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Solution crystallization is a part of the synthesis of materials ranging from geological and biological minerals to pharmaceuticals, fine chemicals, and advanced electronic components. Attempts to predict the structure, growth rates and properties of emerging crystals have been frustrated, in part, by the poor understanding of the correlations between the oligomeric state of the solute, the growth unit, and the crystal symmetry. To explore how a solute monomer or oligomer is selected as the unit that incorporates into kinks and how crystal symmetry impacts this selection, we combine scanning probe microscopy, optical spectroscopy, and all-atom molecular simulations using as examples two organic materials, olanzapine (OZPN) and etioporphyrin I (EtpI). The dominance of dimeric structures in OZPN crystals has spurred speculation that the dimers preform in the solution, where they capture the majority of the solute, and then assemble into crystals. By contrast, EtpI in crystals aligns in parallel stacks of flat EtpI monomers unrelated by point symmetry. Raman and absorption spectroscopies show that solute monomers are the majority solute species in solutions of both compounds. Surprisingly, the kinetics of incorporation of OZPN into kinks is bimolecular, indicating that the growth unit is a solute dimer, a minority solution component. The disconnection between the dominant solute species, the growth unit, and the crystal symmetry is even stronger with EtpI, for which the (010) face grows by incorporating monomers, whereas the growth unit of the (001) face is a dimer. Collectively, the crystallization kinetics results with OZPN and EtpI establish that the structures of the dominant solute species and of the incorporating solute complex do not correlate with the symmetry of the crystal lattice. In a broader context, these findings illuminate the immense complexity of crystallization scenarios that need to be explored on the road to the understanding and control of crystallization. 

The structure and composition of the crystal growth unit are of huge fundamental and practical consequence. We propose a method to identify the solute species that incorporates into the growth site on crystal surfaces, the kinks, which rests on the kinetics of the elementary reaction at the kinks. We use as model crystals olanzapine, an antipsychotic medication, and etioporphyrin I, a field‐effect transistor. We combine time‐resolvedin situatomic force microscopy with Raman and absorption spectroscopies, complemented by density functional theory and all‐atom molecular dynamics modeling of the solutions. We show that the structure of the growth unit cannot be deduced neither from the solute oligomers nor from the crystal structure. Chemical kinetics analyses reveal that if the dominant solute species is the one that incorporates into the crystal growth sites, then the kinetics of layer growth complies with a monomolecular rate law. By contrast, if the crystal growth unit assembles from two units of the dominant solute form, a bimolecular rate law ensues. Solutions of both olanzapine and etioporphyrin I are dominated by solute monomers, which exist in equilibrium with a minority of dimers. Whereas numerous olanzapine crystal structures incorporate dimer motifs, etioporphyrin I crystals organize as stacks of monomers. Olanzapine crystal grow by incorporation of dimers. One of the studied face of etioporphyrin I grows by incorporation of the majority monomers, whereas the other one selects the minority dimers as a growth unit. The results highlight the power of the crystallization kinetics analyses to identify the growth unit and illuminate one of the most challenging issues of crystal growth.

 

The integration of highly luminescent CsPbBr₃quantum dots on nanowire waveguides has enormous potential applications in nanophotonics, optical sensing, and quantum communications. On the other hand, CsPb₂Br₅nanowires have also attracted a lot of attention due to their unique water stability and controversial luminescent property. Here, the growth of CsPbBr₃nanocrystals on CsPb₂Br₅nanowires is reported first by simply immersing CsPbBr₃powder into pure water, CsPbBr_3−γ X_γ(X = Cl, I) nanocrystals on CsPb₂Br_5−γ X_γnanowires are then synthesized for tunable light sources. Systematic structure and morphology studies, including in situ monitoring, reveal that CsPbBr₃powder is first converted to CsPb₂Br₅microplatelets in water, followed by morphological transformation from CsPb₂Br₅microplatelets to nanowires, which is a kinetic dissolution–recrystallization process controlled by electrolytic dissociation and supersaturation of CsPb₂Br₅. CsPbBr₃nanocrystals are spontaneously formed on CsPb₂Br₅nanowires when nanowires are collected from the aqueous solution. Raman spectroscopy, combined photoluminescence, and SEM imaging confirm that the bright emission originates from CsPbBr_3−γ X_γnanocrystals while CsPb₂Br_5−γ X_γnanowires are transparent waveguides. The intimate integration of nanoscale light sources with a nanowire waveguide is demonstrated through the observation of the wave guiding of light from nanocrystals and Fabry–Perot interference modes of the nanowire cavity.