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Delicate morphology and defect control are crucial for high-performance optoelectronics. For metal halide perovskites, antisolvent precipitation is the most common process to realize the control and develop the state-of-art devices. However, the solute/solvent/antisolvent interactions and their influence on the film formation process are unclear. Here, we propose a novel solubility parameter δDN to measure the coordinate interaction between solvent and perovskite precursors. A combination of δDN and Hansen’s solubility parameters allows for the first comprehensive analysis of interactions between pure liquids and the perovskite precursors. The relative energy difference (RED) between antisolvent and solvent is used to quantify the supersaturation level during film deposition. Dense morphology films form in the maximum supersaturation region (0.85 [less than] RED [less than] 1.00). Perovskite properties are controlled by the interaction behavior difference in antisolvent/solutes. The photovoltaic performance increases by 53% when RED increases from 0.416 to 0.858. We demonstrate that detailed knowledge of the physicochemical characteristics of the solutions used to form films of perovskites is a valuable tool in the discovery of optimum film formation conditions and consequently in attaining efficient optoelectronic performance.

A series of symmetrically bis?4?methoxybenzyl (4MB) N?substituted 1,4?diketopyrrolo[3,4?c]pyrrole (DPP) derivatives have been synthesized. The 4MB unit makes the DPP core soluble, and shows subtle modification of up to 0.2?eV in ground and excited states of the core when compared with related alkyl derivatives. Absorption and emission spectroscopy, as well as electrochemical and computational methods have been employed to prove the importance of the peripheral aryl units on the donor/ acceptor properties of the molecules. The 4MB products are highly fluorescent (quantum yields approaching 100?% in solution), with a unique distribution of frontier states shown by spectroelectrochemistry. The solid?state fluorescence correlates with the X?ray crystal structures of the compounds, a Stokes shift of approximately 80?nm is seen for two of the compounds. The frontier energy levels show that this subtle substitutional change could be of future use in molecular energy level tailoring in these, and related, materials for organic (opto)electronics.

Molecular walkers standing on two or more “feet” on an anisotropic periodic potential of a crystal surface may perform a one-dimensional Brownian motion at the surface-vacuum interface along a particular direction in which their mobility is the largest. In thermal equilibrium the molecules move with equal probabilities both ways along this direction, as expected from the detailed balance principle, well-known in chemical reactivity and in the theory of molecular motors. For molecules that possess an asymmetric potential energy surface (PES), we propose a generic method based on the application of a time-periodic external stimulus that would enable the molecules to move preferentially in a single direction thereby performing as Brownian ratchets. To illustrate this method, we consider a prototypical synthetic chiral molecular walker, the 1,3-bis(imidazol-1-ylmethyl)-5(1phenylethyl)benzene, diffusing on the anisotropic Cu(110) surface along the Cu rows. As unveiled by our kinetic Monte Carlo simulations based on the rates calculated using ab initio density functional theory, this molecule moves to the nearest equivalent lattice site via the so-called inchworm mechanism in which it steps first with the rear and then with the front foot. As a result, the molecule diffuses via a two-step mechanism, and due to its inherent asymmetry, the corresponding PES is also spatially asymmetric. Taking advantage of this fact, we show how the external stimulus can be tuned to separate molecules of different chirality, orientation and conformation. The consequences of these findings for molecular machines and the separation of enantiomers are also discussed.

© 2019 World Scientific Publishing Company. The generation of singlet oxygen (SO), primarily by using a combination of light and photosensitizers in the presence of a dissolved gas, finds applications in both chemistry and medicine. The efficiency of its formation can be enhanced by immobilization of the photosensitizers. In this work, we have explored the covalent functionalization in suspension of hexahedral slab-like polysilicon microparticles (μP, with a largest dimension of three microns) with a model photosensitizer, 5-(4-isothiocyanatophenyl)-10,15,20-(triphenyl)porphyrin (ITC-P), and evaluated the singlet oxygen generation of this photosensitizer in solution and after immobilization (ITC-P-μP) in suspension. The SO-detection experiment on the functionalized microparticles was performed using a hydrogel as the matrix supporting the microparticles (to avoid their settling), and revealed that ITC-P-μPin suspension is capable of generating SO more efficiently than free ITC-P in solution.

Chiral thiophene-diketopyrrolopyrrole derivatives have been synthesised to investigate the potential of stereochemistry and symmetry as a means of modulating properties by influencing self-assembly of these purely organic materials. In particular, derivatives of diketopyrrolopyrrole were employed because of their proven interest as dyes, especially for organic solar cells. The natural product myrtenal was used as the source of stereochemistry, introduced through a Kröhnke reaction of a thiophenebearing pyridinium salt and diketopyrrolopyrroles were prepared through Suzuki coupling with this chiral moiety at one end only as well as at both ends. Absorption spectroscopy and electrochemistry confirmed the potential suitability of the compounds for photovoltaic devices. The nanostructures formed by the compounds have been probed with circular dichroism spectroscopy in solution and in films. It is shown that a chiral C2 symmetric molecule assembles in solution giving a strong circular dichroic signal while as a film this optical activity is nulled, whereas an asymmetric homologue is most optically active as a thin film. The X-ray crystal structure of the asymmetric compound shows a polar order of the molecules that might explain this observation. The lack of optical activity in solution is very likely a result of the high solubility of the compound. The results reaffirm the sensitivity of circular dichroism spectroscopy to inter-chromophore organisation, whereas absorption spectroscopy in the visible region reveals only slight changes to the bands. The differing order in the compounds also affects their performance in bulk heterojunction photovoltaic devices. Atomic force microscopy of the blended thin films with the fullerene derivative usually employed (PC61BM) showed that smooth and well mixed films were achieved, with the conditions required during spin coating depending greatly on the derivative, because of their differing solubility. The apparently better performance of the symmetrical compound (although with very low efficiency) is probably a result of the alignment of the molecules inferred by the circular dichroism experiments, whereas the asymmetric compound presumably adopts a twisted supramolecular organisation.

It is shown here that controlled mixing of a gelator, drug, solvent, and antisolvent in a microfluidic channel leads to faster setting gels and more robust materials with longer release profiles than the physical gels of the same composition obtained using random mixing in solution. The system is similar to a related gelator system we had studied previously, but we were unable to apply the same gelling procedure because of the instability of the colloid caused by the small structural modification (length of the alkyl chain in the bis-imidazolium head group). This situation holds true for the gels formed with varying compositions and under different conditions (gelator/drug ratio, solvent proportion, and flow rates), with the most significant differences being the improved gel rheology and slower drug release rates. Very importantly, the gels (based on a previously unexplored system) have a higher water content ratio (water/EtOH 4:1) than others in the family, making their medicinal application more attractive. The gels were characterized by a variety of microscopy techniques, X-ray diffraction and infrared spectroscopy, and rheology. Salts of the antiinflammatory drugs ibuprofen and indomethacin were successfully incorporated into the gels. The diffraction experiments indicate that these composite gels with relatively short alkyl chains in the gelator component contrast to previous systems, in that they exhibit structural order and the presence of crystalline areas of the drug molecule implying partial phase separation (even though these drug crystallites are not discernible by microscopy). Furthermore, the release study with the gel incorporating ibuprofenate showed promising results that indicate a possible drug delivery vehicle application for this and related systems.

A cationic bis-imidazolium-based amphiphile was used to form thermoreversible nanostructured supramolecular hydrogels incorporating neutral and cationic drugs for the topical treatment of rosacea. The concentration of the gelator and the type and concentration of the drug incorporated were found to be factors that strongly influenced the gelling temperature, gel-formation period, and overall stability and morphology. The incorporation of brimonidine tartrate resulted in the formation of the most homogeneous material of the three drugs explored, whereas the incorporation of betamethasone resulted in a gel with a completely different morphology comprising linked particles. NMR spectroscopy studies proved that these gels kept the drug not only at the interstitial space but also within the fibers. Due to the design of the gelator, drug release was up to 10 times faster and retention of the drug within the skin was up to 20 times more effective than that observed for commercial products. Experiments in vivo demonstrated the rapid efficacy of these gels in reducing erythema, especially in the case of the gel with brimonidine. The lack of coulombic attraction between the gelator–host and the guest–drug seemed particularly important in highly effective release, and the intermolecular interactions operating between them were found to lie at the root of the excellent properties of the materials for topical delivery and treatment of rosacea.