Cross-nucleation between ROY polymorphs

Cross-nucleation between polymorphs is a newly discovered phenomenon important for understanding and controlling crystal polymorphism. It contradicts Ostwald's law of stages and other theories of crystallization in polymorphic systems. We studied the phenomenon in the spontaneous and seeded melt crystallization of 5-methyl-2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile (ROY), currently the most polymorphic system of known structures. We observed extensive and sometimes selective cross-nucleation between ROY polymorphs. Certain polymorphs could not nucleate without the aid of others. The new polymorph was found to be more or less thermodynamically stable than the initial one but to always grow faster than or as fast as the initial one. The temperature and surface characteristics of the seed crystals affected the occurrence of cross-nucleation. Our results show that the pathway of crystallization in polymorphic systems is not determined solely by the initial nucleation, but also by cross-nucleation between polymorphs and the different growth rates of polymorphs. This study identified a new metastable polymorph of ROY, the 10th of the family.     

Study of Surface Cell Madelung Constant and Surface Free Energy of Nanosized Crystal Grain

1 INTRODUCTION 2. 1 Madelung constant of crystal Surface energy of crystal grain has crucial influ- The Madelung constant, which is used to calculate ence on the electrical and mechanical performances lattice energy and so on[1], is of central importance in of material, especially for material making up of na- the theory of ionic crystal and property of crystal nosized crystal grains because all outstanding per- structure. There is no special difficulty in calculating formances of the mat…     

The influence of minor components on the structural reorganization in glassforming materials

Correlation of structure parameters of glasses and related crystals formed in homogeneous or heterogeneous nucleation processes by thermal treatment is discussed on the basis of DTA, TG and EGA measurements in relation to the textural patterns of the materials. For cordierite glass, crystallization of metastable disordered cordierite polymorphs is related to an exothermic heat evolution and simultaneous with a small weight loss (appr. 0.025%). By MS-EGA, evolution of water was determined during the transformation of the metastable melt to a metastable intermediate crystalline phase. Interpretation of the crystallization by comparing the available structure parameters of cordierite glasses and crystals alone is insufficient to explain the role of water in the kinetics of crystallization. Optical and electron microscopy of the primary crystallization phenomena show the metastable solid solution with low quartz-type structure. Interpretation of the crystallization behaviour in terms of conventional theory of nucleation and crystal growth is impossible.     

Luminescence Color‐Tuning through Polymorph Doping: Preparation of a White‐Emitting Solid from a Single Gold(I)–Isocyanide Complex by Simple Precipitation

We report the luminescent color tuning of a new complex, 2‐benzothiophenyl(4‐methoxyphenyl isocyanide)gold(I) ( 1 ), by using a new “polymorph doping” approach. The slow crystallization of the complex 1 afforded three different pure polymorphic crystals with blue, green, and orange emission under UV‐light irradiation. The crystal structures of pure polymorphs of 1 were investigated in detail by means of single‐crystal X‐ray analyses. Theoretical calculations based on the single‐crystal structures provided qualitative explanation of the difference in the excited energy‐levels of the three polymorphs of 1 . In sharp contrast, the rapid precipitation of 1 , with the optimized conditions reproducibly afforded homogeneous powder materials showing solid‐state white‐emission with Commission Internationale de l’Éclairage (CIE) 1931 chromaticity coordinates of (0.33, 0.35), which is similar to pure white. New “polymorphic doping” has been revealed to be critical to this white emission through spectroscopic and X‐ray diffraction analyses. The coexistence of the multiple polymorphs of 1 within the homogeneous powder materials and the ideal mixing of multiple luminescent colors gave its white emission accompanied with energy transfer from the predominant green‐emitting polymorph to the minor orange‐emitting polymorph.     

Gel-induced selective crystallization of polymorphs

Although nanoporous materials have been explored for controlling crystallization of polymorphs in recent years, polymorphism in confined environments is still poorly understood, particularly from a kinetic perspective, and the role of the local structure of the substrate has largely been neglected. Herein, we report the use of a novel material, polymer microgels with tunable microstructure, for controlling polymorph crystallization from solution and for investigating systematically the effects of nanoconfinement and interfacial interactions on polymorphic outcomes. We show that the polymer microgels can improve polymorph selectivity significantly. The polymorphic outcomes correlate strongly with the gel-induced nucleation kinetics and are very sensitive to both the polymer microstructure and the chemical composition. Further mechanistic investigations suggest that the nucleation-templating effect and the spatial confinement imposed by the polymer network may be central to achieving polymorph selectivity. We demonstrate polymer microgels as promising materials for controlling crystal polymorphism. Moreover, our results help advance the fundamental understanding of polymorph crystallization at complex interfaces, particularly in confined environments.     

Concomitant Polymorphs

The simultaneous appearance of polymorphs of a substance has long been recognized but rarely noted or systematically studied. This phenomenon can be useful in the investigation of solid materials and in understanding the relative crystal energetics of polymorphic materials. This review covers the thermodynamic and kinetic factors that govern competitive and concomitant polymorphic crystallization. One of the many examples surveyed is a cyanine/oxonol complex, for which different relative molecular orientations in two of the many reported polymorphs are shown.     

Melting temperature of Pb nanostructural materials from free energy calculation

The thermodynamic properties of lead, including the entropy, heat capacity, Gibbs free energy, and surface free energy have been studied. Based on bulk thermodynamic properties of lead, Gibbs free energy for nanostructural materials is obtained and used to calculate the size-dependent melting point depression for lead nanostructural materials. The studies indicate that the surface free energy difference between solid phase and liquid phase is a decisive factor for the size-dependent melting of nanostructural materials. The calculated results are in agreement with recent experimental values and the available molecular dynamics simulation data.     

Molecular mechanism for the cross-nucleation between polymorphs

We use molecular simulations to study the early stages of crystallization in a supercooled liquid of Lennard-Jones particles. We observe the onset of concomitant polymorphism and demonstrate that this phenomenon results from the cross-nucleation of a metastable polymorph on the stable polymorph. We also show that cross-nucleation is selective as it only takes place between polymorphs of almost equivalent free energy. Our simulations provide detailed insights into the molecular mechanism underlying concomitant polymorphism and cross-nucleation between polymorphs.     

Encapsulation of Metalloporphyrins in Nanometer-sized Zeolites:Synthesis,Characterization and Catalysis

The lasting extensive interest in zeolite molecular sieves, a class of nanoporous aluminosilicate oxidic crystals, lies in their three special properties:(a) the nanoscale porous cage that can serve as size- and/or shape-based host to recognize, select, and discriminate among the molecules, (b) the well-defined and controllable charge environment and charge strength inside pores that can facilitate or inhibit certain chemical processes, and (c) the well-organized pores/channels that can host the organization and assembly of molecules to display novel optical or electrochemical properties. Zeolitic materials possess yet another very important property, namely, their huge surface-to-volume ratio. Conventionally synthesized zeolites are quite large crystals with grain size at micrometer scale. This implies that the dominant portion of the "overall surface area" is attributable to the " interior surface" of nanopores/nanochannels instead of the "exterior surfaces" of the crystal powders. In many situations, this has limited the efficacy of zeolite materials, particularly in many catalysis-related applications. In order to improve the efficiency of catalysis of zeolite materials, it is often desirable to achieve a balanced ratio (~1) between interior-surface-area and exterior-surface-area, namely, to significantly reduce the size of zeolite crystals.     

Factors influencing deformation stability of binary glasses

A possible mechanism of strain accommodation in large deformation of glasses is crystallization; deformation stability is a measure of the resistance of glasses to crystallization. We study the effect of atomic size ratio and atomic stiffness parameter (related to the curvature of the interatomic potential) on deformation stability of binary glasses using molecular static simulations. The deformation stability of a glass is found to increase with increasing atomic size ratio and magnitude of the atomic stiffness, which is proportional to the bulk modulus of the pure crystalline system, as well as the ratio of atomic stiffnesses of constituent atoms. To understand the role of the above parameters on deformation stability, misfit energies of randomly substituted solid solution fcc crystals and glasses are compared for various atomic size ratios and atomic stiffness values. Unlike in fcc solid solution, the misfit energy of binary glasses is found to be insensitive to the atomic size ratio. It is also found that the packing fraction of glasses is insensitive to the atomic size ratio, consistent with the above result. Beyond a critical atomic size ratio, the misfit energy of fcc solid solution exceeds the energy of the glass, thus making the amorphous state completely stable to deformation induced crystallization. Our analysis shows that critical atomic size ratio decreases with increasing atomic stiffness which leads to an increase in the deformation stability of glasses.     

Simulations of energy and switching in AFLCDs with different boundary conditions

Using standard expressions for the various terms in the Gibbs free energy, the switching in antiferroelectric liquid crystal (AFLC) displays is simulated and the time evolution of various energy terms and of the liquid crystal director distributions are calculated. It is shown that when returning from a strong positive voltage to zero, one can reach two types of antiferroelectric state: the normal alternating state with the two bulk polarizations perpendicular to the electrodes and opposite to each other, and the alternative splayed symmetric state with two bulk polarizations parallel to the electrodes and again opposite to each other. The former case gives rise to tri-state switching characteristics, the latter to V-shaped switching. In general strong polar interaction with the alignment layer favours V-shaped switching while weak or no polar interaction give rise to tri-state switching characteristics. Since the V-shaped characteristic has so far only been demonstrated experimentally in ferroelectric liquid crystals (or antiferroelectric liquid crystals being in the ferroelectric state), the difference in AFLCs is discussed and the conditions for continuous switching are modelled. The simulations show that the switching characteristics of the antiferroelectric display can be controlled by the surface parameters.     

Supramolecular Interactions and Morphology Control in Microwave Synthesis of Nanoporous Materials

Application of a microwave technique to the conventional hydrothermal process is gaining importance, especially, in the synthesis of nanoporous materials. This microwave technique is regarded as a novel synthesis tool because it gives several beneficial advantages such as homogeneous nucleation, rapid synthesis, formation of uniform crystals, and small crystallites, facile morphology control, energy efficiency and so on. Recently, it was found that it offers an efficient way to control the crystal morphology, size and orientation, and even crystalline phase which are required for many emerging applications of nanoporous materials. This review summarizes recent work on the microwave effect, supramolecular interactions and control of crystal morphology upon microwave synthesis of nanoporous materials performed by the present authors. Synthesis and morphology control of nanoporous materials such as ZSM-5, zeolite beta, metallosilicates, AlPO, MCM-41, SBA-15, SBA-16, etc. have been accomplished with microwave irradiation. In particular, the rapid nucleation and crystallization of ZSM-5 zeolite under microwave irradiation made it possible to enable the continuous microwave synthesis, implying a great industrial and technological importance. The formation of nanoporous materials, especially, silicate or aluminosilicate molecular sieves was described on the basis of supramolecular interactions between organic template molecules and silicate species under microwave irradiation. Besides decreasing synthesis time, it was duly demonstrated that the microwave technique provides an effective way to control particle size distribution and macroscopic morphology in the synthesis. Moreover, for the application of these porous materials, microwave-induced nanofabrication of microporous and mesoporous materials is more important than that of simple porous materials.     

Role of liquid polymorphism during the crystallization of silicon

Using molecular simulation, we establish the pivotal role played by liquid polymorphs during the crystallization of silicon. When undercooled at a temperature 20% below the melting point, a silicon melt is under the form of the highly coordinated, high-density liquid (HDL) polymorph. We find that crystallization starts with the formation, within the HDL liquid, of a nanosized droplet of the least stable liquid polymorph, known as the almost tetracoordinated low-density liquid (LDL) polymorph. We then show that the crystalline embryo forms within the LDL droplet, close to the interface with the surrounding HDL liquid, thereby following a pathway associated with a much lower free energy barrier than the direct formation of the crystalline embryo from the HDL liquid would have required. This implies that, for substances exhibiting liquid polymorphs, theories, like the classical nucleation theory, and empirical rules, like Ostwald's rule, should be modified to account for the role of liquid polymorphs in the nucleation process.     

Measuring free-energy difference between crystal polymorphs through eutectic melting

We describe a method to measure the free-energy difference, DeltaG, between crystal polymorphs from their calorimetric data of eutectic melting with a common additive. The use of different additives yields DeltaG as a function of temperature. The method is suitable for crystals that chemically decompose or physically transform before melting. It applies to not only true polymorphs but also pairs of racemate and conglomerate of resolvable enantiomers. We illustrate the method with the polymorphs of glycine, d-mannitol, and tazofelone and report a new value (123 degrees C) for the enantiotropic transition temperature of alpha and gamma glycine. We show how different additives (including a liquid additive, water) can be used for different compounds. The DeltaG data thus obtained are important for structure-stability studies and controlling crystallization in polymorphic systems.     

Selection and discovery of polymorphs of platinum complexes facilitated by polymer-induced heteronucleation

Polymer-induced heteronucleation was utilized for the selective crystallization of the color polymorphic platinum complexes Pt(bpy)Cl2 and Pt(phen)Cl2. Crystal structures of two polymorphs of Pt(phen)Cl2 were determined and reveal that, as in the case of Pt(bpy)Cl2, this compound has one form with Pt...Pt interactions (orange crystals) and another lacking these contacts (yellow crystals). Free energy measurements reveal that the polymorphs of Pt(bpy)Cl2 and Pt(phen)Cl2 without Pt...Pt interactions are more stable in both cases by 0.67(2) and 0.53(1) kJ/mol, respectively, and this finding is consistent with the principle of close packing. Furthermore, a search of the Cambridge Structural Database reveals that, for polymorphic platinum complexes, shorter intermolecular Pt...Pt interactions generally result in less dense structures.     

Crystallization Force—A Density Functional Theory Concept for Revealing Intermolecular Interactions and Molecular Packing in Organic Crystals

Organic molecules are prone to polymorphic formation in the solid state due to the rich diversity of functional groups that results in comparable intermolecular interactions, which can be greatly affected by the selection of solvent and other crystallization conditions. Intermolecular interactions are typically weak forces, such as van der Waals and stronger short‐range ones including hydrogen bonding, that are believed to determine the packing of organic molecules during the crystal‐growth process. A different packing of the same molecules leads to the formation of a new crystal structure. To disclose the underlying causes that drive the molecule to have various packing motifs in the solid state, an electronic concept or function within the framework of conceptual density functional theory has been developed, namely, crystallization force. The concept aims to describe the local change in electronic structure as a result of the self‐assembly process of crystallization and may likely quantify the locality of intermolecular interactions that directs the molecular packing in a crystal. To assess the applicability of the concept, 5‐methyl‐2‐[(2‐nitrophenyl)amino]‐3‐thiophenecarbonitrile, so‐called ROY, which is known to have the largest number of solved polymorphs, has been examined. Electronic calculations were conducted on the seven available crystal structures as well as on the single molecule. The electronic structures were analyzed and crystallization force values were obtained. The results indicate that the crystallization forces are able to reveal intermolecular interactions in the crystals, in particular, the close contacts that are formed between molecules. Strong correlations exist between the total crystallization force and lattice energy of a crystal structure, further suggesting the underlying connection between the crystallization force and molecular packing.     

Combinatorial Crystal Synthesis: Structural Landscape of Phloroglucinol:1,2‐bis(4‐pyridyl)ethylene and Phloroglucinol:Phenazine

A large number of crystal forms, polymorphs and pseudopolymorphs, have been isolated in the phloroglucinol‐dipyridylethylene (PGL:DPE) and phloroglucinol‐phenazine (PGL:PHE) systems. An understanding of the intermolecular interactions and synthon preferences in these binary systems enables one to design a ternary molecular solid that consists of PGL, PHE, and DPE, and also others where DPE is replaced by other heterocycles. Clean isolation of these ternary cocrystals demonstrates synthon amplification during crystallization. These results point to the lesser likelihood of polymorphism in multicomponent crystals compared to single‐component crystals. The appearance of several crystal forms during crystallization of a multicomponent system can be viewed as combinatorial crystal synthesis with synthon selection from a solution library. The resulting polymorphs and pseudopolymorphs that are obtained constitute a crystal structure landscape.     

非传统晶体生长的早期观察

晶体早期生长的研究揭示,在某些体系中,晶体生长可能并不遵循传统路径.借由某些聚合物或生物分子的帮助,无机晶体的前驱体或纳米晶体在生长初期有可能聚集为无序的大块颗粒.这些聚集体表面晶化形成高结晶度高密度的外壳,随后完成从表面到核心的晶化过程.此逆向晶体生长机理在一些诸如沸石、钙钛矿、金属和金属氧化物等无机化合物体系中均已被发现,在其他材料体系里也将得到验证.认识这一新的晶体生长路径将给予我们更多的自由度来实现晶体形态控制,也有助于我们对于许多天然矿物形成机制的理解.本文简要回顾了最近本领域研究中一些典型逆向晶体生长的例子.     

Differentiating calcium carbonate polymorphs by surface analysis techniques—an XPS and TOF‐SIMS study

Calcium carbonate has evoked interest owing to its use as a biomaterial, and for its potential in biomineralization. Three polymorphs of calcium carbonate, i.e. calcite, aragonite, and vaterite were synthesized. Three conventional bulk analysis techniques, Fourier transform infrared (FTIR), X‐ray diffraction (XRD), and SEM, were used to confirm the crystal phase of each polymorphic calcium carbonate. Two surface analysis techniques, X‐ray photoelectron spectroscopy (XPS) and time‐of‐flight secondary ion mass spectroscopy (TOF‐SIMS), were used to differentiate the surfaces of these three polymorphs of calcium carbonate. XPS results clearly demonstrate that the surfaces of these three polymorphs are different as seen in the Ca(2p) and O(1s) core‐level spectra. The different atomic arrangement in the crystal lattice, which provides for a different chemical environment, can explain this surface difference. Principal component analysis (PCA) was used to analyze the TOF‐SIMS data. Three polymorphs of calcium carbonate cluster into three different groups by PCA scores. This suggests that surface analysis techniques are as powerful as conventional bulk analysis to discriminate calcium carbonate polymorphs. Copyright © 2008 John Wiley & Sons, Ltd.     

Polymer induced changes of the crystallization scenario in suspensions of hard sphere like microgel particles

We investigated the crystallization scenario of highly cross linked polystyrene particles dispersed in the good solvent 2-ethylnaphtalene and their mixtures with non-adsorbing low molecular weight polysterene polymer using time resolved static light scattering. The samples were prepared slightly below the melting volume fraction of the polymer free system. For the polymer free samples, we obtained polycrystalline solids via crystallization scenario known from hard sphere suspensions with little competition of wall crystal formation. Addition of non-adsorbing low molecular weight polystyrene polymer leads to a considerably slowing down of the bulk crystallization kinetics. We observed a delay of the precursor to crystal conversion for the bulk crystallization while the induction times for the wall nucleation are reduced. The increased polymer concentration thus shifts the balance between the two competing crystallization pathways giving the possibility to tune the relative amount of wall based crystals.