Halogen bonding with carbon: directional assembly of non-derivatised aromatic carbon systems into robust supramolecular ladder architectures
Halogen bonding with carbon: directional assembly of non-derivatised aromatic carbon systems into robust supramolecular ladder architectures
Carbon, 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 propose and validate a different paradigm for the reliable assembly of carbon-only aromatic systems into predictable supramolecular architectures: not through non-directional π-stacking, but via specific and directional halogen bonding. We present 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.
13031-13041
Vainauskas, Jogirdas
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Borchers, Tristan H.
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Arhangelskis, Mihails
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McCormick McPherson, Laura J.
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Spilfogel, Toni S.
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Hamzehpoor, Ehsan
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Topić, Filip
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Coles, Simon J.
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Perepichka, Dmytro F.
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Barrett, Christopher J.
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Friščić, Tomislav
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22 November 2023
Vainauskas, Jogirdas
d18a1081-1168-47d0-962a-6c4cb112f9ae
Borchers, Tristan H.
cadf1cdd-36d0-48d0-93e6-dadd1ee48d26
Arhangelskis, Mihails
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McCormick McPherson, Laura J.
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Spilfogel, Toni S.
77486150-4472-480d-ae6c-1f99ab48eb3c
Hamzehpoor, Ehsan
30fa6f46-39a6-4ae9-a919-36dd0431484e
Topić, Filip
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Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Perepichka, Dmytro F.
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Barrett, Christopher J.
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Friščić, Tomislav
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Vainauskas, Jogirdas, Borchers, Tristan H., Arhangelskis, Mihails, McCormick McPherson, Laura J., Spilfogel, Toni S., Hamzehpoor, Ehsan, Topić, Filip, Coles, Simon J., Perepichka, Dmytro F., Barrett, Christopher J. and Friščić, Tomislav
(2023)
Halogen bonding with carbon: directional assembly of non-derivatised aromatic carbon systems into robust supramolecular ladder architectures.
Chemical Science, 14 (45), .
(doi:10.1039/d3sc04191c).
Abstract
Carbon, 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 propose and validate a different paradigm for the reliable assembly of carbon-only aromatic systems into predictable supramolecular architectures: not through non-directional π-stacking, but via specific and directional halogen bonding. We present 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.
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d3sc04191c
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Submitted date: 10 August 2023
Accepted/In Press date: 9 October 2023
e-pub ahead of print date: 24 October 2023
Published date: 22 November 2023
Additional Information:
Funding Information: we acknowledge the support of McGill University, Natural Sciences and Engineering Research Council of Canada (NSERC) Discovery Grant (RGPIN-2017-06467; RGPIN-2018-06500); John C. Polanyi Award (JCP 562908-2022), the Government of Canada for Tier-1 Canada Research Chair Program (TF), the National Science Center of Poland (NCN) OPUS Grant (2020/37/B/ST5/02638), the Leverhulme Trust (Leverhulme International Professorship, LIP-2021-011) and the University of Birmingham. We thank the UK Engineering and Physical Sciences Research Council for funding the National Crystallography Service (EP/W02098X/1). Fonds de recherche du Québec – Nature et technologies (FRQNT) is acknowledged for a doctoral scholarship (EH).
This journal is © The Royal Society of Chemistry.
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Local EPrints ID: 486008
URI: http://eprints.soton.ac.uk/id/eprint/486008
ISSN: 2041-6520
PURE UUID: ba59b102-0e94-4475-b2b9-88a20d2ba340
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Date deposited: 05 Jan 2024 17:46
Last modified: 18 Mar 2024 02:50
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Contributors
Author:
Jogirdas Vainauskas
Author:
Tristan H. Borchers
Author:
Mihails Arhangelskis
Author:
Laura J. McCormick McPherson
Author:
Toni S. Spilfogel
Author:
Ehsan Hamzehpoor
Author:
Filip Topić
Author:
Dmytro F. Perepichka
Author:
Christopher J. Barrett
Author:
Tomislav Friščić
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