Functionalized fullerenes in self-assembled monolayers

Anisotropy of intermolecular and molecule-substrate interactions holds the key to controlling the arrangement of fullerenes into 2D self-assembled monolayers (SAMs). The chemical reactivity of fullerenes allows functionalization of the carbon cages with sulfur-containing groups, thiols and thioethers, which facilitates the reliable adsorption of these molecules on gold substrates. A series of structurally related molecules, eight of which are new fullerene compounds, allows systematic investigation of the structural and functional parameters defining the geometry of fullerene SAMs. Scanning tunnelling microscopy (STM) measurements reveal that the chemical nature of the anchoring group appears to be crucial for the long-range order in fullerenes: the assembly of thiol-functionalized fullerenes is governed by strong molecule-surface interactions, which prohibit formation of ordered molecular arrays, while thioether-functionalized fullerenes, which have a weaker interaction with the surface than the thiols, form a variety of ordered 2D molecular arrays owing to noncovalent intermolecular interactions. A linear row of fullerene molecules is a recurring structural feature of the ordered SAMs, but the relative alignment and the spacing between the fullerene rows is strongly dependent on the size and shape of the spacer group linking the fullerene cage and the anchoring group. Careful control of the chemical functionality on the carbon cages enables positioning of fullerenes into at least four different packing arrangements, none of which have been observed before. Our new strategy for the controlled arrangement of fullerenes on surfaces at the molecular level will advance the development of practical applications for these nanomaterials.     

Dynamics of the glycosidic bond: conformational space of lactose

The dynamics of the glycosidic bond of lactose was studied by a paramagnetic tagging‐based NMR technique, which allowed the collection of an unusually large series of NMR data for a single compound. By the use of distance‐ and orientation‐dependent residual dipolar couplings and pseudocontact shifts, the simultaneous fitting of the probabilities of computed conformations and the orientation of the magnetic susceptibility tensor of a series of lanthanide complexes of lactose show that its glycosidic bond samples syn/syn, anti/syn and syn/anti ?/ψ regions of the conformational space in water. The analysis indicates a higher reliability of pseudocontact shift data as compared to residual dipolar couplings with the presently available weakly orienting paramagnetic tagging technique. The method presented herein allows for an improved understanding of the dynamic behaviour of oligosaccharides.     

Faster proton transfer dynamics of water on SnO2 compared to TiO2

Proton jump processes in the hydration layer on the iso-structural TiO(2) rutile (110) and SnO(2) cassiterite (110) surfaces were studied with density functional theory molecular dynamics. We find that the proton jump rate is more than three times faster on cassiterite compared with rutile. A local analysis based on the correlation between the stretching band of the O-H vibrations and the strength of H-bonds indicates that the faster proton jump activity on cassiterite is produced by a stronger H-bond formation between the surface and the hydration layer above the surface. The origin of the increased H-bond strength on cassiterite is a combined effect of stronger covalent bonding and stronger electrostatic interactions due to differences of its electronic structure. The bridging oxygens form the strongest H-bonds between the surface and the hydration layer. This higher proton jump rate is likely to affect reactivity and catalytic activity on the surface. A better understanding of its origins will enable methods to control these rates.     

Broadening the reactivity spectrum of a phthalocyanine catalyst while suppressing its nucleophilic, electrophilic and radical degradation pathways

A robust molecule that resists degradation via nucleophilic, electrophilic and radical attacks is described. Coordinated O(2) is reduced catalytically, producing efficiently thyil radicals in spite of the extreme electronic deficiency of the catalyst.     

ThermoData Engine (TDE): software implementation of the dynamic data evaluation concept. 5. Experiment planning and product design

ThermoData Engine (TDE) is the first full-scale software implementation of the dynamic data evaluation concept, as reported recently in this journal. In the present paper, we describe development of an algorithmic approach to assist experiment planning through assessment of the existing body of knowledge, including availability of experimental thermophysical property data, variable ranges studied, associated uncertainties, state of prediction methods, and parameters for deployment of prediction methods and how these parameters can be obtained using targeted measurements, etc., and, indeed, how the intended measurement may address the underlying scientific or engineering problem under consideration. A second new feature described here is the application of the software capabilities for aid in the design of chemical products through identification of chemical systems possessing desired values of thermophysical properties within defined ranges of tolerance. The algorithms and their software implementation to achieve this are described. Finally, implementation of a new data validation and weighting system is described for vapor-liquid equilibrium (VLE) data, and directions for future enhancements are outlined.     

ThermoData Engine (TDE): software implementation of the dynamic data evaluation concept. 6. Dynamic web-based data dissemination through the NIST Web Thermo Tables

ThermoData Engine (TDE) is the first full-scale software implementation of the dynamic data evaluation concept, as reported recently in this journal. In the present paper, we describe the development of a World Wide Web-based interface to TDE evaluations of pure compound properties, including critical properties, phase boundary equilibria (vapor pressures, sublimation pressures, and crystal-liquid boundary pressures), densities, energetic properties, and transport properties. This includes development of a system for caching evaluation results to maintain high availability and an advanced window-in-window interface that leverages modern Web-browser technologies. Challenges associated with bringing the principal advantages of the TDE technology to the Web are described, as are compromises to maintain general access and speed of interaction while remaining true to the tenets of dynamic data evaluation. Future extensions of the interface and associated Web-services are outlined.     

An unconditional proof of the Andr���COort conjecture for Hilbert modular surfaces

We give an unconditional proof of the André?COort conjecture for Hilbert modular surfaces asserting that an algebraic curve contained in such a surface and containing an infinite set of special points, is special. The proof relies on a combination of Galois-theoretic techniques and results from the theory of o-minimal structures.     

IR spectra of C2H5(+)-N2 isomers: evidence for dative chemical bonding in the isolated ethanediazonium ion

The potential energy surface (PES) of C(2)H(5)(+)-N(2) is characterized in detail by infrared photodissociation (IRPD) spectroscopy of mass-selected ions in a quadrupole tandem mass spectrometer and ab initio calculations at the MP2/6-311G(2df,2pd) level. The PES features three nonequivalent minima. Two local minima, 1-N(2)(H) and 1-N(2)(C), are adduct complexes with binding energies of D(0) = 18 and 12 kJ/mol, in which the N(2) ligand is weakly bonded by electrostatic forces to either the acidic proton or the electrophilic carbon atom of the nonclassical C(2)H(5)(+) ion (1), respectively. The global minimum 3 is the ethanediazonium ion, featuring a weak dative bond of D(0) = 38 kJ/mol. This interaction strength is sufficient to switch the C(2)H(5)(+) structure from nonclassical to classical. The 1-N(2)(C) isomer corresponds to the entrance channel complex for addition of N(2) to 1 yielding the product 3. This reaction involves a small barrier of 7 kJ/mol as a result of the rearrangement of the C(2)H(5)(+) ion. The partly rotationally resolved IRPD spectrum of C(2)H(5)(+)-N(2) recorded in the C-H stretch range is dominated by four bands assigned to 3 and one weak transition attributed to 1-N(2)(H). The abundance ratio of 1-N(2)(H) and 3 estimated from the IRPD spectrum as ～1% is consistent with the calculated free energy difference of 12 kJ/mol. As the ethanediazonium ion escaped previous mass spectrometric detection, the currently accepted value for the ethyl cation affinity of N(2) is revised from -ΔH(0) = 15.5 ± 1.5 to ～42 kJ/mol. The first experimental identification and characterization of 3 provides a sensitive probe of the electrophilic character and fluxionality of the ethyl cation. Comparison of 3 with related alkanediazonium ions reveals the drastic effect of the size of the alkyl chain on their chemical reactivity, which is relevant in the context of hydrocarbon plasma chemistry of planetary atmospheres and the interstellar medium, as well as alkylation reactions of (bio)organic molecules (e.g., carcinogenesis and mutagenesis of DNA material).     

Phenomenological model of spin crossover in molecular crystals as derived from atom-atom potentials

The method of atom-atom potentials, previously applied to the analysis of pure molecular crystals formed by either low-spin (LS) or high-spin (HS) forms (spin isomers) of Fe(II) coordination compounds (Sinitskiy et al., Phys. Chem. Chem. Phys., 2009, 11, 10983), is used to estimate the lattice enthalpies of mixed crystals containing different fractions of the spin isomers. The crystals under study were formed by LS and HS isomers of Fe(phen)(2)(NCS)(2) (phen = 1,10-phenanthroline), Fe(btz)(2)(NCS)(2) (btz = 5,5',6,6'-tetrahydro-4H,4'H-2,2'-bi-1,3-thiazine), and Fe(bpz)(2)(bipy) (bpz = dihydrobis(1-pyrazolil)borate, and bipy = 2,2'-bipyridine). For the first time the phenomenological parameters Γ pertinent to the Slichter-Drickamer model (SDM) of several materials were independently derived from the microscopic model of the crystals with use of atom-atom potentials of intermolecular interaction. The accuracy of the SDM was checked against the numerical data on the enthalpies of mixed crystals. Fair semiquantitative agreement with the experimental dependence of the HS fraction on temperature was achieved with use of these values. Prediction of trends in Γ values as a function of chemical composition and geometry of the crystals is possible with the proposed approach, which opens a way to rational design of spin crossover materials with desired properties.