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<p>Chiral organometallic complexes hold great potential for a broad range of applications. However, achieving metal-induced chirality in square-planar systems remains highly challenging because their inherent two-dimensional geometry often makes them easily superimposable on their mirror images. Herein, we present an efficient strategy employing anti-isomer arrangements of two cyclometalated ligands and two bridged ligands to build novel metal-induced planar chirality based on half-lantern binuclear Pd(II) complexes. The resulting Pd(II) assemblies display exceptional phosphorescence quantum yields of up to 98.5% in the solid states, enabled by the synergistic cooperation of soft bridged N^S thiolate ligands to finely control intramolecular Pd–Pd distances and cyclometalated σ-donor C^C* carbene ligands to destabilize low-lying d-d states, and circularly polarized luminescence with asymmetry factors in the range of 1.6 × 10<sup>−3</sup>–3.5 × 10<sup>−3</sup>. Furthermore, the metal-induced planar chirality undergoes highly diastereoselective self-sorting (&gt;99%) driven by chiral soft bridged thiolate ligands. This work thus provides a straightforward and versatile design principle for establishing planar chirality in square-planar complexes, offering new opportunities for chiroptical and circularly polarized luminescence applications.</p>

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Constructing half-lantern binuclear Pd(II) complexes: metal-induced planar chirality, chirality self-sorting and near 100% phosphorescence quantum yields

  • 期刊论文

  • 发表日期：

    2026年5月19日

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  • Bao Zhang,
  • Baojia Yang,
  • Jincheng Zhang,
  • Hailong Chen,
  • Yinshuang Shi,
  • Jing Huang,
  • Ran Deng,
  • Wanrong Xie,
  • Hailiang Ni,
  • Peng Cao,
  • Ping Hu,
  • Bi-Qin Wang,
  • Ke-Qing Zhao,
  • Xian-Kai Chen,
  • Haifeng Xiang,
  • Jintong Song

摘要

Chiral organometallic complexes hold great potential for a broad range of applications. However, achieving metal-induced chirality in square-planar systems remains highly challenging because their inherent two-dimensional geometry often makes them easily superimposable on their mirror images. Herein, we present an efficient strategy employing anti-isomer arrangements of two cyclometalated ligands and two bridged ligands to build novel metal-induced planar chirality based on half-lantern binuclear Pd(II) complexes. The resulting Pd(II) assemblies display exceptional phosphorescence quantum yields of up to 98.5% in the solid states, enabled by the synergistic cooperation of soft bridged N^S thiolate ligands to finely control intramolecular Pd–Pd distances and cyclometalated σ-donor C^C* carbene ligands to destabilize low-lying d-d states, and circularly polarized luminescence with asymmetry factors in the range of 1.6 × 10−3–3.5 × 10−3. Furthermore, the metal-induced planar chirality undergoes highly diastereoselective self-sorting (>99%) driven by chiral soft bridged thiolate ligands. This work thus provides a straightforward and versatile design principle for establishing planar chirality in square-planar complexes, offering new opportunities for chiroptical and circularly polarized luminescence applications.