Azobased iminopyridine ligands and their rhenium metal complexes: Syntheses, spectroscopic, trans-cis photoisomerization and theoretical studies

Mohamed Ali Benmensour (1, 2) , Awatef Ayadi (3) , Huriye Akdas-Kilig (4) , Abdou Boucekkine (4) , Jean-Luc Fillaut (4) , Abdelkrim El-Ghayoury (3)

1 UMMTO - Université Mouloud Mammeri [Tizi Ouzou]
2 USTHB - Université des Sciences et de la Technologie Houari Boumediene = University of Sciences and Technology Houari Boumediene [Alger]
3 MOLTECH-Anjou
4 ISCR - Institut des Sciences Chimiques de Rennes

The reaction of rhenium(I) pentacarbonyl chloride Re(CO)5Cl with N,N-dimethyl-4-((E)-(pyridin-2-ylmethylene) amino)phenyl) diazenyl) aniline L1 and (E)-4-((E)-(4-nitrophenyl)diazenyl)-N-(pyridin-2-ylmethylene) aniline L2 affords two rhenium metal complexes [ReL1(CO)3Cl] (ReL1) and [ReL2(CO)3Cl] (ReL2), respectively. These Re(I) complexes were characterized in detail, including their single crystal structures, absorption spectra and electronic structures using DFT calculations. Trans to cis photoisomerization of the free ligands and complexes was investigated experimentally and rationalized theoretically. Interestingly, light-induced photoisomerization of the azo fragment is observed for free ligand L1 while inhibition of this process is produced upon coordination to Re metal cation.

Keywords: Rhenium complex; UV–vis spectroscopy; Iminopyridine; X-ray diffraction; DFT; Azobenzene

Domains: Chemical Sciences

Mohamed Ali Benmensour, Awatef Ayadi, Huriye Akdas-Kilig, Abdou Boucekkine, Jean-Luc Fillaut, et al.. Azobased iminopyridine ligands and their rhenium metal complexes: Syntheses, spectroscopic, trans-cis photoisomerization and theoretical studies. Journal of Photochemistry and Photobiology A: Chemistry, 2019, 368, pp.78-84. ⟨10.1016/j.jphotochem.2018.09.023⟩. ⟨hal-01943754⟩