Reaction amplification with a gain: Triplet exciton-mediated quantum chain using mixed crystals with a tailor-made triplet sensitizer.

Photochemical valence bond isomerization of a crystalline Dewar benzene (DB) diacid monoanion salt with an acetophenone-linked piperazinium cation that serves as an intramolecular triplet energy sensitizer (DB-AcPh-Pz) exhibits a quantum chain reaction with as many as 450 product molecules per photon absorbed (Φ ≈ 450). By contrast, isomorphous crystals of the DB diacid monosalt of an ethylbenzene-linked piperazinium (DB-EtPh-Pz) lacking a triplet sensitizer showed a less impressive quantum yield of ca. Φ ≈ 22. To establish the critical importance of a triplet excited state carrier in the adiabatic photochemical reaction we prepared mixed crystals with DB-AcPh-Pz as a dilute triplet sensitizer guest in crystals of DB-EtPh-Pz. As expected from their high structural similarities, solid solutions were easily formed with the triplet sensitizer salt in the range of 0.1 to 10%. Experiments carried out under conditions where light is absorbed by the triplet sensitizer-linked DB-AcPh-Pz can be used to initiate a triplet state adiabatic reaction from 3DB-AcPh-Pz to 3HB*-AcPh-Pz, which can serve as a chain carrier and transfer energy to an unreacted DB-EtPh-Pz where exciton delocalization in the crystalline solid solution can help carry out an efficient energy transfer and enable a quantum chain employing the photoproduct as a triplet chain carrier. Excitation of mixed crystals with as little as 0.1% triplet sensitizer resulted in an extraordinarily high quantum yield Φ ≈ 517.

Designing Organic π-Conjugated Molecules for Crystalline Solid Solutions: Adamantane-Substituted Naphthalenes.

We showcase herein organic crystalline solid solutions (CSSs) based on the simplest polycyclic aromatic hydrocarbon (PAH) scaffold, naphthalene, stabilized by dispersion forces induced by adamantane substitution. High thermal stability of the host and guest molecules synthesized by cross-coupling of dibromonaphthalene derivatives and 4-(1-adamantyl)phenyl boronic ester enabled formation of crystals by sublimation. We could generate binary monocrystalline solid solution systems proven by X-ray crystallography, the first system of designed CSSs stabilized exclusively via dispersion forces with structural evidence. These observations are additionally supported by lattice energy calculations and spectroscopic examinations. For the generation of CSSs, it is of utmost importance that the host and guest molecules have similar lattice energies and spatial compatibility. We anticipate that the thermostable organic CSS design demonstrated herein would be beneficial for functional materials and further investigation towards materials with unique properties.

Co-Crystalline Solid Solution Affords a High-Soluble and Fast-Absorbing Form of Praziquantel.

Praziquantel (PZQ) is a chiral class-II drug, and it is used as a racemate for the treatment of schistosomiasis. The knowledge of several cocrystals with dicarboxylic acids has prompted the realization of solid solutions of PZQ with both enantiomers of malic acid and tartaric acid. Here, the solid form landscape of such a six-component system has been investigated. In the process, two new cocrystals were structural-characterized and three non-stoichiometric, mixed crystal forms identified and isolated. Thermal and solubility analysis indicates a fourfold solubility advantage for the newly prepared solid solutions over the pure drug. In addition, a pharmacokinetic study was conducted in rats, which involved innovative mini-capsules for the oral administration of the solid samples. The available data indicate that the faster dissolution rate of the solid solutions translates in faster absorption of the drug and helps maintain a constant steady-state concentration.

Epitaxies of Ca sulfates on calcite. II. The main {010}, {001} and {100} forms of bassanite epi-deposited on the {10.4} substrate form of calcite.

2D and 3D epitaxies of the main {010}, {001} and {100} forms of deposited bassanite (CaSO4·0.5H2O) on {10.4} calcite (CaCO3) as a substrate are described to provide a theoretical crystallographic background for the replacement of calcite by bassanite both in nature and in the laboratory and by weathering linked to cultural heritage. First, epitaxy in the third dimension, perpendicular to the investigated interfaces, has been verified in order to establish whether adsorption/absorption can occur (as anomalous mixed crystals) at the bassanite/calcite epi-contacts. Secondly, and by applying the Hartman-Perdok method, 2D lattice coincidences have been obtained from the physical-geometric matches of bonds running in the common directions within the elementary slices facing the substrate/deposit interfaces. This research represents the second and more detailed part of a wider program extended to the epi-interactions between the following pairs: (i) {010}-gypsum/{10.4}-calcite (just published); (ii) bassanite/{10.4}-calcite (the present work); and (iii) anhydrite (CaSO4)/{10.4}-calcite (coming soon).

Cortisone and cortisol break hydrogen-bonding rules to make a drug-prodrug solid solution.

Multidrug products enable more effective therapies and simpler administration regimens, provided that a stable formulation is prepared, with the desired composition. In this view, solid solutions have the advantage of combining the stability of a single crystalline phase with the potential of stoichiometry variation of a mixture. Here a drug-prodrug solid solution of cortisone and cortisol (hydrocortisone) is described. Despite the structural differences of the two components, the new phase is obtained both from solution and by supercritical CO2 assisted spray drying. In particular, to enter the solid solution, hydrocortisone must violate Etter's rules for hydrogen bonding. As a result, its dissolution rate is almost doubled.

Tuning the optical isotropic point of mixed crystals of ethylenediammonium sulfate/selenate.

In anisotropic crystals, optical isotropic points are wavelengths where linear birefringence disappears because the refractive indices for both eigenmodes are accidentally equivalent. Here, the optical isotropic point of ethylene-diammonium selenate (EDSe) is tuned by generating a solid-solution series of EDSe doped with sulfate. Mueller matrix polarimetry and single-crystal X-ray diffraction are used to correlate changes in linear birefringence with the crystal composition of EDS x Se1-x . A scheme for using mixed crystals with isotropic points as tunable birefringent optical bandpass filters is proposed and their performance is modeled.

Nanoscale Effects in One-Dimensional Columnar Supramolecular Ferroelectrics.

Organic ferroelectrics have been actively developed with the goal of fabricating environmentally friendly and low-cost memory devices. The remanent polarization of hydrogen-bonded organic ferroelectrics approaches that of the inorganic ones. Nanoscale fabrication of organic ferroelectrics is an essential aspect of high-density memory devices. A pyrene derivative with four tetradecylamide (-CONHC14 H29 ) chains (1) formed an amide-type N-H⋅⋅⋅O hydrogen-bonded one-dimensional (1D) column, which demonstrated ferroelectricity in the discotic hexagonal columnar (Colh ) liquid crystalline phase through the inversion of the orientation of the hydrogen-bonded chains. On the contrary, similar chiral pyrene derivatives bearing 3,7-dimethyl-1-octhylamide chains (S-2 and R-2) did not indicate the Colh phase and ferroelectricity. Homogeneous mixed liquid crystals (1)1-x (S-2)x (i.e., between the ferroelectric 1 and the non-ferroelectric S-2) enable the control of the nanoscale aggregation state of the organic ferroelectrics, resulting in a nanoscale effect of the 1D supramolecular ferroelectrics. Ferroelectric mixed liquid crystals (1)1-x (S-2)x were observed at x≦0.03, where one S-2 molecule was inserted after every thirty-three 1 molecule in the mixed liquid crystal (1)33 (S-2). An average (1)34 length of approximately 12 nm was required to maintain the 1D ferroelectricity, which was similar to the nanoscale limit of inorganic ferroelectrics, such as hafnium oxide thin film (≈15 nm).

Implementation of High-Quality Warm-White Light-Emitting Diodes by a Model-Experimental Feedback Approach Using Quantum Dot-Salt Mixed Crystals.

In this work, a model-experimental feedback approach is developed and applied to fabricate high-quality, warm-white light-emitting diodes based on quantum dots (QDs) as color-conversion materials. Owing to their unique chemical and physical properties, QDs offer huge potential for lighting applications. Nevertheless, both emission stability and processability of the QDs are limited upon usage from solution. Incorporating them into a solid ionic matrix overcomes both of these drawbacks, while preserving the initial optical properties. Here borax (Na2B4O7·10H2O) is used as a host matrix because of its lower solubility and thereby reduced ionic strength in water in comparison with NaCl. This guarantees the stability of high-quality CdSe/ZnS QDs in the aqueous phase during crystallization and results in a 3.4 times higher loading amount of QDs within the borax crystals compared to NaCl. All steps from the synthesis via mixed crystal preparation to the warm-white LED preparation are verified by applying the model-experimental feedback, in which experimental data and numerical results provide feedback to each other recursively. These measures are taken to ensure a high luminous efficacy of optical radiation (LER) and a high color rendering index (CRI) of the final device as well as a correlated color temperature (CCT) comparable to an incandescent bulb. By doing so, a warm-white LED with a LER of 341 lm/Wopt, a CCT of 2720 K and a CRI of 91.1 is produced. Finally, we show that the emission stability of the QDs within the borax crystals on LEDs driven at high currents is significantly improved. These findings indicate that the proposed warm-white light-emitting diodes based on QDs-in-borax hold great promise for quality lighting.

Diarylethene Self-Assembled Monolayers: Cocrystallization and Mixing-Induced Cooperativity Highlighted by Scanning Tunneling Microscopy at the Liquid/Solid Interface.

Stimulus control over 2D multicomponent molecular ordering on surfaces is a key technique for realizing advanced materials with stimuli-responsive surface properties. The formation of 2D molecular ordering along with photoisomerization was monitored by scanning tunneling microscopy at the octanoic acid/highly oriented pyrolytic graphite interface for a synthesized amide-containing diarylethene, which underwent photoisomerization between the open- and closed-ring isomers and also a side-reaction to give the annulated isomer. The nucleation (Kn) and elongation (Ke) equilibrium constants were determined by analysis of the concentration dependence of the surface coverage by using a cooperative model at the liquid/solid interface. It was found that the annulated isomer has a very large equilibrium constant, which explains the predominantly observed ordering of the annulated isomer. It was also found that the presence of the closed-ring isomer induces cooperativity into the formation of molecular ordering composed of the open-ring isomer. A quantitative analysis of the formation of ordering by using the cooperative model has provided a new view of the formation of 2D multicomponent molecular ordering.

Kitaigorodsky revisited: polymorphism and mixed crystals of acridine/phenazine.

Non-stoichiometric molecular mixed crystals have potential as functional materials, the properties of which can be tailored by rationally changing their composition. The guidelines for their preparation were summarized over thirty years ago by Alexander Kitaigorodsky. Here those principles are revised in light of new studies on the acridine/phenazine system, and solvent-assisted grinding is presented as a convenient synthetic procedure to afford a more homogeneous product than traditional solvent-evaporation methods. Finally, the proposed prerequisite of crystal isostructurality/isomorphicity for the pure compounds, which seems to be violated in the present case, is discussed.

Unusual Disordered Crystal Structure of a Racemate Exhibiting a Novel Enantiomeric Resolution: Preferential Enrichment.

Simple recrystallization of racemic (±)-NC leads to preferential enrichment of one enantiomer in the mother liquor, which allows the efficient resolution of the two enantiomers. In the unique disordered crystal structure of the racemate, the two enantiomers form centrosymmetric dimers as the major component.