TY - JOUR

T1 - Halogen bonded supramolecular assemblies constructed from azulene derivatives and perfluorinated di-/triiodobenzenes

AU - Dogaru, Andreea

AU - Apostol, Adrian A.

AU - Maxim, Catalin

AU - Raduca, Mihai

AU - Novikov, Alexander S.

AU - Nicolescu, Alina

AU - Deleanu, Calin

AU - Nica, Simona

AU - Andruh, Marius

PY - 2023/11

Y1 - 2023/11

N2 - Two series of binary halogen-bonded co-crystals involving perfluorinated di- and triiodobenzene (1,2-ditfb, 1,4-ditfb and 1,3,5-titfb) and 1,3-azulenedicarboxaldehyde (azdicho) 1 and 1,3-bis(4-pyridyl)azulene (azbbpy) 2 are reported. The crystal structures of the six new co-crystals show primarily O⋯I or N⋯I interactions, and the subsidiary weak C-H⋯F and π-π interactions of the aromatic units. Because the halogen-bond acceptors contain different heteroatoms and length size, the supramolecular recognition in the co-crystal is quite different. Besides novel structural features formed via halogen-bonding interactions, our results showed that the azulene moiety plays a unique organizing role in the formation and stabilization of supramolecular aggregates through π-π stacking interactions. These non-covalent interactions are investigated by theoretical studies through Hirshfeld surface analysis and DFT calculations followed by topological analysis of the electron density distribution within the QTAIM approach. The co-crystals were also investigated in solution by NMR spectroscopy through 19F-NMR and 1H,15N-HMBC experiments.

AB - Two series of binary halogen-bonded co-crystals involving perfluorinated di- and triiodobenzene (1,2-ditfb, 1,4-ditfb and 1,3,5-titfb) and 1,3-azulenedicarboxaldehyde (azdicho) 1 and 1,3-bis(4-pyridyl)azulene (azbbpy) 2 are reported. The crystal structures of the six new co-crystals show primarily O⋯I or N⋯I interactions, and the subsidiary weak C-H⋯F and π-π interactions of the aromatic units. Because the halogen-bond acceptors contain different heteroatoms and length size, the supramolecular recognition in the co-crystal is quite different. Besides novel structural features formed via halogen-bonding interactions, our results showed that the azulene moiety plays a unique organizing role in the formation and stabilization of supramolecular aggregates through π-π stacking interactions. These non-covalent interactions are investigated by theoretical studies through Hirshfeld surface analysis and DFT calculations followed by topological analysis of the electron density distribution within the QTAIM approach. The co-crystals were also investigated in solution by NMR spectroscopy through 19F-NMR and 1H,15N-HMBC experiments.

UR - https://www.mendeley.com/catalogue/16dcc0a1-8510-324a-8149-88d6b49c5546/

U2 - 10.1039/d3ce00752a

DO - 10.1039/d3ce00752a

M3 - Article

VL - 25

SP - 5243

EP - 5261

JO - CrystEngComm

JF - CrystEngComm

SN - 1466-8033

IS - 37

ER -