Halogen bonding stabilizes a cis-azobenzene derivative in the solid state : A crystallographic study
Saccone, Marco; Siiskonen, Antti; Fernandez-Palacio, Franisco; Priimägi, Arri; Terraneo, Giancarlo; Resnati, Giuseppe; Metrangolo, Pierangelo (2017-04-01)
Saccone, Marco
Siiskonen, Antti
Fernandez-Palacio, Franisco
Priimägi, Arri
Terraneo, Giancarlo
Resnati, Giuseppe
Metrangolo, Pierangelo
01.04.2017
Julkaisun pysyvä osoite on
https://urn.fi/URN:NBN:fi:tuni-202005085078
https://urn.fi/URN:NBN:fi:tuni-202005085078
Kuvaus
Peer reviewed
Tiivistelmä
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.
Kokoelmat
- TUNICRIS-julkaisut [16929]