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

chemistry Medicinal and pharmaceutical chemistry Nano- and molecular-scale electronics Nano-biomaterials and bioscience Nanomagnetics Nanomaterials, thin films and nanointerfaces Nanomedicine Nanometrology and nanomechanics Nano-optics Nanopatterning, self-assembly and nanofabrication Nanostructures for energy and sensing applications Natural products chemistry Organo main group chemistry Other nanotechnology (unclassified) Other organic chemistry (unclassified) Photochemistry and photovoltaics Physical organic chemistry Supramolecular chemistry 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 (glum) 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.

axial chirality; circularly polarized luminescence (CPL); platinum(II) complex; phosphorescence; chiral chemistry | Format: DOCX | Size: 4.1 MB | Download | When a peer-reviewed version of this preprint is available, this information will be updated in the information box above. If no peer-reviewed version is available, please cite this preprint using the following information: Tauchi, D.; Ogura, S.; Sakura, M.; Tsubaki, K.; Hasegawa, M. Beilstein Arch. 2025, 202553. doi:10.3762/bxiv.2025.53.v1 Citation data can be downloaded as file using the "Download" button or used for copy/paste from the text window below. Citation data in RIS format can be imported by all major citation management software, including EndNote, ProCite, RefWorks, and Zotero. © 2025 Tauchi et al.; licensee Beilstein-Institut. This is an open access work licensed under the terms of the Beilstein-Institut Open Access License Agreement (https://www.beilstein-archives.org/xiv/terms), which is identical to the Creative Commons Attribution 4.0 International License (https://creativecommons.org/licenses/by/4.0). The reuse of material under this license requires that the author(s), source and license are credited. Third-party material in this work could be subject to other licenses (typically indicated in the credit line), and in this case, users are required to obtain permission from the license holder to reuse the material.