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1. NHC-Stabilized Au ₁₀ Nanoclusters and Their Conversion to Au ₂₅ Nanoclusters

   https://doi.org/10.1021/jacsau.2c00004  

   Lummis, Paul A.; Osten, Kimberly M.; Levchenko, Tetyana I.; Sabooni Asre Hazer, Maryam; Malola, Sami; Owens-Baird, Bryan; Veinot, Alex J.; Albright, Emily L.; Schatte, Gabriele; Takano, Shinjiro; et al (April 2022, JACS Au)
2. A topological isomer of the Au ₂₅ (SR) ₁₈ ⁻ nanocluster

   https://doi.org/10.1039/D0CC03334K  

   Matus, María Francisca; Malola, Sami; Kinder Bonilla, Emily; Barngrover, Brian M.; Aikens, Christine M.; Häkkinen, Hannu (July 2020, Chemical Communications)

   null (Ed.)

   Energetically low-lying structural isomers of the much-studied thiolate-protected gold cluster Au 25 (SR) 18 − are discovered from extensive (80 ns) molecular dynamics (MD) simulations using the reactive molecular force field ReaxFF and confirmed by density functional theory (DFT). A particularly interesting isomer is found, which is topologically connected to the known crystal structure by a low-barrier collective rotation of the icosahedral Au 13 core. The isomerization takes place without breaking of any Au–S bonds. The predicted isomer is essentially iso-energetic with the known Au 25 (SR) 18 − structure, but has a distinctly different optical spectrum. It has a significantly larger collision cross-section as compared to that of the known structure, which suggests it could be detectable in gas phase ion-mobility mass spectrometry. 

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3. Observation of Core Phonon in Electron–Phonon Coupling in Au ₂₅ Nanoclusters

   https://doi.org/10.1021/acs.jpclett.1c00050  

   Liu, Zhongyu; Li, Yingwei; Shin, Wonyong; Jin, Rongchao (February 2021, The Journal of Physical Chemistry Letters)

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4. Elucidating the active sites for CO ₂ electroreduction on ligand-protected Au ₂₅ nanoclusters

   https://doi.org/10.1039/c8cy01099d  

   Austin, Natalie; Zhao, Shuo; McKone, James R.; Jin, Rongchao; Mpourmpakis, Giannis (January 2018, Catalysis Science & Technology)

   Using density functional theory (DFT) calculations, we investigated the electrochemical reduction of CO 2 and the competing H 2 evolution reaction on ligand-protected Au 25 nanoclusters (NCs) of different charge states, Au 25 (SR) 18 q ( q = −1, 0, +1). Our results showed that regardless of charge state, CO 2 electroreduction over Au 25 (SR) 18 q NCs was not feasible because of the extreme endothermicity to stabilize the carboxyl (COOH) intermediate. When we accounted for the removal of a ligand (both –SR and –R) from Au 25 (SR) 18 q under electrochemical conditions, surprisingly we found that this is a thermodynamically feasible process at the experimentally applied potentials with the generated surface sites becoming active centers for electrocatalysis. In every case, the negatively charged NCs, losing a ligand from their surface during electrochemical conditions, were found to significantly stabilize the COOH intermediate, resulting in dramatically enhanced CO 2 reduction. The generated sites for CO 2 reduction were also found to be active for H 2 evolution, which agrees with experimental observations that these two processes compete. Interestingly, we found that the removal of an –R ligand from the negatively charged NC, resulted in a catalyst that was both active and selective for CO 2 reduction. This work highlights the importance of both the overall charge state and generation of catalytically active surface sites on ligand-protected NCs, while elucidating the CO 2 electroreduction mechanisms. Overall, our work rationalizes a series of experimental observations and demonstrates pathways to convert a very stable and catalytically inactive NC to an active electrocatalyst. 

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5. The Influence of Passivating Ligand Identity on Au ₂₅ (SR) ₁₈ Spin-Polarized Emission

   https://doi.org/10.1021/acs.jpclett.5c00723  

   Smith, Nathanael L; Herbert, Patrick J; Tofanelli, Marcus A; Knappenberger, Jane A; Ackerson, Christopher J; Knappenberger, Kenneth L (May 2025, The Journal of Physical Chemistry Letters)