Crystals of trans- and cis-isomers of a fluorinated azobenzene derivative have been prepared and characterized by single-crystal X-ray diffraction. The presence of F atoms on the aromatic core of the azobenzene increases the lifetime of the metastable cis-isomer, allowing single crystals of the cis-azobenzene to be grown. Structural analysis on the cis-azobenzene, complemented with density functional theory calculations, highlights the active role of the halogen-bond contact (N...I synthon) in promoting the stabilization of the cis-isomer. The presence of a long aliphatic chain on the azobenzene unit induces a phase segregation that stabilizes the molecular arrangement for both the trans- and cis-isomers. Due to the rarity of cis-azobenzene crystal structures in the literature, our paper makes a step towards understanding the role of non-covalent interactions in driving the packing of metastable azobenzene isomers. This is expected to be important in the future rational design of solid-state, photoresponsive materials based on halogen bonding. We show by single-crystal X-ray diffraction studies and computational analysis that halogen bonding can stabilize a metastable cis-azobenzene derivative in the solid state.

Saccone M., Siiskonen A., Fernandez-Palacio F., Priimagi A., Terraneo G., Resnati G., et al. (2017). Halogen bonding stabilizes a cis-azobenzene derivative in the solid state: A crystallographic study. ACTA CRYSTALLOGRAPHICA. SECTION B, STRUCTURAL SCIENCE, CRYSTAL ENGINEERING AND MATERIALS, 73(2), 227-233 [10.1107/S2052520617003444].

Halogen bonding stabilizes a cis-azobenzene derivative in the solid state: A crystallographic study

Saccone M.
Supervision
;
2017-01-01

Abstract

Crystals of trans- and cis-isomers of a fluorinated azobenzene derivative have been prepared and characterized by single-crystal X-ray diffraction. The presence of F atoms on the aromatic core of the azobenzene increases the lifetime of the metastable cis-isomer, allowing single crystals of the cis-azobenzene to be grown. Structural analysis on the cis-azobenzene, complemented with density functional theory calculations, highlights the active role of the halogen-bond contact (N...I synthon) in promoting the stabilization of the cis-isomer. The presence of a long aliphatic chain on the azobenzene unit induces a phase segregation that stabilizes the molecular arrangement for both the trans- and cis-isomers. Due to the rarity of cis-azobenzene crystal structures in the literature, our paper makes a step towards understanding the role of non-covalent interactions in driving the packing of metastable azobenzene isomers. This is expected to be important in the future rational design of solid-state, photoresponsive materials based on halogen bonding. We show by single-crystal X-ray diffraction studies and computational analysis that halogen bonding can stabilize a metastable cis-azobenzene derivative in the solid state.
Settore CHIM/07 - Fondamenti Chimici Delle Tecnologie
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Saccone M., Siiskonen A., Fernandez-Palacio F., Priimagi A., Terraneo G., Resnati G., et al. (2017). Halogen bonding stabilizes a cis-azobenzene derivative in the solid state: A crystallographic study. ACTA CRYSTALLOGRAPHICA. SECTION B, STRUCTURAL SCIENCE, CRYSTAL ENGINEERING AND MATERIALS, 73(2), 227-233 [10.1107/S2052520617003444].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10447/398660
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