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<p>Counterions, typically thought to merely balance charge, have now proven to be far from innocent in shaping the structural and functional characteristics of ionic metal nanoclusters (NCs). In contrast to well-established counteranions, the role of countercations—especially in electronic interactions with neighboring NCs—remains largely unexplored due to their repulsion with the positively charged metal centers. Here, we report the significant contributions of acridinium cations (Acr<sup>+</sup>) in facilitating the redox conversion as well as charge transfer to Au<sub>55</sub> anion NCs. The cluster represents the first fully structure-resolved Schmid-type Au<sub>55</sub> species, which features quasi-<i>C</i><sub>2</sub> symmetry with a unique Au<sub>2</sub>-centered Au<sub>27</sub> uncoordinated metal cage. Temperature-dependent absorption spectroscopy discloses countercation effects on electron-phonon interactions within the Au<Stack> <sub>55</sub> <sup>−</sup> </Stack>d on the Bose-Einstein two- component and reveals a substantial suppression of acoustic phonons in <b>Acr·Au</b><sub><b>55</b></sub>, based on the Bose-Einstein two-oscillator model band-gap renormalization analysis. Systematic studies through fluorescence titration, electron paramagnetic resonance spectroscopy, and femtosecond transient absorption spectroscopy provide strong support for the photoinduced electron transfer from the locally excited singlet state of Acr<sup>+</sup> cation to the Au<Stack> <sub>55</sub> <sup>−</sup> </Stack> cluster. This work marks the first observation of the countercation effect on charge transfer in metal NCs and unlocks a new avenue for their functional manipulation.</p>

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Countercation-driven oxidative conversion to Schmid-type Au55 anion nanoclusters with interionic charge transfer

  • 期刊论文

  • 发表日期：

    2026年7月30日

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  • Si-Rui Shen,
  • Xia-Xi Lei,
  • De-Bo Hao,
  • Lan-Fang Liang,
  • Xu-Hang Zhong,
  • Shang-Fu Yuan,
  • Bing-Zhe Wang,
  • Wen-Wu Xu,
  • Tao Wu,
  • Dan Li

摘要

Counterions, typically thought to merely balance charge, have now proven to be far from innocent in shaping the structural and functional characteristics of ionic metal nanoclusters (NCs). In contrast to well-established counteranions, the role of countercations—especially in electronic interactions with neighboring NCs—remains largely unexplored due to their repulsion with the positively charged metal centers. Here, we report the significant contributions of acridinium cations (Acr+) in facilitating the redox conversion as well as charge transfer to Au55 anion NCs. The cluster represents the first fully structure-resolved Schmid-type Au55 species, which features quasi-C2 symmetry with a unique Au2-centered Au27 uncoordinated metal cage. Temperature-dependent absorption spectroscopy discloses countercation effects on electron-phonon interactions within the Au 55 − d on the Bose-Einstein two- component and reveals a substantial suppression of acoustic phonons in Acr·Au55, based on the Bose-Einstein two-oscillator model band-gap renormalization analysis. Systematic studies through fluorescence titration, electron paramagnetic resonance spectroscopy, and femtosecond transient absorption spectroscopy provide strong support for the photoinduced electron transfer from the locally excited singlet state of Acr+ cation to the Au 55 − cluster. This work marks the first observation of the countercation effect on charge transfer in metal NCs and unlocks a new avenue for their functional manipulation.