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Chiral metal nanoclusters have recently been attracting great attention. It is challenging to realize asymmetric catalysis via atomically precise metal nanoclusters. Herein, we report the synthesis and total structure determination of chiral clusters [AuAg(dppf)(l-/d-proline)](BF) (-/d-Au). Superatomic clusters l-/d-Au display intense and mirror-image Cotton effects in their CD spectra. Density functional theory (DFT) calculations were carried out to understand the correlation between electronic structures and the optical activity of the enantiomeric pair. Surprisingly, the incorporation of proline in a metal nanocluster can significantly promote the catalytic efficiency in asymmetric Aldol reactions. The increase of catalytic activity of in comparison with organocatalysis by proline is attributed to the cooperative effect of the metal core and prolines, showing the advantages of the integration of metal catalysis and organocatalysis in a metal nanocluster.
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http://dx.doi.org/10.1021/jacs.3c02567 | DOI Listing |
Chem Soc Rev
September 2025
State Key Laboratory of Crystal Materials, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China.
Understanding the excited-state dynamics of atomically precise coinage metal nanoclusters (CMNCs) is pivotal for elucidating their photoluminescence (PL) mechanisms and rationally tuning emission properties-particularly in the near-infrared (NIR) region, where CMNC-based nanomaterials have tremendous potential for biomedical and optoelectronic applications. This review presents a systematic and comprehensive account of recent advances in investigating the excited-state dynamics and PL mechanisms of NIR-emitting CMNCs with atomic precision, leveraging the synergistic integration of time-resolved spectroscopy and time-dependent density functional theory (TD-DFT) calculations. Distinct from previous reviews that offer a broad survey of CMNC properties, the present review focuses specifically on intrinsic factors, highlighting molecular vibrational features and electronic structure modulation as key determinants of NIR emission.
View Article and Find Full Text PDFJ Chem Theory Comput
September 2025
Department of Physics, Nanoscience Center, University of Jyväskylä, Jyväskylä FI 40014, Finland.
-Heterocyclic carbene (NHC)-protected gold nanoclusters (AuNCs) have emerged as promising candidates for biomedical applications due to their high stability and strong photoluminescence. However, their integration into atomistic molecular dynamics (MD) simulations, which facilitates an understanding of their behavior in biological environments, has been hindered by the lack of reliable force field parameters. Here, we present a new set of parameters for classical MD simulations of NHC-protected AuNCs, fully compatible with the AMBER force field.
View Article and Find Full Text PDFTop Curr Chem (Cham)
September 2025
Center for Advanced Materials Research, Research Institute of Sciences and Engineering, University of Sharjah, 27272, Sharjah, United Arab Emirates.
Controlling the size of gold nanoparticles (AuNPs) has been critical in diagnostics, biomolecular sensing, targeted therapy, wastewater treatment, catalysis, and sensing applications. Ultrasmall AuNPs (uAuNPs), with sizes Ranging from 2 to 5 nm, and gold nanoclusters (AuNCs), with sizes less than 2 nm, are often dealt with interchangeably in the literature, making it challenging to review them separately. Although they are grouped in our discussion, their chemical and physical properties differ significantly, partly due to their electronic properties.
View Article and Find Full Text PDFACS Appl Mater Interfaces
September 2025
School of Biomedical Engineering, Shenzhen Key Laboratory for Nano-Biosensing Technology, Guangdong Key Laboratory of Biomedical Measurements and Ultrasound Imaging, Marshall Laboratory of Biomedical Engineering, Shenzhen University Medical School, Shenzhen University, Shenzhen 518060, China.
Electrochemiluminescence (ECL) is rapidly emerging as an excellent electrochemical analytical technique for the specific and sensitive detection of various biomarkers and hazardous trace metals. Among ECL emitters, gold nanoclusters (AuNCs) have proven to be excellent luminophores due to their remarkable luminescent properties, stability, and biocompatibility. However, the low ECL efficiency of AuNCs precludes their application in ultrasensitive biosensing.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
Institutes of Physical Science and Information Technology, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Anhui University, Hefei 230601, P. R. China.
Organic ligand-protected metal nanoclusters feature ultrasmall size, well-defined compositions, and diverse chiral structures. They have the potential to combine the advantages of asymmetric organocatalysis and nanometal catalysis. The major challenge is designing and synthesizing appropriate metal nanocluster structures for achieving high catalytic activity and excellent enantioselectivity.
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