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1. Isomerization-induced enhancement of luminescence in Au ₂₈ (SR) ₂₀ nanoclusters

   https://doi.org/10.1039/d0sc01270j  

   Chen, Yuxiang; Zhou, Meng; Li, Qi; Gronlund, Harrison; Jin, Rongchao (August 2020, Chemical Science)

   null (Ed.)

   Understanding the origin and structural basis of the photoluminescence (PL) phenomenon in thiolate-protected metal nanoclusters is of paramount importance for both fundamental science and practical applications. It remains a major challenge to correlate the PL properties with the atomic-level structure due to the complex interplay of the metal core ( i.e. the inner kernel) and the exterior shell ( i.e. surface Au( i )-thiolate staple motifs). Decoupling these two intertwined structural factors is critical in order to understand the PL origin. Herein, we utilize two Au 28 (SR) 20 nanoclusters with different –R groups, which possess the same core but different shell structures and thus provide an ideal system for the PL study. We discover that the Au 28 (CHT) 20 (CHT: cyclohexanethiolate) nanocluster exhibits a more than 15-fold higher PL quantum yield than the Au 28 (TBBT) 20 nanocluster (TBBT: p-tert -butylbenzenethiolate). Such an enhancement is found to originate from the different structural arrangement of the staple motifs in the shell, which modifies the electron relaxation dynamics in the inner core to different extents for the two nanoclusters. The emergence of a long PL lifetime component in the more emissive Au 28 (CHT) 20 nanocluster reveals that its PL is enhanced by suppressing the nonradiative pathway. The presence of long, interlocked staple motifs is further identified as a key structural parameter that favors the luminescence. Overall, this work offers structural insights into the PL origin in Au 28 (SR) 20 nanoclusters and provides some guidelines for designing luminescent metal nanoclusters for sensing and optoelectronic applications. 

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2. 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)

   null (Ed.)
3. Coherent Vibrational Dynamics of Au ₁₄₄ (SC ₈ H ₉ ) ₆₀ Nanoclusters

   https://doi.org/10.1021/acs.jpclett.3c01477  

   Jeffries, William R.; Malola, Sami; Tofanelli, Marcus A.; Ackerson, Christopher J.; Häkkinen, Hannu; Knappenberger, Kenneth L. (July 2023, The Journal of Physical Chemistry Letters)
4. Heterometal-Doped M ₂₃ (M = Au/Ag/Cd) Nanoclusters with Large Dipole Moments

   https://doi.org/10.1021/acsnano.0c01000  

   Li, Yingwei; Cowan, Michael J.; Zhou, Meng; Taylor, Michael G.; Wang, He; Song, Yongbo; Mpourmpakis, Giannis; Jin, Rongchao (June 2020, ACS Nano)
5. Dissecting Critical Factors for Electrochemical CO ₂ Reduction on Atomically Precise Au Nanoclusters

   https://doi.org/10.1002/anie.202211771  

   Li, Site; Nagarajan, Anantha Venkataraman; Du, Xiangsha; Li, Yingwei; Liu, Zhongyu; Kauffman, Douglas R.; Mpourmpakis, Giannis; Jin, Rongchao (October 2022, Angewandte Chemie International Edition)

   Abstract This work investigates the critical factors impacting electrochemical CO₂reduction reaction (CO₂RR) using atomically precise Au nanoclusters (NCs) as electrocatalysts. First, the influence of size on CO₂RR is studied by precisely controlling NC size in the 1–2.5 nm regime. We find that the electrocatalytic CO partial current density increases for smaller NCs, but the CO Faradaic efficiency (FE) is not directly associated with the NC size. This indicates that the surface‐to‐volume ratio, i.e. the population of active sites, is the dominant factor for determining the catalytic activity, but the selectivity is not directly impacted by size. Second, we compare the CO₂RR performance of Au₃₈isomers (Au₃₈Q and Au₃₈T) to reveal that structural rearrangement of identical size NCs can lead to significant changes in both CO₂RR activity and selectivity. Au₃₈Q shows higher activity and selectivity towards CO than Au₃₈T, and density functional theory (DFT) calculations reveal that the average formation energy of the key *COOH intermediate on the proposed active sites is significantly lower on Au₃₈Q than Au₃₈T. These results demonstrate how the structural isomerism can impact stabilization of reaction intermediates as well as the overall CO₂RR performance of identical size Au NCs. Overall, this work provides important structure–property relationships for tailoring the NCs for CO₂RR. 

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