O-I-O halogen bond of halonium ions.

The reactivity of halonium ions is conveniently modulated by three-center, four-electron halogen bonds. Such stabilized halonium complexes are valuable reagents for oxidations and halofunctionalization reactions. We report the first example of the stabilization of a halenium ion in a three-center, four-electron halogen bond with two oxygen ligands. The influence of electron density and solvent on the stability of the complexes is assessed. O-I-O halogen bond complexes are applicable as synthetic reagents and as supramolecular synthons.

Catalytic Activity of trans-Bis(pyridine)gold Complexes.

Gold catalysis has become one of the fastest growing fields in chemistry, providing new organic transformations and offering excellent chemoselectivities under mild reaction conditions. Methodological developments have been driven by wide applicability in the synthesis of complex structures, whereas the mechanistic understanding of Au(III)-mediated processes remains scanty and have become the Achilles' heel of methodology development. Herein, the systematic investigation of the reactivity of bis(pyridine)-ligated Au(III) complexes is presented, based on NMR spectroscopic, X-ray crystallographic, and DFT data. The electron density of pyridines modulates the catalytic activity of Au(III) complexes in propargyl ester cyclopropanation of styrene. To avoid strain induced by a ligand with a nonoptimal nitrogen-nitrogen distance, bidentate bis(pyridine)-Au(III) complexes convert into dimers. For the first time, bis(pyridine)Au(I) complexes are shown to be catalytically active, with their reactivity being modulated by strain.

Halogen Bonding Helicates Encompassing Iodonium Cations.

The first halonium-ion-based helices were designed and synthesized using oligo-aryl/pyridylene-ethynylene backbones that fold around reactive iodonium ions. Halogen bonding interactions stabilize the iodonium ions within the helices. Remarkably, the distance between two iodonium ions within a helix is shorter than the sum of their van der Waals radii. The helical conformations were characterized by X-ray crystallography in the solid state, by NMR spectroscopy in solution and corroborated by DFT calculations. The helical complexes possess potential synthetic utility, as demonstrated by their ability to induce iodocyclization of 4-penten-1-ol.

Exploring the construction of multicompartmental micelles by halogen bonding of complementary macromolecules.

An approach to the construction of multicompartmental micelles, using halogen bonding between complementary macromolecules, is described. The design involves a sequential assembly protocol, in which the initial compartments are formed by interpolymer halogen bonding, followed by the collapse of a second, hydrophobic compartment upon transfer to aqueous solvent. Triblock terpolymers incorporating a halogen bond accepting segment have been synthesized. Transmission electron microscopy was used to characterize multicompartmental assemblies generated from these terpolymers in the presence of a halogen bond donor-functionalized polystyrene derivative.

Solution-phase self-assembly of complementary halogen bonding polymers.

Noncovalent halogen bonding interactions are explored as a driving force for solution phase macromolecular self-assembly. Conditions for controlled radical polymerization of an iodoperfluoroarene-bearing methacrylate halogen bond donor were identified. An increase in association constant relative to monomeric species was observed for the interaction between halogen bond donor and acceptor polymers in solution. When the polymeric donor was combined with a block copolymer bearing halogen bond-accepting amine groups, higher-order structures were obtained in both organic solvent and in water. Transmission electron microscopy, dynamic light scattering and nuclear magnetic resonance spectroscopic data are consistent with structures having cores composed of the interacting halogen bond donor and acceptor segments.

Polyvinylpyrrolidone molecular weight controls silica shell thickness on Au nanoparticles with diglycerylsilane as precursor.

Several strategies have been described for the preparation of silica-encapsulated gold nanoparticles (SiO(2)-AuNP), which typically suffer from an initial interface between gold and silica that is difficult to control, and layer thicknesses that are very sensitive to minor changes in silane concentration and incubation time. The silica shell thicknesses are normally equal to or larger than the gold particles themselves, which is disadvantageous when the particles are to be used for biodiagnostic applications. We present a facile and reproducible method to produce very thin silica shells (3-5 nm) on gold nanoparticles: the process is highly tolerant to changes in reaction conditions. The method utilized polyvinylpyrrolidone (PVP) of specific molecular weights to form the interface between gold and silica. The method further requires a nontraditional silica precursor, diglycerylsilane, which efficiently undergoes sol-gel processing at neutrality. Under these conditions, higher molecular weight PVP leads to thicker silica shells: PVP acts as the locus for silica growth into an interpenetrating organic-inorganic hybrid structure.

Silica shell/gold core nanoparticles: correlating shell thickness with the plasmonic red shift upon aggregation.

Differences in the wavelengths of the surface plasmon band of gold nanoparticles (AuNP)--before and after particle aggregation--are widely used in bioanalytical assays. However, the gold surfaces in such bioassays can suffer from exchange and desorption of noncovalently bound ligands and from nonspecific adsorption of biomolecules. Silica shells on the surfaces of the gold can extend the available surface chemistries for bioconjugation and potentially avoid these issues. Therefore, silica was grown on gold surfaces using either hydrolysis/condensation of tetraethyl orthosilicate 1 under basic conditions or diglyceroxysilane 2 at neutral pH. The former precursor permitted slow, controlled growth of shells from about 1.7 to 4.3 nm thickness. By contrast, 3-4 nm thick silica shells formed within an hour using diglyceroxysilane; thinner or thicker shells were not readily available. Within the range of shell thicknesses synthesized, the presence of a silica shell on the gold nanoparticle did not significantly affect the absorbance maximum (~5 nm) of unaggregated particles. However, the change in absorbance wavelength upon aggregation of the particles was highly dependent on the thickness of the shell. With silica shells coating the AuNP, there was a significant decrease in the absorbance maximum of the aggregated particles, from ~578 to ~536 nm, as the shell thicknesses increased from ~1.7 to ~4.3 nm, because of increased distance between adjacent gold cores. These studies provide guidance for the development of colorimetric assays using silica-coated AuNP.