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<p>The reversible σ-dimerization of radicals is a fundamental process in bond formation and cleavage, yet achieving this with an isolable heavy carbyne analogue has remained a paramount challenge. Herein, we report the synthesis and characterization of an isolable germylyne radical that demonstrates remarkable ambient stability while undergoing clean, reversible σ-dimerization via a Ge–Ge single bond. This reversible process, which exhibits a pronounced thermochromic response, is thoroughly elucidated through variable-temperature NMR/EPR spectroscopy and X-ray crystallography, revealing a moderate bond dissociation enthalpy. Beyond dimerization, this germylyne radical acts as a versatile synthon for main-group bond activation, readily cleaving chalcogen-chalcogen (S–S, Se–Se), phosphorus-phosphorus (in P₄), and even challenging aromatic carbon-chlorine (C–Cl) bonds. This work provides the direct structural evidence of a heavy carbyne’s dimerization pathway and establishes a new platform for dynamic covalent bonding in main-group chemistry, with implications for stimuli-responsive materials and radical-mediated activation.</p>

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A persistent germylyne radical enabling reversible σ-dimerization and diverse bond activation

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年5月28日

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  • Xingyu Yang,
  • Meirong Song,
  • Liancheng He,
  • Shanshan Kong,
  • Runbo Pei,
  • Quanchun Sun,
  • Wanwan Jia,
  • Shuxuan Tang,
  • Xiao-Song Xue,
  • Xinping Wang

摘要

The reversible σ-dimerization of radicals is a fundamental process in bond formation and cleavage, yet achieving this with an isolable heavy carbyne analogue has remained a paramount challenge. Herein, we report the synthesis and characterization of an isolable germylyne radical that demonstrates remarkable ambient stability while undergoing clean, reversible σ-dimerization via a Ge–Ge single bond. This reversible process, which exhibits a pronounced thermochromic response, is thoroughly elucidated through variable-temperature NMR/EPR spectroscopy and X-ray crystallography, revealing a moderate bond dissociation enthalpy. Beyond dimerization, this germylyne radical acts as a versatile synthon for main-group bond activation, readily cleaving chalcogen-chalcogen (S–S, Se–Se), phosphorus-phosphorus (in P₄), and even challenging aromatic carbon-chlorine (C–Cl) bonds. This work provides the direct structural evidence of a heavy carbyne’s dimerization pathway and establishes a new platform for dynamic covalent bonding in main-group chemistry, with implications for stimuli-responsive materials and radical-mediated activation.