Understanding the synergistic effect between ligands at the atomic level to control the catalytic selectivity of catalysts remains a significant challenge due to the complexity of ligand interactions and limitations i...Understanding the synergistic effect between ligands at the atomic level to control the catalytic selectivity of catalysts remains a significant challenge due to the complexity of ligand interactions and limitations in current analytical techniques.Herein,using precisely structured metal nanoclusters as models,we discovered that altering the electronegativity of substituents on donor thiolate ligands can modulate the bond dissociation energy of coordinated phosphine ligands on the clusters.This change leads to the selective dissociation of ligands during the catalytic process,thereby enabling control over catalytic selectivity with an abrupt increase in formate production from~0%to 23%.This work provides crucial insights into understanding ligand interactions on metal nanoparticle surfaces at the atomic level and lays the foundation for designing highly selective catalysts in the future.展开更多
Atomically precise metal nanoclusters(MNCs)have emerged as tailorable luminescent materials with visible to near-infrared emission modulated by core(kernel)size,metal composition,and ligand engineering.These ultrasmal...Atomically precise metal nanoclusters(MNCs)have emerged as tailorable luminescent materials with visible to near-infrared emission modulated by core(kernel)size,metal composition,and ligand engineering.These ultrasmall clusters exhibit discrete quantum-confined electronic states with strong spin-orbit coupling(SOC),enabling diverse emission pathways.Current research focuses on elucidating emission mechanisms and developing strategies to enhance fluorescence quantum yields.In this review,we emphasize structure-photoluminescence(PL)correlations and the underlying excited-state origins of luminescence:(i)coinage-metal clusters display multiple emissive channels-including prompt fluorescence,room-temperature phosphorescence,and TADF;(ii)the electronic gap and thus emission energy is directly governed by core size and metal identity,with core shrinkage and enhanced SOC generally inducing red-shifts;and(iii)ligand shell properties(identity/rigidity/packing)control charge-transfer pathways and nonradiative decay,while heterometal doping or rigidification modulates state ordering to brighten emission without necessarily shifting band positions.Importantly,many clusters exhibit dual-emission behavior.We propose a coupled core-shell emissive-state model in which one band originates from metal-core excitation and the other from a ligand-or motif-centered charge-transfer state.Finally,we outline future challenges:dissecting core versus shell contributions to PL and boosting quantum efficiency through targeted control of cluster composition and ligand shell.Progress on these fronts is crucial for the rational design of next-generation cluster emitters.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.22301155,22171156,21803001)Taishan Scholar Foundation of Shandong Province(China)+2 种基金the Natural Science Foundation of Shandong Province(No.ZR2023QB122)Shandong Province Excellent Youth Innovation TeamStartup Funds from Qingdao University of Science and Technology
文摘Understanding the synergistic effect between ligands at the atomic level to control the catalytic selectivity of catalysts remains a significant challenge due to the complexity of ligand interactions and limitations in current analytical techniques.Herein,using precisely structured metal nanoclusters as models,we discovered that altering the electronegativity of substituents on donor thiolate ligands can modulate the bond dissociation energy of coordinated phosphine ligands on the clusters.This change leads to the selective dissociation of ligands during the catalytic process,thereby enabling control over catalytic selectivity with an abrupt increase in formate production from~0%to 23%.This work provides crucial insights into understanding ligand interactions on metal nanoparticle surfaces at the atomic level and lays the foundation for designing highly selective catalysts in the future.
基金the financial support provided by the National Natural Science Foundation of China(22571175,22171156,and 21803001)Scientific Research Innovation Capability Support Project for Young Fac-ulty(SRICSPYF-BS2025055)+1 种基金Taishan Scholar Foundation of Shandong Province(China)Shandong Province Excellent Youth Innovation Team and Startup Funds from Qingdao University of Science and Technology.
文摘Atomically precise metal nanoclusters(MNCs)have emerged as tailorable luminescent materials with visible to near-infrared emission modulated by core(kernel)size,metal composition,and ligand engineering.These ultrasmall clusters exhibit discrete quantum-confined electronic states with strong spin-orbit coupling(SOC),enabling diverse emission pathways.Current research focuses on elucidating emission mechanisms and developing strategies to enhance fluorescence quantum yields.In this review,we emphasize structure-photoluminescence(PL)correlations and the underlying excited-state origins of luminescence:(i)coinage-metal clusters display multiple emissive channels-including prompt fluorescence,room-temperature phosphorescence,and TADF;(ii)the electronic gap and thus emission energy is directly governed by core size and metal identity,with core shrinkage and enhanced SOC generally inducing red-shifts;and(iii)ligand shell properties(identity/rigidity/packing)control charge-transfer pathways and nonradiative decay,while heterometal doping or rigidification modulates state ordering to brighten emission without necessarily shifting band positions.Importantly,many clusters exhibit dual-emission behavior.We propose a coupled core-shell emissive-state model in which one band originates from metal-core excitation and the other from a ligand-or motif-centered charge-transfer state.Finally,we outline future challenges:dissecting core versus shell contributions to PL and boosting quantum efficiency through targeted control of cluster composition and ligand shell.Progress on these fronts is crucial for the rational design of next-generation cluster emitters.
