Probing packing rules The crystals of a well-defined ligand-covered gold nanoparticle can reveal how into lattice happens. Zeng et al. synthesized nanoparticles with 246-atom core surrounded by 80 4-methylbenzenethiol ligands. These nearly spherical did not pack cubic arrangement but instead formed lower-symmetry monoclinic structure. A hierarchy interparticle ligand interactions controlled the packing, including sets chiral arrangements that reversed between layers. Science , this issue p. 1580

Structural ordering is widely present in molecules and materials. However, the organization of on curved surface nanoparticles still least understood owing to major limitations current characterization tools. By merits x-ray crystallography, we reveal structural at all scales a super robust 133-gold atom nanoparticle protected by 52 thiolate ligands, which manifested self-assembled hierarchical patterns starting from metal core interfacial -S-Au-S- ladder-like helical "stripes" further...

Understanding how gold nanoclusters nucleate from Au(I)SR complexes necessitates the structural elucidation of with decreasing size. Toward this effort, we herein report crystal structure an ultrasmall nanocluster formulated as Au20(TBBT)16 (TBBT = SPh-t-Bu). The features a vertex-sharing bitetrahedral Au7 kernel and unprecedented "ring" motif-Au8(SR)8. This large ring protects through strong Auring-Aukernel bonding but does not involve S-Aukernel bonding, in contrast to common "staple"...

Revealing the size-dependent periodicities (including formula, growth pattern, and property evolution) is an important task in metal nanocluster research. However, investigation on this major issue has been complicated, as size change often accompanied by a structural change. Herein, with successful determination of Au44(TBBT)28 structure, where TBBT = 4-tert-butylbenzenethiolate, missing family Au28(TBBT)20, Au36(TBBT)24, Au52(TBBT)32 nanoclusters filled, neat "magic series" unified formula...

Understanding the isomerism phenomenon at nanoscale is a challenging task because of prerequisites precise composition and structural information on nanoparticles. Herein, we report ligand-induced, thermally reversible isomerization between two thiolate-protected 28-gold-atom nanoclusters, i.e. Au28(S-c-C6H11)20 (where -c-C6H11 = cyclohexyl) Au28(SPh-(t)Bu)20 -Ph-(t)Bu 4-tert-butylphenyl). The intriguing ligand effect in dictating stability Au28(SR)20 structures further investigated via...

Abstract The evolution from the metallic (or plasmonic) to molecular state in metal nanoparticles constitutes a central question nanoscience research because of its importance revealing origin bonding and offering fundamental insights into birth surface plasmon resonance. Previous has not been able probe transition due unavailability atomically precise 1–3 nm size regime. Herein, we investigate by performing ultrafast spectroscopic studies on thiolate-protected Au 25 , 38 144 333 ∼520 ∼940...

Atomic packing controls exciton lifetime Like semiconductors, small metallic clusters can absorb light and create excitons (electron-hole pairs). In ligand-capped gold of 30 to 40 atoms (Au Au ) that adopt the usual face-centered cubic packing, these is ∼100 nanoseconds. Zhou et al. found atomic molecular orbital overlap greatly affect carrier lifetimes. Despite having similar bandgaps those clusters, a hexagonal close-packed cluster had much shorter (∼1 nanosecond), body-centered 38 ∼5...

We report the structure determination of a large gold nanocluster formulated as Au130(p-MBT)50, where p-MBT is 4-methylbenzenethiolate. The constructed in four-shell manner, with 55 atoms assembled into two-shell Ino decahedron. surface protected exclusively by -S-Au-S- staple motifs, which self-organize five ripple-like stripes on barrel-shaped Au105 kernel. Au130(p-MBT)50 can be viewed an elongated version Au102(SR)44. Comparison recently discovered icosahedral Au133(p-TBBT)52 (where...

Structures of gold clusters resemble the benzene and DNA molecules reveal a “supermolecule” origin magic-sized clusters.

Controlling nanoparticles with atomic precision has long been a major dream of nanochemists. This first realized in the case gold nanoparticles. We previously discussed size-focusing methodology for syntheses atomically precise nanoclusters protected by thiolate ligands (referred to as Aun(SR)m, where n and m represent exact numbers atoms surface ligands). led molecularly pure such Au25(SR)18, Au38(SR)24, Au144(SR)60, many others recent work. In this Perspective article, we shall further...

Abstract We report the X‐ray structure of a gold nanocluster with 30 atoms protected by 18 1‐adamantanethiolate ligands (formulated as Au (S‐Adm) ). This exhibits threefold rotationally symmetrical, hexagonal‐close‐packed (HCP) kernel six dimeric 2 (SR) 3 staple motifs. new is distinctly different from previously reported S(S‐ t Bu) tert ‐butylthiolate and one sulfido ligand face‐centered cubic (FCC) 22 kernel. The has an anomalous solubility (it only soluble in benzene but not other common...

ConspectusMetal nanoclusters containing a few to several hundred atoms with sizes ranging from sub-nanometer ∼2 nm occupy an intermediate size regime that bridges larger plasmonic nanoparticles and smaller metal complexes. With strong quantum confinement, exhibit molecule-like properties. This Account focuses on noble are synthesized within single stranded DNA template. Compared other ligand protected nanoclusters, DNA-templated manifest intriguing physical chemical properties heavily...

Toward controlling the magic sizes of atomically precise gold nanoclusters, herein we have devised a new strategy by exploring para-, meta-, ortho-methylbenzenethiol (MBT) for successful preparation pure Au130(p-MBT)50, Au104(m-MBT)41 and Au40(o-MBT)24 nanoclusters. The decreasing size sequence is in line with increasing hindrance methyl group to interfacial Au–S bond. That subtle change ligand structure can result drastically different under otherwise similar reaction conditions indeed...

Unveiling the ligand binding mode on crystalline surfaces is important for deciphering long-standing structural enigma in self-assembled monolayers (SAMs). Here, and patterning structures of thiolates (SR) Au(100) facet are revealed basis atomic structure a highly regular, single Au92(SR)44 nanocrystal. The six exposed facets this tetragonal nanocrystal give rise to pieces "nanoSAMs". We found that bind planar (100) via simple bridge-like assembled into an overlayer with c(2 × 2) symmetry....

We investigate the catalytic properties of water-soluble Aun(SG)m nanocluster catalysts (H-SG = glutathione) different sizes, including Au15(SG)13, Au18(SG)14, Au25(SG)18, Au38(SG)24, and captopril-capped Au25(Capt)18 nanoclusters. These Aun(SR)m nanoclusters (SR represents thiolate generally) are used as homogeneous (i.e., without supports) in chemoselective hydrogenation 4-nitrobenzaldehyde (4-NO2PhCHO) to 4-nitrobenzyl alcohol (4-NO2PhCH2OH) with ∼100% selectivity water using H2 gas (20...

The catalytic activity of Au25(SR)18 nanoclusters (R = C2H4Ph) for the aldehyde hydrogenation reaction in presence a base, e.g., ammonia or pyridine, and transition-metal ions Mz+, such as Cu+, Cu2+, Ni2+ Co2+, Lewis acid is studied. addition found to significantly promote Au25(SR)18/CeO2 benzaldehyde number its derivatives. Matrix-assisted laser desorption ionization (MALDI) electrospray (ESI) mass spectrometry conjunction with UV–vis spectroscopy confirm generation new species,...

A simple and efficient way was developed to enhance the visible-light-driven water-splitting performance by varying number of β-ketoenamine linkages in covalent organic frameworks.

Pancreatic cancer is characterized by early metastasis and high mortality. In this study, the role of miR-143 in invasion was investigated pancreatic cells. expression established an adenovirus-carried cassette. mRNA protein levels gene were examined RT-PCR Western blot assay, respectively. Rho GTPases activity measured pull down assay. The migration Panc-1 cells tested vitro. antimetastatic effect a liver model, while its antitumor growth xenograft tumor model. Results demonstrated that...

We report a new magic-sized gold nanocluster of atomic precision formulated as Au64(S-c-C6H11)32. The Au64 was obtained in relatively high yield (∼15%, Au atom basis) by two-step size-focusing methodology. Obtaining this magic size through the previously established "size focusing" method relies on introduction synthetic "parameter"—the type protecting thiolate ligand. It found that Au64(S-c-C6H11)32 most thermodynamically stable specie cyclohexanethiolate-protected nanoclusters range from...

We report the synthesis of a Au44(SR)28 nanocluster (SR = 4-tert-butylbenzenethiolate). Based on structural rules learned from known Au28(SR)20 and Au36(SR)24 structures, we propose plausible structure for Au44(SR)28, which is predicted to comprise six-interpenetrating cuboctahedral Au36 kernel protected by four dimeric staples sixteen bridging thiolates, i.e. Au36[Au2(SR)3]4(SR)16.