Megalamane S. Bootharaju 교수

Synthesis of atom-precise alloy nanoclusters with uniform composition is challenging when the alloying atoms are similar in size (for example, Ag and Au). A galvanic exchange strategy has been devised to produce a compositionally uniform [Ag24Au(SR)18](-) cluster (SR: thiolate) using a pure [Ag25(SR)18](-) cluster as a template. Conversely, the direct synthesis of Ag24Au cluster leads to a mixture of [Ag(25-x)Au(x)(SR)18](-), x=1-8. Mass spectrometry and crystallography of [Ag24Au(SR)18](-) reve

The properties of atomically monodisperse noble metal nanoclusters (NCs) are intricately intertwined with their precise molecular formula. The vast majority of size-specific NC syntheses start from the reduction of the metal salt and thiol ligand mixture. Only in gold was it recently shown that ligand-exchange could induce the growth of NCs from one atomically precise species to another, a process of yet unknown reversibility. Here, we present a process for the ligand-exchange-induced growth of

Thiols and phosphines are the most widely used organic ligands to attain atomically precise metal nanoclusters (NCs). Here, we used simple hydrides (e.g., H^-) as ligands along with phosphines, such as triphenylphosphine (TPP), 1,2-bis(diphenylphosphino)ethane [DPPE], and tris(4-fluorophenyl)phosphine [TFPP] to design and synthesize a new class of hydride-rich silver NCs. This class includes [Ag₁₈H₁₆(TPP)₁₀]²⁺, [Ag₂₅H₂₂(

Atomically precise self-assembled architectures of noble metals with unique surface structures are necessary for prospective applications. However, the synthesis of such structures based on silver is challenging because of their instability. In this work, by developing a selective and controlled doping strategy, we synthesized and characterized a rod-shaped, charge-neutral, diplatinum-doped Ag nanocluster (NC) of [Pt₂Ag₂₃Cl₇(PPh₃)₁₀]. Its cr

Abstract Synthesis of atom‐precise alloy nanoclusters with uniform composition is challenging when the alloying atoms are similar in size (for example, Ag and Au). A galvanic exchange strategy has been devised to produce a compositionally uniform [Ag 24 Au(SR) 18 ] − cluster (SR: thiolate) using a pure [Ag 25 (SR) 18 ] − cluster as a template. Conversely, the direct synthesis of Ag 24 Au cluster leads to a mixture of [Ag 25− x Au x (SR) 18 ] − , x =1–8. Mass spectrometry and crystallography of [

Modulating the structure–property relationship in atomically precise nanoclusters (NCs) is vital for developing novel NC materials and advancing their applications. While promising biphasic ligand-exchange (LE) strategies have been developed primarily to attain novel NCs, understanding the mechanistic aspects involved in tuning the core and the ligand-shell of NCs in such biphasic processes is challenging. Here, we design a single phase LE process that enabled us to elucidate the mechanism of ho

Atomically precise metal nanoclusters (NCs) containing more than one type of metal atom (i.e., doped or alloyed), due to synergistic effects, open new avenues for engineering the catalytic and optical properties of NCs in a manner that homometal NCs cannot. Unfortunately, it is still a major challenge to controllably introduce multimetallic dopants in NCs, understanding the dopants' positions, mechanism, and synergistic effects. To overcome these challenges, we designed a metal-exchange approach

The lack of structurally distinct nanoclusters (NCs) of identical size and composition prevented the mechanistic understanding of their structural effects on ion pairing and concomitant optical properties. To produce such highly sought NCs, we designed a new monothiolate-for-dithiolate exchange strategy that enabled the selective transformation of the structure of a NC without affecting its metal atomicity or composition. Through this method, a bimetallic [PtAg28(BDT)12(PPh3)4]4– NC (1) was succ

Heteroatom doping of atomically precise nanoclusters (NCs) often yields a mixture of doped and undoped products of single-atom difference, whose separation is extremely difficult. To overcome this challenge, novel synthesis methods are required to offer monodisperse doped NCs. For instance, the direct synthesis of PtAg₂₈ NCs produces a mixture of [Ag₂₉(BDT)₁₂(TPP)₄]^3- and [PtAg₂₈(BDT)₁₂(TPP)₄]^4- NC

The catalytic activity and product selectivity of the electrochemical CO₂ reduction reaction (eCO₂RR) depend strongly on the local microenvironment of mass diffusion at the nanostructured catalyst and electrolyte interface. Achieving a molecular-level understanding of the electrocatalytic reaction requires the development of tunable metal-ligand interfacial structures with atomic precision, which is highly challenging. Here, the synthesis and molecular structure of a 25-ato

While core-shell nanomaterials are highly desirable for realizing enhanced optical and catalytic properties, their synthesis with atomic-level control is challenging. Here, the synthesis and crystal structure of [Au₁₂ Ag₃₂ (SePh)₃₀ ]^4- , the first example of selenolated Au-Ag core-shell nanoclusters, comprising a gold icosahedron core trapped in a silver dodecahedron, which is protected by an Ag₁₂ (SePh)₃₀ shell, is presented. The

Understanding the origin of chirality in the nanostructured materials is essential for chiroptical and catalytic applications. Here we report a chiral AgCu superatomic cluster, [Ag₂₂ Cu₇ (C≡CR)₁₆ (PPh₃ )₅ Cl₆ ](PPh₄ ), Ag₂₂ Cu₇ , protected by an achiral alkynyl ligand (HC≡CR: 3,5-bis(trifluoromethyl)phenylacetylene). Its crystal structure comprises a rare interpenetrating biicosahedral Ag<sub>17</s

ConspectusAtomically precise metal chalcogenide clusters (MCCs) are model molecular compounds of scientifically and technologically important semiconductor nanocrystals, which are known as quantum dots (QDs). The significantly high ambient stability of MCCs of particular sizes, as compared to that of slightly smaller or larger sizes, made them be termed "magic-sized clusters" (MSCs). In other words, MSCs with specific sizes between sizes of precursors (typically, metal-ligand complexes) and nano

Achieving atomic precision in nanostructured materials is essential for comprehending formation mechanisms and elucidating structure-property relationships. Within the realm of nanoscience and technology, atomically precise ligand-protected noble metal nanoclusters (NCs) have emerged as a rapidly expanding area of interest. These clusters manifest quantum confinement-induced optoelectronic, photophysical, and chemical properties, along with remarkable catalytic capabilities. Among coinage metals