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Although the desirability of developing synthetic molecular machine systems that can function on surfaces is widely recognized, to date the only well-characterized examples of electrochemically switchable rotaxane-based molecular shuttles which can do so are based on the tetracationic viologen macrocycle pioneered by Stoddart. Here, we report on a [2]rotaxane which features succinamide and naphthalene diimide hydrogen-bonding stations for a benzylic amide macrocycle that can shuttle and switch its net position both in solution and in a monolayer. Three oxidation states of the naphthalene diimide unit can be accessed electrochemically in solution, each one with a different binding affinity for the macrocycle and, hence, corresponding to a different distribution of the rings between the two stations in the molecular shuttle. Cyclic voltammetry experiments show the switching to be both reversible and cyclable and allow quantification of the translational isomer ratios (thermodynamics) and shuttling dynamics (kinetics) for their interconversion in each state. Overall, the binding affinity of the naphthalene diimide station can be changed by 6 orders of magnitude over the three states. Unlike previous electrochemically active amide-based molecular shuttles, the reduction potential of the naphthalene diimide unit is sufficiently positive (-0.68 V) for the process to be compatible with operation in self-assembled monolayers on gold. Incorporating pyridine units into the macrocycle allowed attachment of the shuttles to an acid-terminated self-assembled monolayer of alkane thiols on gold. The molecular shuttle monolayers were characterized by X-ray photoelectron spectroscopy and their electrochemical behavior probed by electrochemical impedance spectroscopy and double-potential step chronoamperometry, which demonstrated that the redox-switched shuttling was maintained in this environment, occurring on the millisecond time scale.

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A new family of mono- and dinuclear ruthenium polypyridyl complexes containing 5-aryltetrazolate ligands such as the deprotonated form of 4-(1H-tetrazol-5-yl)benzonitrile (4-TBNH) and bis(1H-tetrazol-5-yl)benzene (BTBH(2)) have been synthesized and thoroughly characterized. The reactivity of the mononuclear species toward different electrophiles such as H(+) and CH(3)(+) has been investigated, and the effects of the resulting regioselective electrophilic attacks on the electronic and structural properties of the tetrazolate ligand have been studied by NMR ((1)H, (13)C) spectroscopy and X-ray crystal structures. Absorption and emission spectroscopy, together with an electrochemical and UV-vis-NIR spectroelectrochemical investigation of the uncoordinated ligand and complexes, has been performed, highlighting a rather good luminescence efficiency and a poor bridge-mediated electronic communication between the metal centers of the dinuclear complexes. The electrogenerated chemiluminescence (ECL) of the dinuclear species has been explored, and for one of these, an exceptionally high ECL efficiency has been observed, comparable to that of [Ru(bpy)(3)](2+), which is considered a standard in ECL studies.

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The voltammetric generation of corannulene anions was investigated over a large range of experimental conditions comprising either "traditional" electrochemical solvents, such as dimethylformamide, acetonitrile, and tetrahydrofuran, or "unconventional" solvents, such as liquid ammonia, liquid methylamine, or liquid dimethylamine, and several different supporting electrolytes. Strong ion pairing effects were found to dominate the electrochemical generation of corannulene higher anions, and through the suitable choice of the solvent/electrolyte system, we observed, for the first time, the reversible electrochemical generation of up to the triply reduced corannulene. The standard potentials obtained experimentally compared rather well with the theoretical values calculated by ab initio and density functional methods, in which solvation and ion pairing effect were explicitly taken into account. In particular, the calculations considered the effect of the electrolyte cation size on ion pairing in order to rationalize the occurrence of the third reduction within the experimental potential window.

Stardust grains recovered from meteorites provide highprecision\ud snapshots of the isotopic composition of the stellar\ud environment in which they formed1. Attributing their origin\ud to specific types of stars, however, often proves difficult.\ud Intermediate-mass stars of 4–8 solar masses are expected\ud to have contributed a large fraction of meteoritic stardust2,3.\ud Yet, no grains have been found with the characteristic isotopic\ud compositions expected for such stars4,5. This is a long-standing\ud puzzle, which points to serious gaps in our understanding of\ud the lifecycle of stars and dust in our Galaxy. Here we show that\ud the increased proton-capture rate of 17O reported by a recent\ud underground experiment6 leads to 17O/16O isotopic ratios that\ud match those observed in a population of stardust grainsfor\ud proton-burning temperatures of 60–80 MK. These temperatures\ud are achieved at the base of the convective envelope\ud during the late evolution of intermediate-mass stars of\ud 4–8 solar masses7–9, which reveals them as the most likely site\ud of origin of the grains. This result provides direct evidence\ud that these stars contributed to the dust inventory from which\ud the Solar System formed

Electrochemiluminescence of corannulene in acetonitrile by the use of coreactants is reported here for the first time. The investigation has been carried out utilizing both benzoyl peroxide as a sacrificial coreactant and arylamine derivatives as nonsacrificial species to perform mixed-annihilation processes. The electrochemiluminescence produces an intense blue light. The use of different tris(arylamines) as mixed-annihilation coreactants gives rise to exciplexes with corannulene that emit at different wavelengths, thus allowing the emission color to be tuned by changing the coreactant molecule. This opens a potential pathway to exploitation of such an intriguing carbon structure for building efficient blue-light emitting devices.