Design and synthesis of axially chiral platinum(II) complex and its CPL properties in PMMA matrix

A pair of axially chiral platinum(II) complex was synthesized via Sonogashira coupling and subsequent coordination of a pincer ligand to a precursor. The complex exhibited a broad absorption band ranging from 250 to 700 nm in the UV–vis spectrum, with TD-DFT calculations indicating mixed ligand-to-ligand charge transfer (LL′CT) and metal-to-ligand charge transfer (MLCT) character. Photoluminescence measurements in CH 2 Cl 2 solution revealed dual emission peaks at 427 nm and 596 nm, with a quantum yield of 3%. In PMMA matrix, the emission peaks were blue-shifted to 408 nm and 558 nm, and the quantum yield slightly increased to 4%. CD spectra showed distinct Cotton effects in the MLCT region, and CPL signals were observed only in the PMMA matrices, with a dissymmetry factor ( g lum ) of |0.4 × 10⁻³|. These results demonstrate that axial chirality can be effectively transferred to the metal center and induce CPL activity under restricted molecular motion, providing a promising strategy for designing chiral phosphorescent materials.

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Publication Details

Published
2025-09-01
DOI
https://doi.org/10.3762/bxiv.2025.53.v1
Primary Topic
Axial and Atropisomeric Chirality Synthesis
Type
article
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article

Design and synthesis of axially chiral platinum(II) complex and its CPL properties in PMMA matrix

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Axial and Atropisomeric Chirality Synthesis
article

Design and synthesis of axially chiral platinum(II) complex and its CPL properties in PMMA matrix

Masashi Hasegawa, Shinji Ogura, Kazunori Tsubaki, Misa Sakura, Daiki Tauchi
article en

Abstract

A pair of axially chiral platinum(II) complex was synthesized via Sonogashira coupling and subsequent coordination of a pincer ligand to a precursor. The complex exhibited a broad absorption band ranging from 250 to 700 nm in the UV–vis spectrum, with TD-DFT calculations indicating mixed ligand-to-ligand charge transfer (LL′CT) and metal-to-ligand charge transfer (MLCT) character. Photoluminescence measurements in CH 2 Cl 2 solution revealed dual emission peaks at 427 nm and 596 nm, with a quantum yield of 3%. In PMMA matrix, the emission peaks were blue-shifted to 408 nm and 558 nm, and the quantum yield slightly increased to 4%. CD spectra showed distinct Cotton effects in the MLCT region, and CPL signals were observed only in the PMMA matrices, with a dissymmetry factor ( g lum ) of |0.4 × 10⁻³|. These results demonstrate that axial chirality can be effectively transferred to the metal center and induce CPL activity under restricted molecular motion, providing a promising strategy for designing chiral phosphorescent materials.

Kitasato University, Japan Science and Technology Agency, Core Research for Evolutional Science and Technology
Openalex Percentile: Top 83%
Axial and Atropisomeric Chirality Synthesis
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