Low-temperature oxidation of aqueous magnetite nanoparticles to maghemite has been monitored via the loss of near-IR optical absorbance. The kinetics closely follows the diffusion in a sphere model as suggested by previous literature reports. The temperature dependence of the diffusion constant is described by an Arrhenius equation with an activation energy of 21.0 kcal/mol. No intermediate optical spectra are observed, which confirms the extremely local nature of the optical transitions. A careful search for photooxidation establishes a small upper limit for the possible increase in the diffusion constant under illumination.

A novel metal-free, organocatalytic approach to living polymerization is presented. N-heterocyclic carbenes were employed as nucleophilic catalysts for the ring-opening polymerization (ROP) of cyclic ester monomers. The catalysts is used in combination with an initiator, such as an alcohol, which generates an alpha-end group bearing the ester from the initiating alcohol upon ring-opening and a hydroxyl functional omega-chain end that propagates the chain. This class of catalyst proved to be more reactive than tertiary amine and phosphine nucleophiles, producing narrowly dispersed polymers of predictable molecular weights at room temperature in 1-2 h. Catalysis with respect to both initiating alcohol and monomer was observed. Control of the alpha and omega end-groups was demonstrated with a pyrene-labeled initiator, allowing the preparation of well-defined macromolecular architectures. Analogous to the ROP of cyclic esters using biocatalysts, the polymeriztion pathway using the N-heterocyclic carbenes is believed to ensue through a monomer-activated mechanism.

In a twist: A design strategy for molecule‐based electronic materials using aromatic compounds with a nonplanar core is presented. A new class of hexabenzocoronene is put forth that has its core severely distorted out of planarity into a corrugated structure. When substituted with four alkoxy side chains, this material self‐assembles into infinitely long columns through stacking (see picture) and acts as an active layer in field‐effect transistors.

This work details a method to make efficacious field-effect transistors from monolayers of polycyclic aromatic hydrocarbons that are able to sense and respond to their chemical environment. The molecules used in this study are functionalized so that they assemble laterally into columns and attach themselves to the silicon oxide surface of a silicon wafer. To measure the electrical properties of these monolayers, we use ultrasmall point contacts that are separated by only a few nanometers as the source and drain electrodes. These contacts are formed through an oxidative cutting of an individual metallic single-walled carbon nanotube that is held between macroscopic metal leads. The molecules assemble in the gap and form transistors with large current modulation and high gate efficiency. Because these devices are formed from an individual stack of molecules, their electrical properties change significantly when exposed to electron-deficient molecules such as tetracyanoquinodimethane (TCNQ), forming the basis for new types of environmental and molecular sensors.chemistry ͉ electronic materials ͉ nanoscience ͉ self-assembly T his work details a method to make chemoresponsive transistors by making devices out of a monolayer of polycyclic aromatic hydrocarbons that are chemically attached to surfaces. The devices are formed through a self-assembly process of organic semiconductors on the oxide surface of a silicon wafer (Fig. 1A) (1, 2). Previous studies on organic field-effect transistors (OFETs) (3, 4) have shown that the path for electrical current is through at most the first few layers of molecules at the oxide interface (5-7). In general, when the semiconducting layers of typical OFETs are scaled down to a monolayer, their properties become poor, presumably due to discontinuities or defects in the films (8-11). The strategy used here circumvents this problem by a chemical functionalization of the molecular semiconductors ( Fig. 1B) so that they both assemble laterally and chemically attach themselves to the substrate (Fig. 1C). The important result is that when ultrasmall point contacts separated by molecular length-scales are used as the source and drain (S͞D) electrodes, transistors can be made that have high gate efficiency and large ON͞OFF ratios from only a monolayer of molecules. The electrical properties of these monolayers are responsive to electron acceptors such as tetracyanoquinodimethane (TCNQ). Results and DiscussionDevice Fabrication. We first describe the devices used to measure the properties of the monolayers and then the structural and electrical characterization of these monolayers. Fig. 2 shows a schematic and micrograph of the devices used. Au (50 nm) on Cr (5 nm) pads, which are separated by 20 m, form the contact to an individual single-walled carbon nanotube (SWNT). The nanotubes were grown by a chemical vapor deposition (CVD) process described elsewhere (12, 13). The nanotube is then oxidatively cut by using an ultrafine lithographic process that produces a very small gap between the nan...

We describe a new strategy for the in situ growth of molecular wires predicated on the synthesis of a trifunctional "primed" contact formed from metal-carbon multiple bonds. The ruthenium-carbon pi bond provides structural stability to the molecular linkages under ambient conditions, and density functional calculations indicate the formation of an efficient conduit for charge carriers to pass between the metal and the molecule. Moreover, the metal-carbon pi bond provides a chemically reactive site from which a conjugated molecular wire can be grown in situ through an olefin metathesis reaction.