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...

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...

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...

The optical properties of metal nanoparticles have attracted wide interest. Recent progress in controlling with atomic precision (often called nanoclusters) provide new opportunities for investigating many fundamental questions, such as the transition from excitonic to plasmonic state, which is a central question nanoparticle research because it provides insights into origin surface plasmon resonance (SPR) well formation metallic bond. However, this still remains elusive extreme difficulty...

One of the important factors that determine photoluminescence (PL) properties gold nanoclusters pertain to surface. In this study, four Au52(SR)32 feature a series aromatic thiolate ligands (-SR) with different bulkiness at para-position are synthesized and investigated. The near-infrared (NIR) (peaks 900-940 nm) quantum yield (QY) is largely enhanced decrease in ligand's para-bulkiness. Specifically, capped least bulky p-methylbenzenethiolate (p-MBT) exhibits highest PLQY (18.3% room...

We report a method for heavy doping of the Au25(SR)18 nanocluster (where R = C6H11) with silver through Ag(I)-thiolate complex induced size/structure transformation Au23(SR)16(-) into Au25-xAgx(SR)18(-). X-ray crystallographic analysis revealed that Ag dopants are distributed not only in icosahedral core but also surface staple motifs; latter was achieved earlier studies alloy Au25-xAgx nanoclusters.

Atomically precise metal nanoclusters with tailored surface structures are important for both fundamental studies and practical applications. The development of new methods tailoring the structure in a controllable manner has long been sought. In this work, we report reconstruction induced by cadmium doping into [Au23(SR)16]- (R = cyclohexyl) nanocluster, which two neighboring Au atomic sites "coalesce" one Cd site and, accordingly, bimetal [Au19Cd2(SR)16]-, is produced. Interestingly,...

Solving the atomic structure of large-sized metal nanoclusters is a highly challenging task yet critically important for understanding properties and developing applications. Herein, we report stable silver nanocluster—Ag146Br2(SR)80 (where SR = 4-isopropylbenzenethiolate)—with its solved by X-ray crystallography. Gram-scale synthesis with high yield has been achieved one-pot reaction, which offers opportunities functionalization This nanocluster possesses core–shell Ag51 core surrounded...

Atomically precise control over anisotropic nanoclusters constitutes a grand challenge in nanoscience. In this work, we report our success achieving periodic series of atomically gold quantum rods (abbrev. Au QRs) with unusual excitonic properties. These QRs possess hexagonal close-packed kernels constant three-atom diameter but increasing aspect ratios (ARs) from 6.3 to 18.7, all being protected by the same thiolate (SR) ligand. The are

The linear trinuclear compound Co3(dpa)4Cl2 (1; dpa = di(2-pyridyl)amide anion) crystallizes from CH2Cl2 solution in two forms simultaneously, namely, an orthorhombic form 1·CH2Cl2 and a tetragonal 1·2CH2Cl2. three linearly arranged cobalt atoms 1 are supported by four ligands spiral configuration. chain of is symmetrical 1·CH2Cl2, but unsymmetrical Both crystal structures have been studied at various temperatures. A reversible second-order phase transition (165 K) (Pnn2) to monoclinic (Pn)...

We report the preparation, crystallization, and solid-state characterization of ethyl (3)- butyl (4)-substituted spiro-biphenalenyl radicals. Both these compounds are found to be conducting face-to-face π-dimers in solid state but with different room-temperature magnetic ground states. At room temperature, 4 exists as a diamagnetic π-dimer (interplanar separation ∼3.1 Å), whereas 3 is paramagnetic ∼3.3 both show phase transitions between forms. Electrical resistivity measurements single...

Alkylation of the zwitterionic heterocycle 8-chloro-bis[1,2,3]dithiazolo[4,5-b:5',4'-e]pyridine (ClBP) with alkyl triflates affords 8-chloro-4-alkyl-4H-bis[1,2,3]dithiazolo[4,5-b:5',4'-e]pyridin-2-ium [ClBPR][OTf] (R = Me, Et, Pr). Reduction these salts decamethylferrocene corresponding ClBPR radicals as thermally stable crystalline solids. The have been characterized in solution by cyclic voltammetry and EPR spectroscopy. Measured electrochemical cell potentials computed (B3LYP/6-31G)...

Macrocyclic propargyl acetates containing a furan ring were prepared by using CrCl(2)-promoted reaction. In the presence of either Au(I) or Au(III) catalyst, tandem 3,3-rearrangement/transannular [4+3] cycloaddition reaction occurred to give that are regio- and diastereospecific. The regiochemistry product is controlled position acetoxy group in starting material stereochemistry depends on size.

The photophysical and electrochemical properties of a platinum(II) diimine complex bearing the bidentate diacetylide ligand tolan-2,2'-diacetylide (tda), Pt(dbbpy)(tda) [dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine] (1), are compared with two reference compounds, Pt(dbbpy)(C[triple bond]CPh)(2) (2) Pt(dppp)tda [dppp 1,3-bis(diphenylphosphino)propane] (3), respectively. X-ray crystal structure 1 is reported, which illustrates nearly perfect square planarity exhibited by this metallacycle....

Abstract We report an anomalous structural transformation of a Cu(I) cluster into two different types copper‐silver (CuAg) alloy nanoclusters. Different from previous reports, we demonstrate that under specifically designed reaction conditions, the Ag‐doping could induce substantial growth starting Cu 15 and Ag 13 20 nanocluster was obtained via unexpected insertion kernel inside Cu(I)‐S shell. demonstrates high activity to initiate photopolymerization previously hard‐to‐print inorganic...

An open-flow helium cryostat for single-crystal X-ray diffraction experiments capable of reaching 14 K has been developed using off-the-shelf components. Solid/liquid air build-up is prevented the transfer-line back-flow and a heated nozzle. The system run over 30 h with no frost build-up. effectiveness demonstrated test data oxalic acid, terbium vanadate dysprosium vanadate.

The molecular structures and magnetic properties of six dinitroxide biradicals are described. Five the dinitroxides trimethylenemethane-type (TMM-type) biradicals; that is, intramolecular exchange parameter, J, is modulated by a carbon-carbon double bond. However, efficacy bond as an coupler determined conformation. Our results show parameters correlate with phenyl-ring torsion angles (phi) via simple Karplus-Conroy-type relation: J = 44 cos(2) phi - 17. Comparison these to those obtained...

The rare earth vanadate TbVO4, undergoes a crystallographic phase transition below 33 K induced by cooperative Jahn-Teller effect. Twinning of the crystal occurs upon this from tetragonal high temperature to orthorhombic low resulting in domain structure. Single x-ray analyses and twinned verify reduction site symmetry Tb ion D2d (m2-dodecahedral) for D2 (222-distorted dodecahedral) phase. Concomitantly, space group is lowered D194h (I41/amd) D242h (Fddd). described as domains related each...

We report isomer-pure synthesis of thieno[2,3-f:5,4-f ']bis[1]benzothiophene and thieno[3,2-f:4,5-f ']bis[1]benzothiophene, the anti syn isomers a pentacyclic compound consisting alternating thiophene benzene rings. The optical electrochemical properties both are reported. In isomer, ribbonlike embedding three units leads to near-planar molecule with favorable π−π stacking behavior in solid state as shown by X-ray crystal structure analysis.

Synthesis and full characterization of cationic isostructural "sandwich" diimine-coinage metal ethylene complexes are reported. Ethylene self-exchange kinetics proceeds by an associative exchange mechanism for Cu Au complexes. The fastest ligand was observed Ag complex 8a. upper limit ΔG⧧, assuming exchange, found to be ca. 5.0 kcal/mol. in 7b with ΔG298⧧ = 12.9 ± 0.1 kcal/mol, while the is slowest 9, 16.7 Copper unusually stable can survive air years.

An Au36(S-tBu)22 nanocluster (NC) is synthesized using the bulky tert-butyl thiol as ligand. Single-crystal X-ray crystallography reveals that it has an Au25 core which evolves from Au22 in previously reported Au30(S-tBu)18, and protected by longer staple-like surface motifs. The new Au36 NC extends members of face-centered cubic structural evolution adding Au3 triangle Au4 tetrahedron unit. Additionally, found emits near-infrared photoluminescence at 863 nm with a quantum yield (QY) 4.3%,...

For the majority of gold nanoclusters (NCs), their water insolubility, low photoluminescence (PL) intensity, and less understood photostability are three critical factors that limit application in biomedical photocatalysis fields. In this study, we report a polymer wrapping method for phase transfer organic soluble NCs into aqueous without degrading electronic optical properties, such materials further demonstrated robust water. We first synthesized Au18(DMBT)14 NC (DMBT =...