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Searching for New Polymorphs by Epitaxial Growth.

ABSTRACT: The formation of unknown polymorphs due to the crystallization at a substrate surface is frequently observed. This phenomenon is much less studied for epitaxially grown molecular crystals since the unambiguous proof of a new polymorph is a challenging task. The existence of multiple epitaxial alignments of the crystallites together with the simultaneous presence of different polymorphs does not allow simple phase identification. We present grazing incidence X-ray diffraction studies on conjugated molecules like perylenetetracarboxylic dianhydride (PTCDA), pentacene, dibenzopentacene (trans-DBPen), and dicyanovinylquater-thiophene (DCV4T-Et2) grown by physical vapor deposition on single crystalline surfaces like Ag(111), Cu(111), and graphene. A new method for indexing the observed Bragg peaks allows the determination of the crystallographic unit cells so that the type of crystallographic phase can be clearly identified. This approach even works when several polymorphs are simultaneously present within a single sample as shown for DCV4T-Et2 on Ag(111). Additionally, epitaxial relationships between the epitaxially grown crystallites and the single crystalline surfaces are determined. In a subsequent step, the experimental data are used for the crystal structure solution of an unknown polymorph, as shown for the example trans-DBPen grown on Cu(111).

SUBMITTER: Simbrunner J

PROVIDER: S-EPMC7818500 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature

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Searching for New Polymorphs by Epitaxial Growth.

Simbrunner Josef J Schrode Benedikt B Hofer Sebastian S Domke Jari J Fritz Torsten T Forker Roman R Resel Roland R

The journal of physical chemistry. C, Nanomaterials and interfaces 20201228 1

The formation of unknown polymorphs due to the crystallization at a substrate surface is frequently observed. This phenomenon is much less studied for epitaxially grown molecular crystals since the unambiguous proof of a new polymorph is a challenging task. The existence of multiple epitaxial alignments of the crystallites together with the simultaneous presence of different polymorphs does not allow simple phase identification. We present grazing incidence X-ray diffraction studies on conjugate ...[more]

PMID: 33488907

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Project description:The phenomenon of molecular crystal polymorphism is of central importance for all those industries that rely on crystallisation for the manufacturing of their products. Computational methods for the evaluation of thermodynamic properties of polymorphs have become incredibly accurate and a priori prediction of crystal structures is becoming routine. The computational study and prediction of the kinetics of crystallisation impacting polymorphism, however, have received considerably less attention despite their crucial role in directing crystallisation outcomes. This is mainly due to the lack of available experimental data, as nucleation and growth kinetics of polymorphs are generally difficult to measure. On the one hand, the determination of overall nucleation and growth kinetics through batch experiments suffers from unwanted polymorphic transformations or the absence of experimental conditions under which several polymorphs can be nucleated. On the other hand, growth rates of polymorphs obtained from measurements of single crystals are often only recorded along a few specific crystal dimensions, thus lacking information about overall growth and rendering an incomplete picture of the problem. In this work, we measure the crystal growth kinetics of three polymorphs (I, II and IX) of tolfenamic acid (TFA) in isopropanol solutions, with the intention of providing a meaningful comparison of their growth rates. First, we analyse the relation between the measured growth rates and the crystal structures of the TFA polymorphs. We then explore ways to compare their relative growth rates and discuss their significance when trying to determine which polymorph grows faster. Using approximations for describing the volume of TFA crystals, we show that while crystals of the metastable TFA-II grow the fastest at all solution concentrations, crystals of the metastable TFA-IX become kinetically competitive as the driving force for crystallisation increases. Overall, both metastable forms TFA-II and TFA-IX grow faster than the stable TFA-I.

Dataset Information

Searching for New Polymorphs by Epitaxial Growth.

Publications

Searching for New Polymorphs by Epitaxial Growth.

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