Physical properties of materials derived from diamondoid molecules.

Diamondoids are small hydrocarbon molecules which have the same rigid cage structure as bulk diamond. They can be considered the smallest nanoparticles of diamond. They exhibit a mixture of properties inherited from bulk cubic diamond as well as a number of unique properties related to their size and structure. Diamondoids with different sizes and shapes can be separated and purified, enabling detailed studies of the effects of size and structure on the diamondoids' properties and also allowing the creation of chemically functionalized diamondoids which can be used to create new materials. Most notable among these new materials are self-assembled monolayers of diamondoid-thiols, which exhibit a number of unique electron emission properties.

Experimental determination of the ionization potentials of the first five members of the nanodiamond series.

The ionization potentials of size- and isomer-selected diamondoids (nanodiamond containing one to five crystal cages) have been measured by means of total-ion-yield spectroscopy. We find a monotonic decrease of the ionization potential with increasing diamondoid size. This experimental result is compared to recent theoretical predictions and comparable investigations on related carbon clusters, the fullerenes, which show isomer effects to be stronger than size dependence.

Monochromatic electron photoemission from diamondoid monolayers.

We found monochromatic electron photoemission from large-area self-assembled monolayers of a functionalized diamondoid, [121]tetramantane-6-thiol. Photoelectron spectra of the diamondoid monolayers exhibited a peak at the low-kinetic energy threshold; up to 68% of all emitted electrons were emitted within this single energy peak. The intensity of the emission peak is indicative of diamondoids being negative electron affinity materials. With an energy distribution width of less than 0.5 electron volts, this source of monochromatic electrons may find application in technologies such as electron microscopy, electron beam lithography, and field-emission flat-panel displays.

Molecular limits to the quantum confinement model in diamond clusters.

The electronic structure of monodispersed, hydrogen-passivated diamond clusters (diamondoids) in the gas phase has been studied with x-ray absorption spectroscopy. The data show that the bulk-related unoccupied states do not exhibit any quantum confinement. Additionally, density of states below the bulk absorption edge appears, consisting of features correlated to CH and CH2 hydrogen surface termination, resulting in an effective redshift of the lowest unoccupied states. The results contradict the commonly used and very successful quantum confinement model for semiconductors, which predicts increasing band edge blueshifts with decreasing particle size. Our findings indicate that in the ultimate size limit for nanocrystals a more molecular description is necessary.

Isolation and structure of higher diamondoids, nanometer-sized diamond molecules.

We exploited the exceptional thermal stability and diverse molecular shapes of higher diamondoids (C22 and higher polymantanes) to isolate them from petroleum. Molecules containing 4 to 11 diamond-crystal cages were isolated and crystallized, and we obtained single-crystal x-ray structures for representatives from three families. Rigidity, strength, remarkable assortments of three- dimensional shapes, including resolvable chiral forms, and multiple, readily derivatizable attachment sites make them valuable nanometer-size molecular building blocks.