Naslov
Exploring the Stoichiometric Diversity and Mechanochemical Reactions of Halogen-Bonded Cocrystals

Autori
Topić, Filip ; Arhangelskis, Mihails ; Hindle, Poppy ; Tran, Ricky ; Lisac, Katarina ; Morris, Andrew J. ; Cinčić, Dominik ; Friščić, Tomislav

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni

Izvornik
4th International symposium on halogen bonding / - , 2020, 84-84

Skup
4th International symposium on halogen bonding

Mjesto i datum
Stellenbosch, Južnoafrička Republika, 02.11.2020. - 05.11.2020

Vrsta sudjelovanja
Predavanje

Vrsta recenzije
Međunarodna recenzija

Ključne riječi
halogen bond ; cocrystals ; mechnanochemical reactions

Sažetak
Solid-state studies havebeen fundamental for the understandingof halogen bonding, with crystallography as the most important tool. Particularly, cocrystallization has offeredinsight into the influence of varyingdonors and acceptors on the halogen bond properties. Other interactions, such as weak C−H hydrogen bondsand aromatic ring stacking can also compete with halogen bonding. Using di-or multi-topic halogen bond donors and acceptors often gives rise to cocrystals comprising same components in different stoichiometric ratios –stoichiomorphs, as not all donor/acceptor sites necessarily engage in halogen bonding. Moreover, polymorphism can also complicate the structural landscape of even a very simple halogen-bonded cocrystal system. Mechanochemistry is anefficient, rapid cocrystallization screening method. Avoiding solubility issues, two or more coformers can be directly transformed into a cocrystalof thedesiredstoichiometry. Furthermore, cocrystals of different stoichiometries can be easily interconvertedby the addition of the respective coformer and grinding. In our work, we focused on a set of simple bromine-or iodine-based halogen bond donors and nitrogen-based acceptors. Their cocrystallization was studied by neat or liquid- assisted grinding, with varying milling times and stoichiometric ratios. State-of-the-art periodic DFT calculations were used to establish the relative stabilities of different phases. Mechanochemical screening revealed the remarkablephase diversity inthe studiedsystems. Whilethe coformer ratiowas found to reliably determine the stoichiometryof the final products, different stoichiomorphs and polymorphs were observed as intermediatesduring mechanochemical cocrystallization. DFT calculations were successfulinpredictingthe final products, with entropic contributionsemergingas critical for stabilizingsome of the obtained cocrystals.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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