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.

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.

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.

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.

Vertical-Substrate MPCVD Epitaxial Nanodiamond Growth.

Color center-containing nanodiamonds have many applications in quantum technologies and biology. Diamondoids, molecular-sized diamonds have been used as seeds in chemical vapor deposition (CVD) growth. However, optimizing growth conditions to produce high crystal quality nanodiamonds with color centers requires varying growth conditions that often leads to ad-hoc and time-consuming, one-at-a-time testing of reaction conditions. In order to rapidly explore parameter space, we developed a microwave plasma CVD technique using a vertical, rather than horizontally oriented stage-substrate geometry. With this configuration, temperature, plasma density, and atomic hydrogen density vary continuously along the vertical axis of the substrate. This variation allowed rapid identification of growth parameters that yield single crystal diamonds down to 10 nm in size and 75 nm diameter optically active center silicon-vacancy (Si-V) nanoparticles. Furthermore, this method may provide a means of incorporating a wide variety of dopants in nanodiamonds without ion irradiation damage.

Overcoming lability of extremely long alkane carbon-carbon bonds through dispersion forces.

Steric effects in chemistry are a consequence of the space required to accommodate the atoms and groups within a molecule, and are often thought to be dominated by repulsive forces arising from overlapping electron densities (Pauli repulsion). An appreciation of attractive interactions such as van der Waals forces (which include London dispersion forces) is necessary to understand chemical bonding and reactivity fully. This is evident from, for example, the strongly debated origin of the higher stability of branched alkanes relative to linear alkanes and the possibility of constructing hydrocarbons with extraordinarily long C-C single bonds through steric crowding. Although empirical bond distance/bond strength relationships have been established for C-C bonds (longer C-C bonds have smaller bond dissociation energies), these have no present theoretical basis. Nevertheless, these empirical considerations are fundamental to structural and energetic evaluations in chemistry, as summarized by Pauling as early as 1960 and confirmed more recently. Here we report the preparation of hydrocarbons with extremely long C-C bonds (up to 1.704 Å), the longest such bonds observed so far in alkanes. The prepared compounds are unexpectedly stable--noticeable decomposition occurs only above 200 °C. We prepared the alkanes by coupling nanometre-sized, diamond-like, highly rigid structures known as diamondoids. The extraordinary stability of the coupling products is due to overall attractive dispersion interactions between the intramolecular H•••H contact surfaces, as is evident from density functional theory computations with and without inclusion of dispersion corrections.

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.

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.

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.

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.

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.

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.

Infrared spectroscopy of molecular submonolayers on surfaces by infrared scanning tunneling microscopy: tetramantane on Au111.

We have developed a new scanning-tunneling-microscopy-based spectroscopy technique to characterize infrared (IR) absorption of submonolayers of molecules on conducting crystals. The technique employs a scanning tunneling microscope as a precise detector to measure the expansion of a molecule-decorated crystal that is irradiated by IR light from a tunable laser source. Using this technique, we obtain the IR absorption spectra of [121]tetramantane and [123]tetramantane on Au(111). Significant differences between the IR spectra for these two isomers show the power of this new technique to differentiate chemical structures even when single-molecule-resolved scanning tunneling microscopy (STM) images look quite similar. Furthermore, the new technique was found to yield significantly better spectral resolution than STM-based inelastic electron tunneling spectroscopy, and to allow determination of optical absorption cross sections. Compared to IR spectroscopy of bulk tetramantane powders, infrared scanning tunneling microscopy (IRSTM) spectra reveal narrower and blueshifted vibrational peaks for an ordered tetramantane adlayer. Differences between bulk and surface tetramantane vibrational spectra are explained via molecule-molecule interactions.

Covalent attachment of diamondoid phosphonic acid dichlorides to tungsten oxide surfaces.

Diamondoids (nanometer-sized diamond-like hydrocarbons) are a novel class of carbon nanomaterials that exhibit negative electron affinity (NEA) and strong electron-phonon scattering. Surface-bound diamondoid monolayers exhibit monochromatic photoemission, a unique property that makes them ideal electron sources for electron-beam lithography and high-resolution electron microscopy. However, these applications are limited by the stability of the chemical bonding of diamondoids on surfaces. Here we demonstrate the stable covalent attachment of diamantane phosphonic dichloride on tungsten/tungsten oxide surfaces. X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared (FTIR) spectroscopy revealed that diamondoid-functionalized tungsten oxide films were stable up to 300-350 °C, a substantial improvement over conventional diamondoid thiolate monolayers on gold, which dissociate at 100-200 °C. Extreme ultraviolet (EUV) light stimulated photoemission from these diamondoid phosphonate monolayers exhibited a characteristic monochromatic NEA peak with 0.2 eV full width at half-maximum (fwhm) at room temperature, showing that the unique monochromatization property of diamondoids remained intact after attachment. Our results demonstrate that phosphonic dichloride functionality is a promising approach for forming stable diamondoid monolayers for elevated temperature and high-current applications such as electron emission and coatings in micro/nano electromechanical systems (MEMS/NEMS).

Electronic structure tuning of diamondoids through functionalization.

We investigated the changes in electronic structures induced by chemical functionalization of the five smallest diamondoids using valence photoelectron spectroscopy. Through the variation of three parameters, namely functional group (thiol, hydroxy, and amino), host cluster size (adamantane, diamantane, triamantane, [121]tetramantane, and [1(2,3)4]pentamantane), and functionalization site (apical and medial) we are able to determine to what degree these affect the electronic structures of the overall systems. We show that unlike, for example, in the case of halobenzenes, the ionization potential does not show a linear dependence on the electronegativity of the functional group. Instead, a linear correlation exists between the HOMO-1 ionization potential and the functional group electronegativity. This is due to localization of the HOMO on the functional group and the HOMO-1 on the diamondoid cage. Density functional theory supports our interpretations.

Stable alkanes containing very long carbon-carbon bonds.

The metal-induced coupling of tertiary diamondoid bromides gave highly sterically congested hydrocarbon (hetero)dimers with exceptionally long central C-C bonds of up to 1.71 Å in 2-(1-diamantyl)[121]tetramantane. Yet, these dimers are thermally very stable even at temperatures above 200 °C, which is not in line with common C-C bond length versus bond strengths correlations. We suggest that the extraordinary stabilization arises from numerous intramolecular van der Waals attractions between the neighboring H-terminated diamond-like surfaces. The C-C bond rotational dynamics of 1-(1-adamantyl)diamantane, 1-(1-diamantyl)diamantane, 2-(1-adamantyl)triamantane, 2-(1-diamantyl)triamantane, and 2-(1-diamantyl)[121]tetramantane were studied through variable-temperature (1)H- and (13)C NMR spectroscopies. The shapes of the inward (endo) CH surfaces determine the dynamic behavior, changing the central C-C bond rotation barriers from 7 to 33 kcal mol(-1). We probe the ability of popular density functional theory (DFT) approaches (including BLYP, B3LYP, B98, B3LYP-Dn, B97D, B3PW91, BHandHLYP, B3P86, PBE1PBE, wB97XD, and M06-2X) with 6-31G(d,p) and cc-pVDZ basis sets to describe such an unusual bonding situation. Only functionals accounting for dispersion are able to reproduce the experimental geometries, while most DFT functionals are able to reproduce the experimental rotational barriers due to error cancellations. Computations on larger diamondoids reveal that the interplay between the shapes and the sizes of the CH surfaces may even allow the preparation of open-shell alkyl radical dimers (and possibly polymers) that are strongly held together exclusively by dispersion forces.

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.

Experimental and theoretical study of the absorption properties of thiolated diamondoids.

Nanoscale hybrid systems are a new class of molecular aggregates that offer numerous new possibilities in materials design. Diamondoid thiols are promising nanoscale building blocks for such hybrid systems. They allow the incorporation of functional groups and the investigation of their effects on the unique materials' properties of diamondoids. Here we combine experimental data with ab initio theory to explore the optical properties of diamondoid thiols and their dependence on size and shape. Agreement between theoretically and experimentally obtained absorption spectra allows the identification of the nature of the optical transitions that are responsible for some photophysical and photochemical processes. We show that the optical properties of diamondoid thiols in the deep UV regime depend on the functionalization site but are largely size independent. Our findings provide an explanation for the disappearance of diamondoid UV photoluminescence upon thiolation for smaller diamondoids. However, our theoretical results indicate that for larger diamondoid thiols beyond the critical size of six diamondoid cages the lowest energy transitions are characterized by diamondoidlike states suggesting that UV luminescence may be regained.

Biological sulfur in the blood cells of Ascidia ceratodes: XAS spectroscopy and a cellular-enzymatic hypothesis for vanadium reduction in the ascidians.

Two samples of living blood cells and of cleared blood plasma from the Phlebobranch tunicate Ascidia ceratodes from Bodega Bay, California, and one of fresh Henze solution from A. ceratodes of Monterey Bay, California, have been examined using sulfur K-edge x-ray absorption spectroscopy (XAS). Biological sulfur included sulfate esters, sulfate and bisulfate ions, benzothiazole, thianthrene, epi-sulfide, thiol and disulfide. Glutathione dominated reduced sulfur, from which an average intracellular Voltage of -0.21 V was calculated. Sulfate-bisulfate ratios yielded blood cell pH values of 2.0 and 2.8. Total blood cell [sulfur] was 373±9 mM or 296±73 mM from BaSO4 gravimetry. Two plasma samples (pH 6.9 or 7.0; [S] = 33±6 mM or 26±4 mM) were dominated by sulfate and disulfide. Fresh Henze solution evidenced a sulfur inventory similar to blood cells, with calculated pH = 2.7. A V(III)-sulfonate fraction varied systematically with intracellular pH across six independent blood cell samples, implying a vanadium mobilization pathway. Bodega Bay and Monterey Bay A. ceratodes appear to maintain alternative suites of low-valent sulfur. The significance of the vanabins to vanadium metabolism is critically examined in terms of known protein - V(IV) biochemistry. Finally, a detailed hypothesis for the reduction of [VO4]3- to V(III) in ascidians is introduced. A vanadium oxido-reductase is proposed to span the signet ring membrane and to release V(III) into the inner acidic vacuole. The V(V) to V(III) reduction is predicted require an inner-sphere mechanism, a thiol reductant, 7-coordinate V(III), a biologically accessible Voltage, and proton-facilitated release of V(III).