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 CH₂Cl₂ 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.

Keywords: axial chirality; circularly polarized luminescence (CPL); platinum(II) complex; phosphorescence;  chiral chemistry

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Tauchi, D.; Ogura, S.; Sakura, M.; Tsubaki, K.; Hasegawa, M. Beilstein Arch. 2025, 202553. doi:10.3762/bxiv.2025.53.v1

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