Computational investigation of structural, electronic, and spectroscopic properties of Ni and Zn metalloporphyrins with varying anchoring groups.

Porphyrins are prime candidates for a host of molecular electronics applications. Understanding the electronic structure and the role of anchoring groups on porphyrins is a prerequisite for researchers to comprehend their role in molecular devices at the molecular junction interface. Here, we use the density functional theory approach to investigate the influence of anchoring groups on Ni and Zn diphenylporphyrin molecules.

Atomically precise nanoclusters predominantly seed gold nanoparticle syntheses.

Seed-mediated synthesis strategies, in which small gold nanoparticle precursors are added to a growth solution to initiate heterogeneous nucleation, are among the most prevalent, simple, and productive methodologies for generating well-defined colloidal anisotropic nanostructures. However, the size, structure, and chemical properties of the seeds remain poorly understood, which partially explains the lack of mechanistic understanding of many particle growth reactions. Here, we identify the majority component in the seed solution as an atomically precise gold nanocluster, consisting of a 32-atom Au core with 8 halide ligands and 12 neutral ligands constituting a bound ion pair between a halide and the cationic surfactant: AuX[AQA•X] (X = Cl, Br; AQA = alkyl quaternary ammonium).

Halogenated Carboxylates as Organic Anodes for Stable and Sustainable Sodium-Ion Batteries.

Organic materials are competitive as anodes for Na-ion batteries (NIBs) due to the low cost, abundance, environmental benignity, and high sustainability. Herein, we synthesized three halogenated carboxylate-based organic anode materials to exploit the impact of halogen atoms (F, Cl, and Br) on the electrochemical performance of carboxylate anodes in NIBs. The fluorinated carboxylate anode, disodium 2, 5-difluoroterephthalate (DFTP-Na), outperforms the other carboxylate anodes with H, Cl, and Br, in terms of high specific capacity (212 mA h g), long cycle life (300 cycles), and high rate capability (up to 5 A g).

Au ( Bu P) : A Highly Symmetric Metalloid Gold Cluster in Oxidation State 0.

Metalloid gold clusters have unique properties with respect to size and structure and are key intermediates in studying transitions between molecular compounds and the bulk phase of the respective metal. In the following, the synthesis of the all-phosphine protected metalloid cluster Au ( Bu P) , solely built from gold atoms in the oxidation state of 0 is reported. Single-crystal X-ray analysis revealed a highly symmetric hollow cube-octahedral arrangement of the gold atoms, resembling gold bulk structure.

A new reductant in gold cluster chemistry gives a superatomic gold gallium cluster.

The low valent gallium(i) compound GaCp was primarily used in gold cluster chemistry to synthesize the superatomic cluster [(PPh)AuGaCl], complementing the borane-dominated set of reducing agents in gold chemistry, opening a whole new field for further research. Using density functional theory calculations, the cluster can be described by the jellium model as an 8-electron superatom cluster.

Computational Comparative Analysis of Small Atomically Precise Copper Clusters.

Atomically precise copper clusters (APC) have attracted attention for their promise in sensing, water remediation, and electrochemical technologies. However, smaller-sized APCs and the evolution of their properties as a function of size and composition are not clearly understood. Here, we have performed an investigation into the electronic structure, geometry, and optical properties of small atomically precise copper clusters using density functional theory (DFT) and time-dependent DFT.

ReaxFF MD Simulations of Peptide-Grafted Gold Nanoparticles.

Functionalized gold nanoparticles have critical applications in biodetection with surface-enhanced Raman spectrum and drug delivery. In this study, reactive force field molecular dynamics simulations were performed to study gold nanoparticles, which are modified with different short-chain peptides consisting of amino acid residues of cysteine and glycine in different grafting densities in the aqueous environment. Our study showed slight facet-dependent peptide adsorption on a gold nanoparticle with the 3 nm core diameter.

Synthesis and Characterization of Three Multi-Shell Metalloid Gold Clusters Au (R P) Cl.

Three multi-shell metalloid gold clusters of the composition Au (R P) Cl (R=Et, Pr, Bu) were synthesized in a straightforward fashion by reducing R PAuCl with NaBH in ethanol. The Au core comprises two shells, with the inner one constituting a tilted icosahedron and the outer one showing a distorted dodecahedral arrangement. The outer shell is completed by eight chloride atoms and twelve R P groups.

Balancing the Micro-Mesoporosity for Activity Maximization of N-Doped Carbonaceous Electrocatalysts for the Oxygen Reduction Reaction.

Carbonaceous porous structures have instigated global research interest as promising low-cost electrocatalysts for numerous energy technologies. However, the rational design principle of pore structures for activity maximization is still unclear. In this work, a series of N-doped carbon (N-C) catalysts with exclusively different micro-mesoporosity are investigated for the oxygen reduction reaction (ORR).

[PtZnGe(Hyp)] (Hyp = Si(SiMe)): A Neutral Polynuclear Chain Compound with Ge(Hyp) Units.

The reaction of [ZnGe(Hyp)] (Hyp = Si(SiMe)) with Pt(PPh) gives the neutral polynuclear complex of Ge(Hyp) units [HypZn-Ge(Hyp)-Pt-Ge(Hyp)-ZnHyp], 1. Within 1, the central Pt atom is bound η to both Ge(Hyp) units to which further ZnHyp units are bound again, symmetric η, to the other side of the Ge(Hyp) units, leading to the longest chain compound exhibiting Ge(Hyp) units that is known to date. Dissolved crystals of 1 give a violet solution, showing an absorption maximum around 543 nm.

AuS(PPh): an intermediate sized metalloid gold cluster stabilized by the AuS ring motif and Au-PPh groups.

Reducing (PhP)AuSC(SiMe) with l-Selectride® gives the medium-sized metalloid gold cluster AuS(PPh). Computational studies show that the phosphine bound Au-atoms not only stabilize the electronic structure of AuS(PPh), but also behave as electron acceptors leading to auride-like gold atoms on the exterior.