Routes of Theophylline Monohydrate Dehydration Process Proposed by Mid-Frequency Raman Difference Spectra.

Two routes of the dehydration process of theophylline monohydrate have been proposed in this work from mid-frequency Raman difference spectra (MFRDS) results and experiments. MFRDS can establish short-range order correlations among various theophylline crystal forms. MFRDS results indicate that the short-range order of metastable Form III is most similar to that of monohydrate, which explains that Form III is the main dehydration products in the mild dehydration process. The phenomenon that unstable amorphous theophylline intermediate phase would appear during the dehydration process of theophylline monohydrate was confirmed indirectly by Powder X-ray Diffraction (PXRD) and optical microscope and reported in the previous reports, which could cause the nucleation of Form II, as MFRDS results indicate short-range order of amorphous solid dispersion of theophylline is most similar to that of Form II. MFRDS analysis shows the advantages in studying the phase transformation of small organic molecule crystals.

Evaporative Crystallization of Simvastatin from Different Solutions Using Mid-Frequency Raman Difference Spectra Explanations.

Amorphous simvastatin (amorphous SIM) and Form I of SIM were prepared separately from SIM acetone (AC)/ethyl acetate (ETAC)/ethanol (ET) solutions by simply controlling the solvent evaporation rate, and the kinetic formation of amorphous SIM from SIM AC/ETAC/ET solutions was explained using mid-frequency Raman difference spectra analysis. The mid-frequency Raman difference spectra analysis results indicate that the amorphous phase has close connections with solutions and might be the bridge, playing an important role in the intermediate phase, between solutions and their outcome polymorphs.

Explanation for the selective crystallization from inosine solutions using mid-frequency Raman difference spectra analysis.

Mid-frequency Raman difference spectra (MFRDS) analysis can be used to reveal the selective crystallization from solutions through determining the degree of similarity of the short-range orders between the assemblies of small organic molecules in solutions and their solid phases. Four solid phases of inosine (IR) (α-anhydrous IR (α-IR), ß-anhydrous IR (ß-IR), IR dihydrate (IRD), and amorphous IR (AmIR)) and two IR solutions (aqueous and 70 vol% DMSO aqueous solution) were prepared and characterized using MFRDS here. The MFRDS analysis results indicate that the selective formation of IRD and AmIR from IR aqueous solution and ß-IR from IR 70 vol% DMSO solution are originated from the high similarity of their short-range structures. Moreover, we propose that the formation of α-IR from IR aqueous solution benefits from the appearance of AmIR as an intermediate phase. MFRDS is a robust tool to explain and predict the possible precipitation products from various solutions of small organic molecules.

Temperature-Triggered Supramolecular Assembly of Organic Semiconductors.

Supramolecular assembly is a promising bottom-up approach for producing materials that behave as charge transporting components in electronic devices. Although extensive advances have been made during the past two decades, formidable challenges exist in controlling the local randomness present in supramolecular assemblies. Here, a temperature-triggered supramolecular assembly strategy using heat to heal defects and disorders is reported. The central concept of the molecular design-named the "Tetris strategy" in this research-is to: i) increase the rotational freedom of the molecules through thermal perturbation, ii) induce conformation-fitting of adjacent molecules through two different kinds of intermolecular [π···π] interactions, and finally iii) lock the nearby molecules in inactive co-conformations. Experimentally, upon heating to 57 °C, amorphous solid-state films undergo spontaneous assembly, leading to the growth of uniform and highly ordered microwire arrays. Temperature-triggered supramolecular assembly provides an approach closer to the precision control of assembled structures and presents with a broad canvas to work on in approaching a new generation of supramolecular electronics. Tetris is a registered trademark of Tetris Holding, LLC, used with permission.

Atomically Precise Engineering of Single-Molecule Stereoelectronic Effect.

Charge transport in a single-molecule junction is extraordinarily sensitive to both the internal electronic structure of a molecule and its microscopic environment. Two distinct conductance states of a prototype terphenyl molecule are observed, which correspond to the bistability of outer phenyl rings at each end. An azobenzene unit is intentionally introduced through atomically precise side-functionalization at the central ring of the terphenyl, which is reversibly isomerized between trans and cis forms by either electric or optical stimuli. Both experiment and theory demonstrate that the azobenzene side-group delicately modulates charge transport in the backbone via a single-molecule stereoelectronic effect. We reveal that the dihedral angle between the central and outer phenyl ring, as well as the corresponding rotation barrier, is subtly controlled by isomerization, while the behaviors of the phenyl ring away from the azobenzene are hardly affected. This tunability offers a new route to precisely engineer multiconfigurational single-molecule memories, switches, and sensors.

Crystallization Mechanism of 9,9-Diphenyl-dibenzosilole from Solids.

Organic semiconductor (OSC) crystals have great potential to be applied in many fields, as they can be flexibly designed according to the demands and show an outstanding device performance. However, OSCs with the capacity of solid-state crystallization (SSC) are developing too slowly to meet demands in productions and applications, due to their difficulties in molecular design and synthesis, unclear mechanism and high dependence on experimental conditions. In this work, in order to solve the problems, we synthesized an organic semiconductor capable of SSC at room temperature by adjusting the relationship between conjugated groups and functional groups. The thermodynamic and kinetic properties have been studied to discover the model of film SSC. Moreover, it can be purposefully controlled to prepare the high-quality crystals, and their corresponding organic electronic devices were further fabricated and discussed.

Building nanogapped graphene electrode arrays by electroburning.

Carbon nanoelectrodes with nanogap are reliable platforms for achieving ultra-small electronic devices. One of the main challenges in fabricating nanogapped carbon electrodes is precise control of the gap size. Herein, we put forward an electroburning approach for controllable fabrication of graphene nanoelectrodes from preprocessed nanoconstriction arrays. The electroburning behavior was investigated in detail, which revealed a dependence on the size of nanoconstriction units. The electroburnt nanoscale electrodes showed the capacity to build molecular devices. The methodology and mechanism presented in this study provide significant guidance for the fabrication of proper graphene and other carbon nanoelectrodes.

Switching Effects in Molecular Electronic Devices.

The creation of molecular electronic switches by using smart molecules is of great importance to the field of molecular electronics. This requires a fundamental understanding of the intrinsic electron transport mechanisms, which depend on several factors including the charge transport pathway, the molecule-electrode coupling strength, the energy of the molecular frontier orbitals, and the electron spin state. On the basis of significant progresses achieved in both experiments and theory over the past decade, in this review article we focus on new insights into the design and fabrication of different molecular switches and the corresponding switching effects, which is crucial to the development of molecular electronics. We summarize the strategies developed for single-molecule device fabrication and the mechanism of these switching effects. These analyses should be valuable for deeply understanding the switching effects in molecular electronic devices.