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Halogen bonding with carbon: directional assembly of non-derivatised aromatic carbon systems into robust supramolecular ladder architectures

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dc.abstract.enCarbon, although the central element in organic chemistry, has been traditionally neglected as a target for directional supramolecular interactions. The design of supramolecular structures involving carbon-rich molecules, such as arene hydrocarbons, has been limited almost exclusively to non-directional π-stacking, or derivatisation with heteroatoms to introduce molecular assembly recognition sites. As a result, the predictable assembly of non-derivatised, carbon-only π-systems using directional non-covalent interactions remains an unsolved fundamental challenge of solid-state supramolecular chemistry. Here, we demonstrate an effective, different, and previously overlooked, paradigm for the assembly of carbon-only aromatic systems: not through non-directional π-stacking, but via specific and directional halogen bonding. We present the a systematic experimental, theoretical and database study of halogen bonds to carbon-only π-systems (C-I···πC bonds), focusing on the synthesis and structural analysis of cocrystals with diversely-sized and -shaped non-derivatised arenes, from one-ring (benzene) to 15-ring (dicoronylene) polycyclic atomatic hydrocarbons (PAHs), and fullerene C60, along with theoretical calculations and a systematic analysis of the Cambridge Structural Database. This study establishes C-I···πC bonds as directional interactions to arrange planar and curved carbon-only aromatic systems into predictable supramolecular motifs. In >90% of herein presented structures, the C-I···πC bonds to PAHs lead to a general ladder motif, in which the arenes act as the rungs and halogen bond donors as the rails, establishing a unique example of a supramolecular synthon based on carbon-only molecules. Besides fundamental importance in the solid-state and supramolecular chemistry of arenes, this synthon enables access to materials with exciting properties based on simple, non-derivatised aromatic systems, as seen from large red and blue shifts in solid-state luminescence and room-temperature phosphorescence upon cocrystallisation.
dc.affiliationUniwersytet Warszawski
dc.contributor.authorFriščić, Tomislav
dc.contributor.authorBarrett, Christopher J
dc.contributor.authorPerepichka, Dmytro
dc.contributor.authorColes, Simon
dc.contributor.authorTopić, Filip
dc.contributor.authorHamzehpoor, Ehsan
dc.contributor.authorSpilfogel, Toni S
dc.contributor.authorMcPherson, Laura J. McCormick
dc.contributor.authorArhangelskis, Mihails
dc.contributor.authorBorchers, Tristan H
dc.contributor.authorVainauskas, Jogirdas
dc.date.accessioned2024-01-25T02:54:52Z
dc.date.available2024-01-25T02:54:52Z
dc.date.copyright2023-10-24
dc.date.issued2023
dc.description.accesstimeAT_PUBLICATION
dc.description.financeNie dotyczy
dc.description.versionFINAL_PUBLISHED
dc.identifier.doi10.1039/D3SC04191C
dc.identifier.issn2041-6520
dc.identifier.urihttps://repozytorium.uw.edu.pl//handle/item/108271
dc.identifier.weblinkhttp://pubs.rsc.org/en/content/articlepdf/2023/SC/D3SC04191C
dc.languageeng
dc.pbn.affiliationchemical sciences
dc.relation.ispartofChemical Science
dc.rightsCC-BY
dc.sciencecloudnosend
dc.titleHalogen bonding with carbon: directional assembly of non-derivatised aromatic carbon systems into robust supramolecular ladder architectures
dc.typeJournalArticle
dspace.entity.typePublication