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<p>Stereoselective synthesis of <i>cis-</i> and <i>trans-</i> configurations remain challenging in molecular systems. Here, asymmetric 90<sup>o</sup> Pt(II) acceptors enable stereoselective coordination-driven self-assembly of configuration-specific [Pt<sub>2</sub>L<sub>2</sub>] metallacycles. The coordination of trimethylphosphine or triethylphosphine (PR<sub>3</sub>) and phosphangulene (Phang) to the Pt(II) centers yielded two asymmetric <i>cis</i>-PtCl<sub>2</sub>(PR<sub>3</sub>)(Phang) complexes. Upon ligand exchange, these acceptors assemble with the bispyridyl ligands to form statistical mixtures of <i>cis</i>- and <i>trans</i>- metallacycles. Stereoselective self-assembly is achieved by modifying the bis-pyridyl ligand with <i>N-ortho</i>-bismethyl groups, leveraging intramolecular C–H···π interactions with Phang, steric effects, and 90<sup>o</sup> Pt(II) heteroligation to selectively generate <i>trans</i>- or <i>cis</i>- isomers. The stereochemistry is confirmed by NMR spectrometry, investigation of the mass spectrometry, density functional theory calculations, and single-crystal X-ray diffraction. Notably, hierarchical self-assembly in the crystalline state revealed stark structural divergences between <i>trans</i>- and <i>cis</i>- metallacycles, offering key insights into stereo-controlled supramolecular design.</p><p></p>

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Stereoselective self-assembly of cis- and trans- [Pt2L2] metallacycles via geometrically-asymmetric 90o Pt(II) acceptors

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年11月21日

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  • Jianmin Qin,
  • Desheng Li,
  • Wenqian Liu,
  • Yilin Liao,
  • Liting Tan,
  • Hongyu Bai,
  • Taotao Liu,
  • Ming Wang,
  • Yiliang Wang

摘要

Stereoselective synthesis of cis- and trans- configurations remain challenging in molecular systems. Here, asymmetric 90o Pt(II) acceptors enable stereoselective coordination-driven self-assembly of configuration-specific [Pt2L2] metallacycles. The coordination of trimethylphosphine or triethylphosphine (PR3) and phosphangulene (Phang) to the Pt(II) centers yielded two asymmetric cis-PtCl2(PR3)(Phang) complexes. Upon ligand exchange, these acceptors assemble with the bispyridyl ligands to form statistical mixtures of cis- and trans- metallacycles. Stereoselective self-assembly is achieved by modifying the bis-pyridyl ligand with N-ortho-bismethyl groups, leveraging intramolecular C–H···π interactions with Phang, steric effects, and 90o Pt(II) heteroligation to selectively generate trans- or cis- isomers. The stereochemistry is confirmed by NMR spectrometry, investigation of the mass spectrometry, density functional theory calculations, and single-crystal X-ray diffraction. Notably, hierarchical self-assembly in the crystalline state revealed stark structural divergences between trans- and cis- metallacycles, offering key insights into stereo-controlled supramolecular design.