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<p>Metallocene research has influenced the development of organometallic chemistry, and the metal–nonmetal inverted half-sandwich structure (inverse metallocene) was very recently discovered. However, additional instances are required to propose the concept inverse metallocene and it remains uncertain whether metal five-membered ring structures analogous to the cyclopentadienyl anion structure exist. Herein we report the synthesis of a series of palladium analogs Pd<sub>8</sub>(PPh)<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub>(Ph<sub>2</sub>P=O)(S-Adm)<sub>5</sub> (Pd<sub>8</sub>–P), Pd<sub>6</sub>(PPh)(PPh<sub>3</sub>)(S-Adm)<sub>6</sub> (Pd<sub>6</sub>), Pd<sub>5</sub>(PPh)(S-Adm)<sub>4</sub>[(Ph<sub>2</sub>P)<sub>2</sub>O] (Pd<sub>5</sub>–O), and Pd<sub>5</sub>(PPh)(S-Adm)<sub>4</sub>[(Ph<sub>2</sub>P)<sub>2</sub>CH<sub>2</sub>] (Pd<sub>5</sub>–C), identify their fundamental metal building block named five-membered Pd aromatic ring, and reveal their conjugation‒photothermy correlation. In particular, we report an average NIR-II photothermal conversion efficiency per metal atom of 14.7% and the stability of the five-membered Pd aromatic ring, as illustrated by the fact that Pd<sub>5</sub>–C maintained photothermy performance for &gt;10 heating–cooling cycles even after the ligands were removed. We further demonstrate the great potential of inverse palladocenes in areas such as laser shielding, high-temperature degradation, ignition, and temperature/light control. These results declare the research and application start of a type of materials named inverse palladocenes.</p>

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Inverse palladocenes

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年1月30日

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  • Qing You,
  • Xue-Lian Jiang,
  • Yan Zhao,
  • Wanmiao Gu,
  • Jun Li,
  • Zhikun Wu

摘要

Metallocene research has influenced the development of organometallic chemistry, and the metal–nonmetal inverted half-sandwich structure (inverse metallocene) was very recently discovered. However, additional instances are required to propose the concept inverse metallocene and it remains uncertain whether metal five-membered ring structures analogous to the cyclopentadienyl anion structure exist. Herein we report the synthesis of a series of palladium analogs Pd8(PPh)2(PPh3)2(Ph2P=O)(S-Adm)5 (Pd8–P), Pd6(PPh)(PPh3)(S-Adm)6 (Pd6), Pd5(PPh)(S-Adm)4[(Ph2P)2O] (Pd5–O), and Pd5(PPh)(S-Adm)4[(Ph2P)2CH2] (Pd5–C), identify their fundamental metal building block named five-membered Pd aromatic ring, and reveal their conjugation‒photothermy correlation. In particular, we report an average NIR-II photothermal conversion efficiency per metal atom of 14.7% and the stability of the five-membered Pd aromatic ring, as illustrated by the fact that Pd5–C maintained photothermy performance for >10 heating–cooling cycles even after the ligands were removed. We further demonstrate the great potential of inverse palladocenes in areas such as laser shielding, high-temperature degradation, ignition, and temperature/light control. These results declare the research and application start of a type of materials named inverse palladocenes.