engleski

Theoretical studies of halogen-bonded cocrystallization using periodic DFT calculations

Halogen bonding is a supramolecular interaction based on an attraction between electrophilic region (σ-hole) of a halogen atom and a nucleophilic donor atom. The emergence of XB as an alternative to more commonly used hydrogen bonding opens a new path to the design of wide range of supramolecular architectures and multicomponent molecular crystals. In order to design new halogen-bonded materials more efficiently, it is crucial to understand the energy and directionality of the halogen bonds as a function of donor and acceptor atom types, while also considering the effects of supramolecular interactions besides XB (hydrogen bonding, π-π stacking etc.) This can be achieved by utilizing periodic density functional theory (DFT) calculations, which bring the accuracy of quantum chemical calculations to the realm of crystal structures.This presentation will focus on the use of periodic density functional theory (DFT) calculations to understand the thermodynamic stability of halogen-bonded cocrystals. We have used periodic DFT to explain the formation of cocrystals with unprecedented halogen bonding interactions with the heavy, increasingly metallic elements of the pnictogen group (I...P, I...As, I...Sb).3 In addition, our inability to synthesize the analogous cocrystal with I...Bi interaction was rationalized that way. The presentation will continue with the application of periodic DFT calculations to study stoichiometric diversity of halogen-bonded cocrystals. The ability of periodic DFT calculations to predict stoichiometric interconversions will be demonstrated. Throughout the presentation the challenges in modelling crystal structures containing halogen bonds will be addressed.5 Performance of various DFT methods (functionals and dispersion corrections) will be discussed.

Halogen bond ; cocrystallization ; DFT

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