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R C Haddon

Publications and source records attributed to R C Haddon.

11 recordsLinked to original sources
PubMed2001

Stacking efficiency of diselenadiazolyl pi-dimers. Consequences for electronic structure and transport properties.

The preparation and crystal structure of 5-cyanofuran-2-[1,2,3,5-diselenadiazolyl], [RCN(2)Se(2)] (R = 5-cyanofuran), is reported. Crystal data for C(6)H(2)ON(3)Se(2): monoclinic, space group P2(1), a = 7.1121(7), b= 20.541(2), c =20.923(2) A, beta = 99.785(1) degrees, Z = 16. The crystal structure consists of diselenadiazolyl pi-dimer stacks running parallel to the x direction; the asymmetric unit consists of four pi-dimer units. The dimers are aligned into snakelike ribbons along the y direction, with consecutive dimers linked by head-to-tail CN-Se contacts. Each pi-dimer stack is bordered by two out-of-register stacks, but most interstack Se-Se contacts lie outside the van der Waals separation. Along the pi-dimer stacks, the intradimer Se-Se distances range from 3.183(10) to 3.294(1) A, and the interdimer Se-Se distances range from 3.826(1) to 3.945(1) A. Like other pi-dimer stacked diselenadiazolyls, [C(6)H(2)ON(3)Se(2)](2) is diamagnetic over the temperature range 4-380K. Variable temperature single-crystal conductivity measurements reveal a room-temperature conductivity near 10(-5) S cm(-1) and provide a calculated band gap of 0.72 eV. The structural results and transport properties are interpreted in the light of Extended Hückel band structure calculations.

Journal Article↗
PubMed2001

Chromatographic purification and properties of soluble single-walled carbon nanotubes.

We report an improved chromatographic purification of soluble single-walled carbon nanotubes (s-SWNTs) using gel permeation chromatography. Three fractions are separated by gel permeation chromatography, and the first fraction contains 74% of the s-SWNTs as detected by atomic force microscopy and UV and near-infrared spectroscopy.

Journal Article↗
PubMed2001

Perchlorophenalenyl radical, C13Cl9: a modulated structure with nine threefold-symmetric molecules in the asymmetric unit.

The odd-alternant perchlorophenalenyl radical, C13Cl9, forms molecular stacks centered on crystallographic threefold rotation axes, but the spacing within the stacks (3.78 A) is too large to allow good overlap of the orbitals in which the spin density is localized. The radical is ruffled because of the intramolecular repulsions between alpha Cl atoms (the Cl...Cl peri interactions); the average displacement of an alpha Cl atom from the molecular plane is approximately 0.7 A. The deviations from molecular planarity do not, however, determine the spacing within the stacks, which is determined instead by interactions between stacks. The modulations found in the P3c1 superstructure are a response to the short interstack contacts that would occur in the average pseudocell structure (R3;m, c' = c/6). The primary modulation is a pattern of enantiomeric alternation; a secondary modulation involves small rotations of the molecules around their threefold axes. The number (9) of independent molecules in the true cell is exceptionally large because of the conflict between the preference within the molecular stacks for threefold rotational symmetry and the preference in directions perpendicular to the stack axes for twofold alternation of enantiomers. The structural complexity reduces the precision of the distances and angles determined, but the average values found are in excellent agreement with those calculated by density functional theory.

Journal Article↗
PubMed2001

Perchlorophenalenyl radical.

We report the preparation and solid-state characterization of the perchlorophenalenyl radical (1). The radical is initially obtained as a yellow-green solid by reduction of the perchlorophenalenium salt (12(+)). This solid sublimes in a sealed tube to give black shiny hexagonal crystals of the perchlorophenalenyl radical (1). The structure consists of 1-dimensional stacks of the monomeric radical. The peri-chlorine atoms force the phenalenyl system to be strongly nonplanar leading to a large separation between adjacent molecules within the stacks (3.78 A), and the molecules adopt two distinct stacking motifs (quasisuperimposed and rotated by 60 degrees with respect to neighbors). Because of the packing frustration in the lattice and the large intermolecular spacing, the solid shows Curie paramagnetism in the temperature range 100-400 K, before antiferromagnetic coupling sets in at low temperatures. Due to the narrow bandwidth that results from the isolation of the individual molecules, the solid is a Mott-Hubbard insulator, with a room-temperature conductivity of rho(RT) = 10(-10) S/cm.

Journal Article↗
PubMed2001

Dimeric phenalenyl-based neutral radical molecular conductors.

We report the preparation, crystallization, and solid-state characterization of ethyl (3)- and butyl (4)-substituted spiro-biphenalenyl radicals. Both of these compounds are found to be conducting face-to-face pi-dimers in the solid state but with different room-temperature magnetic ground states. At room temperature, 4 exists as a diamagnetic pi-dimer (interplanar separation of approximately 3.1 A), whereas 3 is a paramagnetic pi-dimer (interplanar separation of approximately 3.3 A), and both compounds show phase transitions between the paramagnetic and diamagnetic forms. Electrical resistivity measurements of single crystals of 3 and 4 show that the transition from the high-temperature paramagnetic pi-dimer form to the low-temperature diamagnetic pi-dimer structure is accompanied by an increase in conductivity by about 2 orders of magnitude. This behavior is unprecedented and is very difficult to reconcile with the usual understanding of a Peierls dimerization, which inevitably leads to an insulating ground state. We tentatively assign the enhancement in the conductivity to a decrease in the on-site Coulombic correlation energy (U), as the dimers form a super-molecule with twice the amount of conjugation.

Journal Article↗
PubMed2001

Effect of van der Waals interactions on the Raman modes in single walled carbon nanotubes.

We have measured the Raman spectrum of individual single walled carbon nanotubes in solution and compare it to that obtained from the same starting material where the tubes are present in ordered bundles or ropes. Interestingly, the radial mode frequencies for the tubes in solution are found to be approximately 10 cm (-1) higher than those observed for tubes in a rope, in apparent contradiction to lattice dynamics predictions. We suggest that there is no such contradiction, and propose that the upshift is due rather to a decreased energy spacing of the Van Hove singularities in isolated tubes over the spacings in a rope, thereby allowing the same laser excitation to excite different diameter tubes in these two samples.

Journal Article↗
PubMed2000

A superconducting field-effect switch.

We report here on a novel realization of a field-effect device that allows switching between insulating and superconducting states, which is the widest possible variation of electrical properties of a material. We chose C(60) as the active material because of its low surface state density and observed superconductivity in alkali metal-doped C(60). We induced three electrons per C(60) molecule in the topmost molecular layer of a crystal with the field-effect device, creating a superconducting switch operating up to 11 kelvin. An insulator was thereby transformed into a superconductor. This technique offers new opportunities for the study of superconductivity as a function of carrier concentration.

Journal Article↗
PubMed2000

Molecular functionalization of carbon nanotubes and use as substrates for neuronal growth.

Carbon nanotubes are strong, flexible, conduct electrical current, and can be functionalized with different molecules, properties that may be useful in basic and applied neuroscience research. We report the first application of carbon nanotube technology to neuroscience research. Methods were developed for growing embryonic rat-brain neurons on multiwalled carbon nanotubes. On unmodified nanotubes, neurons extend only one or two neurites, which exhibit very few branches. In contrast, neurons grown on nanotubes coated with the bioactive molecule 4-hydroxynonenal elaborate multiple neurites, which exhibit extensive branching. These findings establish the feasability of using nanotubes as substrates for nerve cell growth and as probes of neuronal function at the nanometer scale.

Aldehydes↗
PubMed1985

The molecular electronic device and the biochip computer: present status.

The idea that a single molecule might function as a self-contained electronic device has been of interest for some time. However, a fully integrated version--the biochip or the biocomputer, in which both production and assembly of molecular electronic components is achieved through biotechnology-is a relatively new concept that is currently attracting attention both within the scientific community and among the general public. In the present article we draw together some of the approaches being considered for the construction of such devices and delineate the revolutionary nature of the current proposals for molecular electronic devices (MEDs) and biochip computers (BCCs). With the silicon semiconductor conductor industry already in place and in view of the continuing successes of the lithographic process it seems appropriate to ask why the highly speculative MED or BCC has engendered such interest. In some respects the answer is paradigmatic as much as it is real. It is perhaps best stated as the promise of the realm of the molecular. Thus it is envisioned that devices will be constructed by assembly of individual molecular electronic components into arrays, thereby engineering from small upward rather than large downward as do current lithographic techniques. An important corollary of the construction technique is that the functional elements of such an array would be individual molecules rather than macroscopic ensembles. These two aspects of the MED/BCC--assembly of molecular arrays and individually accessible functional molecular units--are truly revolutionary. Both require scientific breakthroughs and the necessary principles, quite apart from the technology, remain essentially unknown. It is concluded that the advent of the MED/BCC still lies well before us. The twin criteria of utilization of individual molecules as functional elements and the assembly of such elements remains as elusive as ever. Biology engineers structures on the molecular scale but biomolecules do not seem to be imbued with useful electronic properties. Molecular beam epitaxy and thin-film techniques produce electronic devices but they "engineer down" and are currently unable to generate individual molecular units. The potential of the MED/BCC field is matched only by the obstacles that must be surmounted for its realization.

Brain↗