a scarcity of non-planar tetradentate ligands with [4+2] coordination mode in OLED applications.

Innovation Solution

A novel molecular design featuring a [4+2] coordination architecture with a tripodal arranged, cross-shaped tetradentate cyclometalated ligand and an auxiliary bidentate ligand, providing enhanced stability and emission properties through a spiro linkage and octahedral iridium (III) emitters.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Device complexity

If tridentate ligands are used in iridium phosphors, then the coordination mode is simplified, but thermal and stereochemical stability is insufficient

Engineering Contradiction:
Improvecoordination mode complexityVSAvoidthermal and stereochemical stability
Core Design Contradiction:
Device complexityVSStability of the object's composition

Solution Approach 1:

The patent combines a tetradentate cyclometalated ligand with a bidentate ancillary ligand to form a composite coordination structure. This composite approach creates a more stable complex by distributing coordination bonds across multiple ligand types with different denticities, resolving the contradiction between structural simplicity and stability.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The coordination sphere is segmented into two functional parts: a tetradentate ligand providing the primary coordination framework and a bidentate ligand completing the octahedral geometry. This segmentation allows each ligand to optimize its binding mode while collectively achieving high stability.

Inventive Principle:
Principle #1Segmentation

2Ease of manufacture

If planar tetradentate ligands are used, then synthesis is easier, but the chelate effect and stability are reduced compared to non-planar structures

Engineering Contradiction:
Improvesynthesis easeVSAvoidchelate effect and stability
Core Design Contradiction:
Ease of manufactureVSStability of the object's composition

Solution Approach 1:

The patent employs a non-planar, three-dimensional tetradentate ligand structure that adopts a curved or twisted geometry around the iridium center. This curvature enhances the chelate effect by pre-organizing the ligand in a geometry that favors binding, thereby improving stability despite increased synthesis complexity.

Inventive Principle:
Principle #14Spheroidality (Curvature)

3Stability of the object's composition

If [4+2] coordination mode with non-planar tetradentate ligand is implemented, then chelate effect and stability are enhanced, but such structures are scarce and more complex to synthesize

Engineering Contradiction:
Improvethermal and chemical stabilityVSAvoidmolecular architecture complexity
Core Design Contradiction:
Stability of the object's compositionVSDevice complexity

Solution Approach 1:

The tetradentate ligand is designed with universal binding capabilities that can accommodate the iridium center in a consistent [4+2] coordination mode. The ligand structure incorporates functional units that can independently coordinate, providing multi-functionality that simplifies the overall molecular design while maintaining high stability.

Inventive Principle:
Principle #6Universality (Multi-functionality)

4Stability of the object's composition

If higher denticity ligands (tridentate, tetradentate, hexadentate) are assembled, then thermal and chemical stability is elevated, but molecular architecture complexity increases

Engineering Contradiction:
Improvethermal and chemical stabilityVSAvoidmolecular architecture complexity
Core Design Contradiction:
Stability of the object's compositionVSDevice complexity

Solution Approach 1:

The patent applies local quality by assigning specific coordination roles to different parts of the ligand system. The tetradentate ligand provides four coordination sites with specific geometric arrangement, while the bidentate ligand provides the remaining two sites. This localized functional differentiation achieves high stability without requiring uniform complexity throughout the entire molecule.

Inventive Principle:
Principle #3Local quality

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The new iridium (III) emitters exhibit high thermal and stereochemical stability, ease of emission color tuning, and high quantum efficiency, with prototype devices achieving maximum luminance and external quantum efficiency of 109,000 cd/m² and 17.0%, respectively.

Implementation Method 1

iridium (III) phosphors bearing two distinctive tridentate ligands in a [3+3] coordination mode and a suite of monodentate, bidentate and tridentate ligands in a [3+2+1] coordination mode

Methodology Applied
Scientific EffectPhosphorescence: Phosphorescence

Data Source

PatentEP4200310B1Spiro-cyclometalated iridium emitters for OLED applications
Publication Date: 2025.11.05 THE UNIVERSITY OF HONG KONG
  • EP4200310B1 patent drawingFigure 1
  • EP4200310B1 patent drawingFigure 2
  • EP4200310B1 patent drawingFigure 3

AI summary

Disclosed are spiro-cyclometalated iridium emitters and their preparation, OLED devices including the spiro-cyclometalated iridium emitters, and methods related thereto.