Synthetic Doping of Diamondoids through Skeletal Editing.

We present a strategy for the skeletal editing of diamondoid structures to selectively displace methylene for heteroatom moieties in the carbon framework. This constitutes a synthetic approach to doping diamond-like structures with electron donor dopants (O, N, and S). The key steps involve two subsequent retro-Barbier fragmentations followed by cage reconstruction in the presence of a dopant. Remarkably, the incorporation of n-dopants reduces the strain of the diamondoid cage as shown through homodesmotic equations.

Facile diamond synthesis from lower diamondoids.

Carbon-based nanomaterials have exceptional properties that make them attractive for a variety of technological applications. Here, we report on the use of diamondoids (diamond-like, saturated hydrocarbons) as promising precursors for laser-induced high-pressure, high-temperature diamond synthesis. The lowest pressure and temperature (P-T) conditions that yielded diamond were 12 GPa (at ~2000 K) and 900 K (at ~20 GPa), respectively. This represents a substantially reduced transformation barrier compared with diamond synthesis from conventional (hydro)carbon allotropes, owing to the similarities in the structure and full sp3 hybridization of diamondoids and bulk diamond. At 20 GPa, diamondoid-to-diamond conversion occurs rapidly within <19 µs. Molecular dynamics simulations indicate that once dehydrogenated, the remaining diamondoid carbon cages reconstruct themselves into diamond-like structures at high P-T. This study is the first successful mapping of the P-T conditions and onset timing of the diamondoid-to-diamond conversion and elucidates the physical and chemical factors that facilitate diamond synthesis.

Experimental measurement of the diamond nucleation landscape reveals classical and nonclassical features.

Nucleation is a core scientific concept that describes the formation of new phases and materials. While classical nucleation theory is applied across wide-ranging fields, nucleation energy landscapes have never been directly measured at the atomic level, and experiments suggest that nucleation rates often greatly exceed the predictions of classical nucleation theory. Multistep nucleation via metastable states could explain unexpectedly rapid nucleation in many contexts, yet experimental energy landscapes supporting such mechanisms are scarce, particularly at nanoscale dimensions. In this work, we measured the nucleation energy landscape of diamond during chemical vapor deposition, using a series of diamondoid molecules as atomically defined protonuclei. We find that 26-carbon atom clusters, which do not contain a single bulk atom, are postcritical nuclei and measure the nucleation barrier to be more than four orders of magnitude smaller than prior bulk estimations. These data support both classical and nonclassical concepts for multistep nucleation and growth during the gas-phase synthesis of diamond and other semiconductors. More broadly, these measurements provide experimental evidence that agrees with recent conceptual proposals of multistep nucleation pathways with metastable molecular precursors in diverse processes, ranging from cloud formation to protein crystallization, and nanoparticle synthesis.

Assigning the absolute configuration of single aliphatic molecules by visual inspection.

Deciphering absolute configuration of a single molecule by direct visual inspection is the next step in compound identification, with far-reaching implications for medicinal chemistry, pharmacology, and natural product synthesis. We demonstrate the feasibility of this approach utilizing low temperature atomic force microscopy (AFM) with a CO-functionalized tip to determine the absolute configuration and orientation of a single, adsorbed [123]tetramantane molecule, the smallest chiral diamondoid. We differentiate between single enantiomers on Cu(111) by direct visual inspection, and furthermore identify molecular dimers and molecular clusters. The experimental results are confirmed by a computational study that allowed quantification of the corresponding intermolecular interactions. The unique toolset of absolute configuration determination combined with AFM tip manipulation opens a route for studying molecular nucleation, including chirality-driven assembly or reaction mechanisms.

One-dimensional hydrogen bonding networks of bis-hydroxylated diamantane formed inside double-walled carbon nanotubes.

1,6-Bis(hydroxymethyl)diamantane spontaneously aligns inside double-walled carbon nanotubes. The encapsulated molecules form a one-dimensional network within the double-walled carbon nanotubes through hydrogen bonding that leads to a highly dense filling as compared to unfunctionalized diamantane. Improving the encapsulation yields of precursors via functionalization is crucial to prepare novel one-dimensional materials.

Sterically controlled mechanochemistry under hydrostatic pressure.

Mechanical stimuli can modify the energy landscape of chemical reactions and enable reaction pathways, offering a synthetic strategy that complements conventional chemistry. These mechanochemical mechanisms have been studied extensively in one-dimensional polymers under tensile stress using ring-opening and reorganization, polymer unzipping and disulfide reduction as model reactions. In these systems, the pulling force stretches chemical bonds, initiating the reaction. Additionally, it has been shown that forces orthogonal to the chemical bonds can alter the rate of bond dissociation. However, these bond activation mechanisms have not been possible under isotropic, compressive stress (that is, hydrostatic pressure). Here we show that mechanochemistry through isotropic compression is possible by molecularly engineering structures that can translate macroscopic isotropic stress into molecular-level anisotropic strain. We engineer molecules with mechanically heterogeneous components-a compressible ('soft') mechanophore and incompressible ('hard') ligands. In these 'molecular anvils', isotropic stress leads to relative motions of the rigid ligands, anisotropically deforming the compressible mechanophore and activating bonds. Conversely, rigid ligands in steric contact impede relative motion, blocking reactivity. We combine experiments and computations to demonstrate hydrostatic-pressure-driven redox reactions in metal-organic chalcogenides that incorporate molecular elements that have heterogeneous compressibility, in which bending of bond angles or shearing of adjacent chains activates the metal-chalcogen bonds, leading to the formation of the elemental metal. These results reveal an unexplored reaction mechanism and suggest possible strategies for high-specificity mechanosynthesis.

Monochromatic Photocathodes from Graphene-Stabilized Diamondoids.

The monochromatic photoemission from diamondoid monolayers provides a new strategy to create electron sources with low energy dispersion and enables compact electron guns with high brightness and low beam emittance for aberration-free imaging, lithography, and accelerators. However, these potential applications are hindered by degradation of diamondoid monolayers under photon irradiation and electron bombardment. Here, we report a graphene-protected diamondoid monolayer photocathode with 4-fold enhancement of stability compared to the bare diamondoid counterpart. The single-layer graphene overcoating preserves the monochromaticity of the photoelectrons, showing 12.5 meV ful width at half-maximum distribution of kinetic energy. Importantly, the graphene coating effectively suppresses desorption of the diamondoid monolayer, enhancing its thermal stability by at least 100 K. Furthermore, by comparing the decay rate at different photon energies, we identify electron bombardment as the principle decay pathway for diamondoids under graphene protection. This provides a generic approach for stabilizing volatile species on photocathode surfaces, which could greatly improve performance of electron emitters.

Host-Guest Complexes of Cyclodextrins and Nanodiamonds as a Strong Non-Covalent Binding Motif for Self-Assembled Nanomaterials.

We report the inclusion of carboxy- and amine-substituted molecular nanodiamonds (NDs) adamantane, diamantane, and triamantane by ß-cyclodextrin and γ-cyclodextrin (ß-CD and γ-CD), which have particularly well-suited hydrophobicity and symmetry for an optimal fit of the host and guest molecules. We studied the host-guest interactions in detail and generally observed 1:1 association of the NDs with the larger γ-CD cavity, but observed 1:2 association for the largest ND in the series (triamantane) with ß-CD. We found higher binding affinities for carboxy-substituted NDs than for amine-substituted NDs. Additionally, cyclodextrin vesicles (CDVs) were decorated with d-mannose by using adamantane, diamantane, and triamantane as non-covalent anchors, and the resulting vesicles were compared with the lectin concanavalin A in agglutination experiments. Agglutination was directly correlated to the host-guest association: adamantane showed lower agglutination than di- or triamantane with ß-CDV and almost no agglutination with γ-CDV, whereas high agglutination was observed for di- and triamantane with γ-CDV.

London Dispersion Directs On-Surface Self-Assembly of [121]Tetramantane Molecules.

London dispersion (LD) acts between all atoms and molecules in nature, but the role of LD interactions in the self-assembly of molecular layers is still poorly understood. In this study, direct visualization of single molecules using atomic force microscopy with CO-functionalized tips revealed the exact adsorption structures of bulky and highly polarizable [121]tetramantane molecules on Au(111) and Cu(111) surfaces. We determined the absolute molecular orientations of the completely sp3-hybridized tetramantanes on metal surfaces. Moreover, we demonstrate how LD drives this on-surface self-assembly of [121]tetramantane hydrocarbons, resulting in the formation of a highly ordered 2D lattice. Our experimental findings were underpinned by a systematic computational study, which allowed us to quantify the energies associated with LD interactions and to analyze intermolecular close contacts and attractions in detail.

Hybrid metal-organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly.

Controlling inorganic structure and dimensionality through structure-directing agents is a versatile approach for new materials synthesis that has been used extensively for metal-organic frameworks and coordination polymers. However, the lack of 'solid' inorganic cores requires charge transport through single-atom chains and/or organic groups, limiting their electronic properties. Here, we report that strongly interacting diamondoid structure-directing agents guide the growth of hybrid metal-organic chalcogenide nanowires with solid inorganic cores having three-atom cross-sections, representing the smallest possible nanowires. The strong van der Waals attraction between diamondoids overcomes steric repulsion leading to a cis configuration at the active growth front, enabling face-on addition of precursors for nanowire elongation. These nanowires have band-like electronic properties, low effective carrier masses and three orders-of-magnitude conductivity modulation by hole doping. This discovery highlights a previously unexplored regime of structure-directing agents compared with traditional surfactant, block copolymer or metal-organic framework linkers.

Effects of Molecular Geometry on the Properties of Compressed Diamondoid Crystals.

Diamondoids are an intriguing group of carbon-based nanomaterials, which combine desired properties of inorganic nanomaterials and small hydrocarbon molecules with atomic-level uniformity. In this Letter, we report the first comparative study on the effect of pressure on a series of diamondoid crystals with systematically varying molecular geometries and shapes, including zero-dimensional (0D) adamantane; one-dimensional (1D) diamantane, [121]tetramantane, [123]tetramantane, and [1212]pentamantane; two-dimensional (2D) [12312]hexamantane; and three-dimensional (3D) triamantane and [1(2,3)4]pentamantane. We find the bulk moduli of these diamondoid crystals are strongly dependent on the diamondoids' molecular geometry with 3D [1(2,3)4]pentamantane being the least compressible and 0D adamantane being the most compressible. These diamondoid crystals possess excellent structural rigidity and are able to sustain large volume deformation without structural failure even after repetitive pressure loading cycles. These properties are desirable for constructing cushioning devices. We also demonstrate that lower diamondoids outperform the conventional cushioning materials in both the working pressure range and energy absorption density.

Ultralow effective work function surfaces using diamondoid monolayers.

Electron emission is critical for a host of modern fabrication and analysis applications including mass spectrometry, electron imaging and nanopatterning. Here, we report that monolayers of diamondoids effectively confer dramatically enhanced field emission properties to metal surfaces. We attribute the improved emission to a significant reduction of the work function rather than a geometric enhancement. This effect depends on the particular diamondoid isomer, with [121]tetramantane-2-thiol reducing gold's work function from ∼ 5.1 eV to 1.60 ± 0.3 eV, corresponding to an increase in current by a factor of over 13,000. This reduction in work function is the largest reported for any organic species and also the largest for any air-stable compound. This effect was not observed for sp(3)-hybridized alkanes, nor for smaller diamondoid molecules. The magnitude of the enhancement, molecule specificity and elimination of gold metal rearrangement precludes geometric factors as the dominant contribution. Instead, we attribute this effect to the stable radical cation of diamondoids. Our computed enhancement due to a positively charged radical cation was in agreement with the measured work functions to within ± 0.3 eV, suggesting a new paradigm for low-work-function coatings based on the design of nanoparticles with stable radical cations.

Correction: Size and shape dependent photoluminescence and excited state decay rates of diamondoids.

Correction for 'Size and shape dependent photoluminescence and excited state decay rates of diamondoids' by Robert Richter et al., Phys. Chem. Chem. Phys., 2014, 16, 3070-3076.

Template Synthesis of Linear-Chain Nanodiamonds Inside Carbon Nanotubes from Bridgehead-Halogenated Diamantane Precursors.

A simple method for the synthesis of linear-chain diamond-like nanomaterials, so-called diamantane polymers, is described. This synthetic approach is primarily based on a template reaction of dihalogen-substituted diamantane precursors in the hollow cavities of carbon nanotubes. Under high vacuum and in the presence of Fe nanocatalyst particles, the dehalogenated radical intermediates spontaneously form linear polymer chains within the carbon nanotubes. Transmission electron microscopy reveals the formation of well-aligned linear polymers. We expect that the present template-based approach will enable the synthesis of a diverse range of linear-chain polymers by choosing various precursor molecules. The present technique may offer a new strategy for the design and synthesis of one-dimensional nanomaterials.

NMR spectral properties of the tetramantanes - nanometer-sized diamondoids.

Tetramantanes, and all diamondoid hydrocarbons, possess carbon frameworks that are superimposable upon the cubic diamond lattice. This characteristic is invaluable in assigning their (1)H and (13)C NMR spectra because it translates into repeating structural features, such as diamond-cage isobutyl moieties with distinctively complex methine to methylene signatures in COSY and HMBC data, connected to variable, but systematic linkages of methine and quaternary carbons. In all tetramantane C22H28 isomers, diamond-lattice structures result in long-range (4)JHH, W-coupling in COSY data, except where negated by symmetry; there are two highly symmetrical and one chiral tetramantane (showing seven (4)JHH). Isobutyl-cage methines of lower diamondoids and tetramantanes are the most shielded resonances in their (13)C spectra (<29.5 ppm). The isobutyl methylenes are bonded to additional methines and at least one quaternary carbon in the tetramantanes. W-couplings between these methines and methylenes clarify spin-network interconnections and detailed surface hydrogen stereochemistry. Vicinal couplings of the isobutyl methylenes reveal positions of the quaternary carbons: HMBC data then tie the more remote spin systems together. Diamondoid (13) C NMR chemical shifts are largely determined by α and ß effects, however γ-shielding effects are important in [123]tetramantane. (1)H NMR chemical shifts generally correlate with numbers of 1,3-diaxial H-H interactions. Tight van der Waals contacts within [123]tetramantane's molecular groove, however, form improper hydrogen bonds, deshielding hydrogen nuclei inside the groove, while shielding those outside, indicated by Δδ of 1.47 ppm for geminal hydrogens bonded to C-3,21. These findings should be valuable in future NMR studies of diamondoids/nanodiamonds of increasing size.

Laser-induced fluorescence of free diamondoid molecules.

We observe the fluorescence of pristine diamondoids in the gas phase, excited using narrow band ultraviolet laser light. The emission spectra show well-defined features, which can be attributed to transitions from the excited electronic state into different vibrational modes of the electronic ground state. We assign the normal modes responsible for the vibrational bands, and determine the geometry of the excited states. Calculations indicate that for large diamondoids, the spectral bands do not result from progressions of single modes, but rather from combination bands composed of a large number of Δv = 1 transitions. The vibrational modes determining the spectral envelope can mainly be assigned to wagging and twisting modes of the surface atoms. We conclude that our theoretical approach accurately describes the photophysics in diamondoids and possibly other hydrocarbons in general.

Deviatoric stress-induced phase transitions in diamantane.

The high-pressure behavior of diamantane was investigated using angle-dispersive synchrotron x-ray diffraction (XRD) and Raman spectroscopy in diamond anvil cells. Our experiments revealed that the structural transitions in diamantane were extremely sensitive to deviatoric stress. Under non-hydrostatic conditions, diamantane underwent a cubic (space group Pa3) to a monoclinic phase transition at below 0.15 GPa, the lowest pressure we were able to measure. Upon further compression to 3.5 GPa, this monoclinic phase transformed into another high-pressure monoclinic phase which persisted to 32 GPa, the highest pressure studied in our experiments. However, under more hydrostatic conditions using silicone oil as a pressure medium, the transition pressure to the first high-pressure monoclinic phase was elevated to 7-10 GPa, which coincided with the hydrostatic limit of silicone oil. In another experiment using helium as a pressure medium, no phase transitions were observed to the highest pressure we reached (13 GPa). In addition, large hysteresis and sluggish transition kinetics were observed upon decompression. Over the pressure range where phase transitions were confirmed by XRD, only continuous changes in the Raman spectra were observed. This suggests that these phase transitions are associated with unit cell distortions and modifications in molecular packing rather than the formation of new carbon-carbon bonds under pressure.

Unconventional molecule-resolved current rectification in diamondoid-fullerene hybrids.

The unimolecular rectifier is a fundamental building block of molecular electronics. Rectification in single molecules can arise from electron transfer between molecular orbitals displaying asymmetric spatial charge distributions, akin to p-n junction diodes in semiconductors. Here we report a novel all-hydrocarbon molecular rectifier consisting of a diamantane-C60 conjugate. By linking both sp(3) (diamondoid) and sp(2) (fullerene) carbon allotropes, this hybrid molecule opposingly pairs negative and positive electron affinities. The single-molecule conductances of self-assembled domains on Au(111), probed by low-temperature scanning tunnelling microscopy and spectroscopy, reveal a large rectifying response of the molecular constructs. This specific electronic behaviour is postulated to originate from the electrostatic repulsion of diamantane-C60 molecules due to positively charged terminal hydrogen atoms on the diamondoid interacting with the top electrode (scanning tip) at various bias voltages. Density functional theory computations scrutinize the electronic and vibrational spectroscopic fingerprints of this unique molecular structure and corroborate the unconventional rectification mechanism.

Selective preparation of diamondoid phosphonates.

We present an effective sequence for the preparation of phosphonic acid derivatives of the diamondoids diamantane, triamantane, [121]tetramantane, and [1(2,3)4]pentamantane. The reactions of the corresponding diamondoid hydroxy derivatives with PCl3 in sulfuric or trifluoroacetic acid give mono- as well as didichlorophosphorylated diamondoids in high preparative yields.

Size and shape dependent photoluminescence and excited state decay rates of diamondoids.

We present photoluminescence spectra and excited state decay rates of a series of diamondoids, which represent molecular structural analogues to hydrogen-passivated bulk diamond. Specific isomers of the five smallest diamondoids (adamantane-pentamantane) have been brought into the gas phase and irradiated with synchrotron radiation. All investigated compounds show intrinsic photoluminescence in the ultraviolet spectral region. The emission spectra exhibit pronounced vibrational fine structure which is analyzed using quantum chemical calculations. We show that the geometrical relaxation of the first excited state of adamantane, exhibiting Rydberg character, leads to the loss of Td symmetry. The luminescence of adamantane is attributed to a transition from the delocalized first excited state into different vibrational modes of the electronic ground state. Similar geometrical changes of the excited state structure have also been identified in the other investigated diamondoids. The excited state decay rates show a clear dependence on the size of the diamondoid, but are independent of the particle geometry, further indicating a loss of particle symmetry upon electronic excitation.