Halogen Bonding to Carbon: a Directional Interaction for the Reliable Design of Supramolecular Architectures Based on Non-derivatized Aromatic Carbon Systems DOI Creative Commons
Jogirdas Vainauskas,

Tristan Borchers,

Mihails Arhangelskis

et al.

Published: April 25, 2023

Carbon, although the central element in organic chemistry has been traditionally neglected as a target for directional supramolecular interactions. The design of structures involving carbon-rich molecules, such arenes, almost exclusively limited to π-stacking aromatic systems, or derivatization with heteroatoms sites molecular recognition. Here, we demonstrate that C-I···Cπ halogen bonds carbon-based π-systems can be reliably used direction-al interactions creation extended based on planar, well curved without any need π-stacking. Specifically, describe first systematic study series cocrystals containing non-derivatized carbon-only systems different sizes and shapes, including polycyclic hydrocarbons (PAHs) fullerene C60, which are held together by carbon atoms. In large majority (~90%) structures, bonding PAHs leads ladder-like motif, act rungs bond donors rails, demonstrating this motif example synthon carbon. These results, supported novel cocrystal theoretical calculations, analysis Cambridge Structural Database, offer new, previously overlooked paradigm assembly not π-stacking, but via specific, bonding. This new ability use car-bon-based direct provides an exciting opportunity create materials modified properties seen from red blue shifts solid-state luminescence pyrene, coronene perylene, appearance room-temperature phosphorescence upon formation.

Language: Английский

Halogen bonding with carbon: directional assembly of non-derivatised aromatic carbon systems into robust supramolecular ladder architectures DOI Creative Commons
Jogirdas Vainauskas,

Tristan H. Borchers,

Mihails Arhangelskis

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(45), P. 13031 - 13041

Published: Jan. 1, 2023

Carbon, although the central element in organic chemistry, has been traditionally neglected as a target for directional supramolecular interactions. The design of structures involving carbon-rich molecules, such arene hydrocarbons, limited almost exclusively to non-directional π-stacking, or derivatisation with heteroatoms introduce molecular assembly recognition sites. As result, predictable non-derivatised, carbon-only π-systems using non-covalent interactions remains an unsolved fundamental challenge solid-state chemistry. Here, we propose and validate different paradigm reliable aromatic systems into architectures: not through but via specific halogen bonding. We present systematic experimental, theoretical database study bonds (C-I⋯πC bonds), focusing on synthesis structural analysis cocrystals diversely-sized -shaped non-derivatised arenes, from one-ring (benzene) 15-ring (dicoronylene) polycyclic atomatic hydrocarbons (PAHs), fullerene C60, along calculations Cambridge Structural Database. This establishes C-I⋯πC arrange planar curved motifs. In >90% herein presented structures, PAHs lead general ladder motif, which arenes act rungs bond donors rails, establishing unique example synthon based molecules. Besides importance chemistry this enables access materials exciting properties simple, systems, seen large red blue shifts luminescence room-temperature phosphorescence upon cocrystallisation.

Language: Английский

Citations

15
Perhalogenated Anilines as Bifunctional Donors of Hydrogen and Halogen Bonds in Cocrystals with Ditopic Nitrogen-Containing Acceptors DOI Creative Commons
Nea Baus Topić, Sibananda G. Dash, Edi Topić

et al.

Crystal Growth & Design, Journal Year: 2024, Volume and Issue: 24(12), P. 5078 - 5088

Published: June 6, 2024

In this study, we examine the experimental and theoretical capabilities of two perhalogenated anilines, 2,3,5,6-tetrafluoro-4-bromoaniline (

Language: Английский

Citations

3
Cooperative effect of weak hydrogen bond that governs cocrystal formation over eutectics DOI

Trishna Rajbongshi,

Kashyap Kumar Sarmah,

Bondita Goswami

et al.

Journal of Molecular Structure, Journal Year: 2025, Volume and Issue: unknown, P. 142700 - 142700

Published: May 1, 2025

Language: Английский

Citations

0
Designing Dynamic Crystals with Multiple Flexibilities through a Cocrystal Strategy for Flexible Photo-controlled Switches DOI
Kui Chen, Wenbo Wu,

Hongtu Zhao

et al.

Crystal Growth & Design, Journal Year: 2023, Volume and Issue: 23(12), P. 8637 - 8645

Published: Aug. 16, 2023

Endowing function crystals with flexibility can further extend their applications in the field of flexible smart devices. Herein, a brittle, photo-driven dynamic crystal was successfully modified into through cocrystal strategy. The fluorescence and photo-response properties were simultaneously improved. More importantly, cocrystals exhibit rare multiple flexibilities, including 2D elastic bending twistable deformation properties, which have not been reported before for cocrystals. mechanisms investigated detailed crystallographic analysis, experimental tests, theoretical calculations. It found that be attributed to strong π-stacked columns connecting weak molecular interactions herringbone arrangements are closely related different orientations intermolecular rotation without spatial hindrance. Finally, taking advantage flexibilities cocrystals, photo-controlled switch designed tested.

Language: Английский

Citations

6
Elucidating mechanochemical reactivity of a ternary halogen-bonded cocrystal system by computational and calorimetric studies DOI
Lavanya Kumar, Sibananda G. Dash, Katarina Leko

et al.

Physical Chemistry Chemical Physics, Journal Year: 2023, Volume and Issue: 25(42), P. 28576 - 28580

Published: Jan. 1, 2023

Mechanochemical interconversions of a three-component halogen-bonded cocrystal system revealed complex landscape multicomponent phases, where all transformations were explained by periodic DFT calculations and dissolution calorimetry measurements.

Language: Английский

Citations

2
Halogen Bonding to Carbon: a Directional Interaction for the Reliable Design of Supramolecular Architectures Based on Non-derivatized Aromatic Carbon Systems DOI Creative Commons
Jogirdas Vainauskas,

Tristan Borchers,

Mihails Arhangelskis

et al.

Published: April 25, 2023

Carbon, although the central element in organic chemistry has been traditionally neglected as a target for directional supramolecular interactions. The design of structures involving carbon-rich molecules, such arenes, almost exclusively limited to π-stacking aromatic systems, or derivatization with heteroatoms sites molecular recognition. Here, we demonstrate that C-I···Cπ halogen bonds carbon-based π-systems can be reliably used direction-al interactions creation extended based on planar, well curved without any need π-stacking. Specifically, describe first systematic study series cocrystals containing non-derivatized carbon-only systems different sizes and shapes, including polycyclic hydrocarbons (PAHs) fullerene C60, which are held together by carbon atoms. In large majority (~90%) structures, bonding PAHs leads ladder-like motif, act rungs bond donors rails, demonstrating this motif example synthon carbon. These results, supported novel cocrystal theoretical calculations, analysis Cambridge Structural Database, offer new, previously overlooked paradigm assembly not π-stacking, but via specific, bonding. This new ability use car-bon-based direct provides an exciting opportunity create materials modified properties seen from red blue shifts solid-state luminescence pyrene, coronene perylene, appearance room-temperature phosphorescence upon formation.

Language: Английский

Citations

0