Self-organization of rotaxane thin films into spatially correlated nanostructures: morphological and structural aspects

The self-organization of rotaxane thin films into spatially correlated nanostructures is shown to occur upon a thermal stimulus. The mechanism of formation of nanostructures and their organization has been investigated using atomic force microscopy, bright field transmission electron microscopy, selected area electron diffraction, and molecular mechanics simulations. The evolution of the nanostructures follows a complex pathway, where a rotaxane thin film first dewets from the substrate to form nanosized droplets. Droplets coalesce by ripening, generating spatially correlated motifs. In a later stage, the larger droplets change shape, nucleate, and coalesce to yield crystallites that grow into larger crystals by incorporating the surrounding droplets. The results show the following: (i) the nanostructures represent a metastable state of a crystallization process; (ii) spatial correlations emerge during ripening, but they are destroyed as stable nuclei are formed and crystallization proceeds to completion; iii) crystallization, either on graphite or amorphous carbon films, leads to a precise basal plane, viz. (010), which has minimum surface energy. The inherent degrees of freedom permitted in the rotaxane architecture favors the re-organization and nucleation of the film in the solid state. Low-energy trajectories leading to crystallites with stable surfaces and minimum energy contact plane are found to occur via concerted, small amplitude, internal motions without disruption of packing and intermolecular contacts.     

Interactions in single wall carbon nanotubes/pyrene/porphyrin nanohybrids

This work provides an in-depth look at a range of physicochemical aspects of (i) single wall carbon nanotubes (SWNT), (ii) pyrene derivatives (pyrene(+)), (iii) porphyrin derivatives (ZnP(8)()(-)() and H(2)()P(8)()(-)()), (iv) poly(sodium 4-styrenesulfonate), and (v) their combinations. Implicit in their supramolecular combinations is the hierarchical integration of SWNT (as electron acceptors), together with ZnP(8)()(-)() or H(2)()P(8)()(-)() (as electron donors), in an aqueous environment mediated through pyrene(+). This supramolecular approach yields novel electron donor-acceptor nanohybrids (SWNT/pyrene(+)/ZnP(8)()(-)() or SWNT/pyrene(+)/H(2)()P(8)()(-)()). In particular, we report on electrochemical and photophysical investigations that as a whole suggest sizeable and appreciable interactions between the individual components. The key step to form SWNT/pyrene(+)()/ZnP(8)()(-)() or SWNT/pyrene(+)()/H(2)()P(8)()(-)() hybrids is pi-pi interactions between SWNT and pyrene(+), for which we have developed for the first time a sensitive marker. The marker is the monomeric pyrene fluorescence, which although quenched is (i) only present in SWNT/pyrene(+) and (ii) completely lacking in just pyrene(+). Electrostatic interactions help to immobilize ZnP(8)()(-)() or H(2)()P(8)()(-)() onto SWNT/pyrene(+) to yield the final electron donor-acceptor nanohybrids. A series of photochemical experiments confirm that long-lived radical ion pairs are formed as a product of a rapid excited-state deactivation of ZnP(8)()(-)() or H(2)()P(8)()(-)(). This formation is fully rationalized on the basis of the properties of the individual moieties. Additional modeling shows that the data are likely to be relevant to the SWNTs present in the sample, which possess wider diameters.     

Adsorption of fumaramide [2]rotaxane and its components on a solid substrate: a coverage-dependent study

The coverage-dependent adsorption on Au(111) of a fumaramide [2]rotaxane and its components, a benzylic amide macrocycle and a fumaramide thread, is studied using high-resolution electron energy loss spectroscopy (HREELS). Up to monolayer coverage, the relative intensity of out-of-plane to in-plane phenyl ring vibrational modes indicates that the macrocycle adopts an orientation with the phenyl rings largely parallel to the surface. The formation of a chemisorption bond is evidenced by the presence of a Au-O stretching vibration. In contrast, the thread shows no evidence of chemisorption or a preferential orientation. The introduction of the thread into the macrocycle partly disrupts the film order so that the resulting chemisorbed rotaxane shows intermediate behavior with a preferential orientation up to 0.5 ML coverage. A decrease in film order and the absence of a preferred molecular orientation is observed for all three molecules at multilayer coverages. The spectral differences are addressed by molecular dynamics simulations in terms of the mobility of the phenyls of the three molecules on Au(111).     

Hydrodynamic modeling of diffusion tensor properties of flexible molecules

We present a computationally efficient implementation of hydrodynamic modeling for the evaluation of diffusion tensors of molecules with internal degrees of freedom, adapted to take into account information from linear scaling computations of solvent accessible surfaces implemented in the framework of last generation continuum solvent models. Torsional angles are taken also explicitly into account, while retaining correct hydrodynamic interactions. A comparison with literature data is presented to prove the effectiveness of the approach for a wide range of molecular dimensions and solvent environments.     

Nanostructured TiO x film on Si substrate: room temperature formation of TiSi x nanoclusters

We present a morphologic and spectroscopic study of cluster-assembled TiO _x films deposited by supersonic cluster beam source on clean silicon substrates. Data show the formation of nanometer—thick and uniform titanium silicides film at room temperature (RT). Formation of such thick TiSi _x film goes beyond the classical interfacial limit set by the Ti/Si diffusion barrier. The enhancement of Si diffusion through the TiO _x film is explained as a direct consequence of the porous film structure. Upon ultra high vacuum annealing beyond 600 °C, TiSi₂ is formed and the oxygen present in the film is completely desorbed. The morphology of the nanostructured silicides is very stable for thermal treatments in the RT—1000 °C range, with a slight cluster size increase, resulting in a film roughness an order of magnitude smaller than other TiO _x /Si and Ti/Si films in the same temperature range. The present results might have a broad impact in the development of new and simple TiSi synthesis methods that favour their integration into nanodevices.     

Quantitative analysis of charge-carrier trapping in organic thin-film transistors from transfer characteristics

A dynamic method for quantifying the amount and mechanism of trapping in organic field effect transistors (OFETs) is proposed. It exploits transfer characteristics acquired upon application of a triangular waveform gate sweep V _G. The analysis of the transfer characteristics at the turning point V _G=−V _max between forward and backward gate sweeps, viz. around the maximum gate voltage V _max applied, provides a differential slope Δm which depends exclusively on trapping. Upon a systematic change of V _max it is possible to extract the initial threshold voltage, equivalent to one of the observables of conventional stress measurements, and assess the mechanism of trapping via the functional dependence on the current. The analysis of the differential logarithmic derivative at the turning point yields the parameters of trapping, as the exponent β and the time scale of trapping τ. In the case of an ultra-thin pentacene OFET we extract β=1 and τ=10²–10³ s, in agreement with an exponential distribution of traps. The analysis of the hysteresis parameter Δm is completely general and explores time scales much shorter than those involved in bias stress measurements, thus avoiding irreversible damage to the device.     

Synthesis and Comparative Investigation of Silicon Transition Metal Silicide Composite Anodes for Lithium Ion Batteries

A significant increase in energy density of lithium ion batteries (LIBs) can be achieved by using high‐capacity, silicon (Si)‐based negative electrode materials. Several challenges arise from the enormous volumetric changes of Si during lithiation/delithiation, such as disintegration/pulverization of the active material and the electrode as well as ongoing electrolyte decomposition, leading to rapid capacity fading. Here, we synthesize and comparatively investigate three different porous transition metal‐Si‐carbon composite materials that are composed of an active Si phase and the corresponding inactive metal‐silicide phases. In this material design, the inactive phases, as well as the pores serve as a buffer to attenuate the previously mentioned detrimental effects. The synthesized materials are studied with respect to their structural and surface properties and are characterized electrochemically regarding their rate performance, and long‐term charge/discharge cycling stability. Thereby, the composite materials show a promising rate capability and a high specific capacity. Their low initial Coulombic efficiency, due to the porous structure, can be partially compensated by pre‐lithiation. This is demonstrated by the application of the synthesized materials in a LIB full‐cell set‐up vs. NMC‐111 cathodes, where the amount of lithium is confined due to anode/cathode capacity balancing.     

Pyridinedicarboxamide strands form double helices via an activated slippage mechanism

The intertwining process of two strands of oligo-pyridinecarboxamides to form a double helix (Nature 2000, 407, 720) is found to consist of a series of discrete steps, where the tail of one of the strands proceeds inside the other single helix in an eddy-like process. While a plethora of minima can be located along the pathway, they exist only for a few, well-defined supramolecular arrangements of the two molecules. The initial transition state for the introduction of one molecule in the pitch of the other has the largest barrier and is therefore the rate-determining step of an activated slippage mechanism, which is characterized by a series of roller-coasting hills. Along the entire pathway, the intramolecular energy that stabilizes the single helices is slowly transformed into intermolecular energy that finally provides the necessary stabilization only near the end of the entwining process. Solvent or other chemical factors, such as the presence of ions, able to destabilize the full formation of the double helix may therefore drastically affect its formation.