Abstract

Abstract

Abstract

Reactions of graphene with zinc enable etching of a single graphene layer.

Abstract

Single-molecule transistors (SMTs) incorporating individual small molecules are unique tools for examining the fundamental physics and chemistry of electronic transport in molecular systems at the single nanometer scale. We describe the fabrication and characterization of such devices, and the synthesis and surface attachment chemistry of novel transition metal complexes that have been incorporated into such SMTs. We present gate-modulated inelastic electron tunneling vibrational spectroscopy of single molecules, strong Kondo physics (T_K ∼ 75 K) as evidence of excellent molecule/electrode electronic coupling, and a demonstration that covalent attachment chemistry can produce SMTs that survive repeated thermal cycling to room temperature. We conclude with a look ahead at the prospects for these nanoscale systems.

A series of multiple [60]fullerene terminated oligo(p-phenylene ethynylene) (OPE) hybrid compounds has been synthesized through a newly developed in situ ethynylation method. Structural and magnetic shielding properties of the highly unsaturated carbon-rich C₆₀ and OPE scaffolds were characterized by 1D and 2D NMR spectroscopic analyses. Electronic interactions between the [60]fullerenes and the OPE backbones were investigated by UV/Vis spectroscopic and cyclic voltammetry (CV) experiments. Our studies clearly show that although the multiple [60]fullerene groups are connected via π-conjugated OPE frameworks, they present diminutive electronic interactions in the ground state, and the electronic behavior of the [60]fullerene cages are only affected by the OPE backbones through modest inductive effects. Interestingly, sizable third-order nonlinear optical (NLO) responses (γ) and enhanced two-photon absorption (TPA) cross-sections (σ⁽²⁾) were determined for the multifullerene–OPE hybrid 31 relative to its OPE precursor from differential optical Kerr effect (DOKE) experiments. Such enhanced NLO performance is presumably due to the occurrence of periconjugation and/or charge transfer effects in the excited state. In addition, comparatively strong excited-state absorption was observed and characterized for OPE pentamer 12. Thus, the use of such fullerene-derivatized conjugated oligomers aids the quest for molecules with large third-order NLO and TPA properties.

The use of carbon nanotubes in materials applications has been slowed due to nanotube insolubility and their incompatibility with polymers. We recently developed two protocols to overcome the insoluble nature of carbon nanotubes by affixing large amounts of addends to the nanotube sidewalls. Both processes involve reactions with aryl diazonium species. First, solvent-free functionalization techniques remove the need for any solvent during the functionalization step. This delivers functionalized carbon nanotubes with increased solubility in organic solvents and processibility in polymeric blends. Additionally, the solvent-free functionalization process can be done on large scales, thereby paving the way for use in bulk applications such as in structural materials development. The second methodology involves the functionalization of carbon nanotubes that are first dispersed as individual tubes in surfactants within aqueous media. The functionalization then ensues to afford heavily functionalized nanotubes that do not re-rope. They remain as individuals in organic solvents giving enormous increases in solubility. This protocol yields the highest degree of functionalization we have obtained thus far—up to one in nine carbon atoms on the nanotube has an organic addend. The proper characterization and solubility determinations on nanotubes are critical; therefore, this topic is discussed in detail.

Abstract

Diazonium reagents functionalize single-walled carbon nanotubes suspended in aqueous solution with high selectivity and enable manipulation according to electronic structure. For example, metallic species are shown to react to the near exclusion of semiconducting nanotubes under controlled conditions. Selectivity is dictated by the availability of electrons near the Fermi level to stabilize a charge-transfer transition state preceding bond formation. The chemistry can be reversed by using a thermal treatment that restores the pristine electronic structure of the nanotube.

Presented here are several convergent synthetic routes to conjugated oligo(phenylene ethynylene)s. Some of these oligomers are free of functional groups, while others possess donor groups, acceptor groups, porphyrin interiors, and other heterocyclic interiors for various potential transmission and digital device applications. The syntheses of oligo(phenylene ethynylene)s with a variety of end groups for attachment to numerous metal probes and surfaces are presented. Some of the functionalized molecular systems showed linear, wirelike, current versus voltage (I(V)) responses, while others exhibited nonlinear I(V) curves for negative differential resistance (NDR) and molecular random access memory effects. Finally, the syntheses of functionalized oligomers are described that can form self-assembled monolayers on metallic electrodes that reduce the Schottky barriers. Information from the Schottky barrier studies can provide useful insight into molecular alligator clip optimizations for molecular electronics.

Eine einfache Modifizierung der Lösungsmittelbedingungen ermöglicht einen leichten Zugang zu supramolekularen Fulleren-Nanostrukturen. Das hier gezeigte Fullerenderivat liefert bei der Selbstorganisation entweder Nanostäbe oder Vesikel. Die Nanostäbe sind länger als 70 μm und haben je nach Gegenion Durchmesser von 10–250 nm. Durch Ultraschallbehandlung erhält man dagegen Vesikel mit einem Durchmesser von 10–70 nm und einer Wandstärke von 3–6 nm, aber keine Nanostäbe.

Simple modification of solution conditions provides facile access to supramolecular fullerene nanostructures. The fullerene derivative shown self-assembles to give nanorods or vesicles. The nanorods have diameters of 10–250 nm, depending on the counterion, and lengths greater than 70 μm. If ultrasonication is used, no nanorods form, but vesicles result having diameters of 10–70 nm and wall thicknesses of 3–6 nm.