Cd12Ag32(SePh)36: Non-Noble Metal Doped Silver Nanoclusters.

While there are numerous recent reports on doping of a ligand-protected noble metal nanocluster (e.g., Au and Ag) with another noble metal, non-noble metal (e.g., Cd) doping remains challenging. Here, we design a phosphine-assisted synthetic strategy and synthesize a Cd doped Ag nanocluster, Cd12Ag32(SePh)36 (SePh: selenophenolate), which exhibits characteristic UV-vis absorption features and rare near-infrared (NIR) photoluminescence at ∼1020 nm. The X-ray single crystal structure reveals an asymmetric two-shell Ag4@Ag24 metal kernel protected by four nonplanar Cd3Ag(SePh)9 metal-ligand frameworks. Furthermore, the electronic structure analysis shows that the cluster is a 20-electron "superatom" and density functional theory predicts that its chiral optical response is comparable to the well-known Au38(SR)24 cluster. Our synthetic approach will pave a new path for introducing other non-noble metals into noble metal nanoclusters for exploring their effect on optical and chemical properties.

[1]  C. Tung,et al.  [Ag48(C≡C tBu)20(CrO4)7]: An Atomically Precise Silver Nanocluster Co-protected by Inorganic and Organic Ligands. , 2019, Journal of the American Chemical Society.

[2]  U. Landman,et al.  Chemistry and Structure of Silver Molecular Nanoparticles. , 2018, Accounts of chemical research.

[3]  O. Bakr,et al.  Atomic-Level Doping of Metal Clusters. , 2018, Accounts of chemical research.

[4]  C. Aikens,et al.  Electronic and Geometric Structure, Optical Properties, and Excited State Behavior in Atomically Precise Thiolate-Stabilized Noble Metal Nanoclusters. , 2018, Accounts of chemical research.

[5]  N. Zheng,et al.  Surface Chemistry of Atomically Precise Coinage-Metal Nanoclusters: From Structural Control to Surface Reactivity and Catalysis. , 2018, Accounts of chemical research.

[6]  Qing Tang,et al.  Insights into Interfaces, Stability, Electronic Properties, and Catalytic Activities of Atomically Precise Metal Nanoclusters from First Principles. , 2018, Accounts of chemical research.

[7]  C. Tung,et al.  Deciphering synergetic core-shell transformation from [Mo6O22@Ag44] to [Mo8O28@Ag50] , 2018, Nature Communications.

[8]  Quan‐Ming Wang,et al.  Alkynyl Approach toward the Protection of Metal Nanoclusters. , 2018, Accounts of chemical research.

[9]  Nathaniel L. Rosi,et al.  Total Structure Determination of Au16(S-Adm)12 and Cd1Au14(S tBu)12 and Implications for the Structure of Au15(SR)13. , 2018, Journal of the American Chemical Society.

[10]  N. Sakthivel,et al.  Aromatic Thiolate-Protected Series of Gold Nanomolecules and a Contrary Structural Trend in Size Evolution. , 2018, Accounts of chemical research.

[11]  R. Jin,et al.  Central Doping of a Foreign Atom into the Silver Cluster for Catalytic Conversion of CO2 toward C-C Bond Formation. , 2018, Angewandte Chemie.

[12]  D. Jiang,et al.  Thiolate-Protected Trimetallic Au∼20Ag∼4Pd and Au∼20Ag∼4Pt Alloy Clusters with Controlled Chemical Composition and Metal Positions. , 2018, The journal of physical chemistry letters.

[13]  Pu Wang,et al.  The Fourth Alloying Mode by Way of Anti-Galvanic Reaction. , 2018, Angewandte Chemie.

[14]  Jun-Hao Wang,et al.  Bidentate Phosphine-Assisted Synthesis of an All-Alkynyl-Protected Ag74 Nanocluster. , 2017, Journal of the American Chemical Society.

[15]  T. Pradeep,et al.  Atomically Precise Clusters of Noble Metals: Emerging Link between Atoms and Nanoparticles. , 2017, Chemical reviews.

[16]  Taeghwan Hyeon,et al.  Chemical Synthesis, Doping, and Transformation of Magic-Sized Semiconductor Alloy Nanoclusters. , 2017, Journal of the American Chemical Society.

[17]  U. Landman,et al.  Confirmation of a de novo structure prediction for an atomically precise monolayer-coated silver nanoparticle , 2016, Science Advances.

[18]  N. Zheng,et al.  Asymmetric Synthesis of Chiral Bimetallic [Ag28Cu12(SR)24]4- Nanoclusters via Ion Pairing. , 2016, Journal of the American Chemical Society.

[19]  R. Jin,et al.  Atomically Precise Colloidal Metal Nanoclusters and Nanoparticles: Fundamentals and Opportunities. , 2016, Chemical reviews.

[20]  W. E. van Zyl,et al.  Polyhydrido Copper Clusters: Synthetic Advances, Structural Diversity, and Nanocluster-to-Nanoparticle Conversion. , 2016, Accounts of chemical research.

[21]  Jinlong Yang,et al.  Mono-cadmium vs Mono-mercury Doping of Au25 Nanoclusters. , 2015, Journal of the American Chemical Society.

[22]  R. Whetten,et al.  Reversible Size Control of Silver Nanoclusters via Ligand-Exchange , 2015 .

[23]  J. Xie,et al.  Recent Advances in the Synthesis and Applications of Ultrasmall Bimetallic Nanoclusters , 2015 .

[24]  P. Li,et al.  Metal exchange method using Au25 nanoclusters as templates for alloy nanoclusters with atomic precision. , 2015, Journal of the American Chemical Society.

[25]  H. Häkkinen,et al.  Ag44(SeR)30: A Hollow Cage Silver Cluster with Selenolate Protection. , 2013, The journal of physical chemistry letters.

[26]  T. Bürgi,et al.  First enantioseparation and circular dichroism spectra of Au38 clusters protected by achiral ligands , 2012, Nature Communications.

[27]  O. Lopez-Acevedo,et al.  Chirality and electronic structure of the thiolate-protected Au38 nanocluster. , 2010, Journal of the American Chemical Society.

[28]  R. Whetten,et al.  A unified view of ligand-protected gold clusters as superatom complexes , 2008, Proceedings of the National Academy of Sciences.

[29]  Pablo D. Jadzinsky,et al.  Structure of a Thiol Monolayer-Protected Gold Nanoparticle at 1.1 Å Resolution , 2007, Science.

[30]  Y. Negishi,et al.  Biicosahedral Gold Clusters [Au25(PPh3)10(SCnH2n+1)5Cl2]2+ (n = 2−18): A Stepping Stone to Cluster-Assembled Materials , 2007 .