0000000001304321
AUTHOR
Megalamane S. Bootharaju
[Cu32(PET)24H8Cl2](PPh4)2: A Copper Hydride Nanocluster with a Bisquare Antiprismatic Core
Atomically precise coinage metal (Au, Ag and Cu) nanoclusters (NCs) have been the subject of immense interest for their intriguing structural, photophysical and catalytic properties. However, the synthesis of Cu NCs is highly challenging because of low reduction potential and high reactivity of copper, demonstrating the need for new synthetic methods using appropriate ligand combinations. By designing a diamine-assisted synthetic strategy, here we report the synthesis and total structure characterization of a box-like dianionic Cu NC, [Cu32(PET)24H8Cl2](PPh4)2 co-protected by 2-phenylethanethiolate (PET), hydride and chloride ligands. Its crystal structure comprises a rare bisquare antipris…
Ag44(EBT)26(TPP)4Nanoclusters With Tailored Molecular and Electronic Structure
Although atomically precise metalloid nanoclusters (NCs) of identical size with distinctly different molecular structures are highly desirable to understand the structural effects on the optical and photophysical properties, their synthesis remains highly challenging. Herein, we employed phosphine and thiol capping ligands featuring appropriate steric effects and synthesized a charge-neutral Ag NC with the formula Ag44 (EBT)26 (TPP)4 (EBT: 2-ethylbenzenethiolate; TPP: triphenylphosphine). The single-crystal X-ray structure reveals that this NC has a hollow metal core of Ag12 @Ag20 and a metal-ligand shell of Ag12 (EBT)26 (TPP)4 . The presence of mixed ligands and long V-shaped metal-ligand …
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 “supe…
Ag44(EBT)26(TPP)4 Nanoclusters with Tailored Molecular and Electronic Structure
Although atomically precise metalloid nanoclusters (NCs) of identical size with distinctly different molecular structures are highly desirable to understand the structural effects on the intriguing optical and photophysical properties, their synthesis remains highly challenging. Herein, we employed phosphine and thiol capping ligands featuring appropriate steric effects and synthesized a charge‐neutral Ag NC with the formula, Ag 44 (EBT) 26 (TPP) 4 (EBT: 2‐ethylbenzenethiolate; TPP: triphenylphosphine). The single‐crystal X‐ray structure reveals that this NC has a hollow metal core of Ag 12 @Ag 20 and a metal‐ligand shell of Ag 12 (EBT) 26 (TPP) 4 . The presence of mixed ligands and long V‐…
Alkynyl‐Protected Chiral Bimetallic Ag22Cu7 Superatom with Multiple Chirality Origins
Understanding the origin of chirality in the nanostructured materials is essential for chiroptical and catalytic applications. Here we report a chiral AgCu superatomic cluster, [Ag22Cu7(C≡CR)16(PPh3)5Cl6](PPh4), Ag22Cu7, protected by an achiral alkynyl ligand (HC≡CR: 3,5-bis(trifluoromethyl)phenylacetylene). Its crystal structure comprises a rare interpenetrating biicosahedral Ag17Cu2 core, which is stabilized by four different types of motifs: one Cu(C≡CR)2, four -C≡CR, two chlorides and one helical Ag5Cu4(C≡CR)10(PPh3)5Cl4. Structural analysis reveals that Ag22Cu7 exhibits multiple chirality origins, including the metal core, the metal-ligand interface and the ligand layer. Furthermore, t…
[Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster
Engineering the surface ligands of metal nanoparticles is critical in designing unique arrangements of metal atoms. Here, we report the synthesis and total structure determination of a large box-shaped Ag67 nanocluster (NC) protected by a mixed shell of thiolate (2,4-dimethylbenzenethiolate, SPhMe2) and phosphine (triphenylphosphine, PPh3) ligands. Single crystal X-ray diffraction (SCXRD) and electrospray ionization mass spectrometry (ESI-MS) revealed the cluster formula to be [Ag67(SPhMe2)32(PPh3)8]3+. The crystal structure shows an Ag23 metal core covered by a layer of Ag44S32P8 arranged in the shape of a box. The Ag23 core was formed through an unprecedented centered cuboctahedron, i.e.,…
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 “supe…
[Cu32(PET)24H8Cl2](PPh4)2: A Copper Hydride Nanocluster with a Bisquare Antiprismatic Core
Atomically precise coinage metal (Au, Ag, and Cu) nanoclusters (NCs) have been the subject of immense interest for their intriguing structural, photophysical, and catalytic properties. However, the synthesis of Cu NCs is highly challenging because of low reduction potential and high reactivity of copper, demonstrating the need for new synthetic methods using appropriate ligand combinations. By designing a diamine-assisted synthetic strategy, here we report the synthesis and total structure characterization of a box-like dianionic Cu NC [Cu32(PET)24H8Cl2](PPh4)2 coprotected by 2-phenylethanethiolate (PET), hydride, and chloride ligands. Its crystal structure comprises a rare bisquare antipri…
[Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster
Engineering the surface ligands of metal nanoparticles is critical in designing unique arrangements of metal atoms. Here, we report the synthesis and total structure determination of a large box-shaped Ag67 nanocluster (NC) protected by a mixed shell of thiolate (2,4-dimethylbenzenethiolate, SPhMe2) and phosphine (triphenylphosphine, PPh3) ligands. Single crystal X-ray diffraction (SCXRD) and electrospray ionization mass spectrometry (ESI-MS) revealed the cluster formula to be [Ag67(SPhMe2)32(PPh3)8]3+. The crystal structure shows an Ag23 metal core covered by a layer of Ag44S32P8 arranged in the shape of a box. The Ag23 core was formed through an unprecedented centered cuboctahedron, i.e.,…
Ag11(SG)7 : A New Cluster Identified by Mass Spectrometry and Optical Spectroscopy
We report a one-step and high yield synthesis of a red-luminescent silver cluster with the molecular formula, Ag11(SG)7 (SG: glutathionate) via reduction of silver ions by sodium borohydride in the presence of the tripeptide, glutathione (GSH). The as-prepared cluster shows prominent absorption features at 485 and 625 nm in its UV-vis absorption spectrum. Aging of the as-prepared cluster solution led to the disappearance of the 625 nm peak, followed by broadening of the 485 nm peak to give three maxima at ?487, 437, and 393 nm in its absorption spectrum. These peaks remain unchanged even after polyacrylamide gel electrophoresis (PAGE), where a single band was observed confirming high purity…
[Pt2Cu34(PET)22Cl4]2–: An Atomically Precise, 10-Electron PtCu Bimetal Nanocluster with a Direct Pt–Pt Bond
Heteroatom-doped metal nanoclusters (NCs) are highly desirable to gain fundamental insights into the effect of doping on the electronic structure and catalytic properties. Unfortunately, their controlled synthesis is highly challenging when the metal atomic sizes are largely different (e.g., Cu and Pt). Here, we design a metal-exchange strategy that enables simultaneous doping and resizing of NCs. Specifically, [Pt2Cu34(PET)22Cl4]2- NC, the first example of a Pt-doped Cu NC, is synthesized by utilizing the unique reactivity of [Cu32(PET)24Cl2H8]2- NC with Pt4+ ions. The single-crystal X-ray structure reveals that two directly bonded Pt atoms occupy the two centers of an unusually interpenet…
CCDC 1521591: Experimental Crystal Structure Determination
Related Article: Mohammad J. Alhilaly, Megalamane S. Bootharaju, Chakra P. Joshi, Tabot M. Besong, Abdul-Hamid Emwas, Rosalba Juarez-Mosqueda, Sami Kaappa, Sami Malola, Karim Adil, Aleksander Shkurenko, Hannu Häkkinen, Mohamed Eddaoudi, and Osman M. Bakr|2016|J.Am.Chem.Soc.|138|14727|doi:10.1021/jacs.6b09007
CCDC 1918141: Experimental Crystal Structure Determination
Related Article: Megalamane S. Bootharaju, Hogeun Chang, Guocheng Deng, Sami Malola, Woonhyuk Baek, Hannu Häkkinen, Nanfeng Zheng, Taeghwan Hyeon|2019|J.Am.Chem.Soc.|141|8422|doi:10.1021/jacs.9b03257
CCDC 2021376: Experimental Crystal Structure Determination
Related Article: Sanghwa Lee, Megalamane S. Bootharaju, Guocheng Deng, Sami Malola, Woonhyuk Baek, Hannu Häkkinen, Nanfeng Zheng, Taeghwan Hyeon|2020|J.Am.Chem.Soc.|142|13974|doi:10.1021/jacs.0c06577
CCDC 2071611: Experimental Crystal Structure Determination
Related Article: Sanghwa Lee, Megalamane S. Bootharaju, Guocheng Deng, Sami Malola, Hannu Häkkinen, Nanfeng Zheng, Taeghwan Hyeon|2021|J.Am.Chem.Soc.|143|12100|doi:10.1021/jacs.1c04002
CCDC 2032634: Experimental Crystal Structure Determination
Related Article: Megalamane S. Bootharaju, Sanghwa Lee, Guocheng Deng, Sami Malola, Woonhyuk Baek, Hannu H��kkinen, Nanfeng Zheng, Taeghwan Hyeon|2021|Angew.Chem.,Int.Ed.|60|9038|doi:10.1002/anie.202015907