Naslov
Perhalogenated aromatic amines as bifunctional donor molecules in cocrystals with ditopic nitrogen-containing acceptors

Autori
Baus Topić, Nea ; Cinčić, Dominik

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

Izvornik
28th Croatian Meeting of Chemists and Chemical Engineers Book of Abstracts / - , 2023, 56-56

Skup
28th Croatian Meeting of Chemists and Chemical Engineers

Mjesto i datum
Rovinj, Hrvatska, 28.03.2023. - 31.03.2023

Vrsta sudjelovanja
Poster

Vrsta recenzije
Podatak o recenziji nije dostupan

Ključne riječi
halogen bond ; hydrogen bond ; cocrystal

Sažetak
Design of cocrystals relies on utilization of predictable and directional intermolecular interactions, predominantly hydrogen (HB) or halogen bonds (XB). [1] Most reports are focused on research of either hydrogen or halogen bonding. In contrast, the examination of competition or cooperation of the two interactions whenever they are present within the same crystal has been much less explored. [2] To characterize the relationship between two interaction types, we have investigated supramolecular propensities of two perhalogenated aromatic amines, 4-bromo-2, 3, 5, 6- tetrafluoroaniline (btfa) and 4-iodo-2, 3, 5, 6- tetrafluoroaniline (itfa), as bifunctional donor molecules with one XB donor (iodine or bromine atom) and one HB donor (amino group) on the same perfluorinated aromatic backbone. These were utilized in preparation of cocrystals with three selected ditopic acceptors: 4, 4'- bipyridine (bpy), 1, 2-bis(4-pyridyl)ethane (bpean) and 1, 4-diazabicyclo[2.2.2]octane (dabco). By crystallization from solution and liquid-assisted grinding, we have prepared nine cocrystals in 1:1 or 2:1 stoichiometric ratio for which crystal structure and thermal stability were determined. Structure analysis revealed that in four cocrystals both NI or NBr halogen and NHN hydrogen bonds were formed, in other four cocrystals with btfa dominant interaction was hydrogen bond, and in one cocrystal with itfa dominant interaction was halogen bond. These results suggest that HB propensity for btfa is, as expected, significantly higher than XB, with bromine atom (that is weaker halogen bond donor than iodine atom) involved only in Br type I interhalogen contacts. On the other hand, HB and XB propensities of itfa are similar, thus itfa has a great potential as a bifunctional donor. Utilizing itfa in crystal engineering of cocrystals could lead to the formation of supramolecular chains based on halogen and hydrogen bonds in a predictable and reliable matter.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA