title: Azobenzene-derived tris-β-diketonate lanthanide complexes: reversible trans-to-cis photoisomerization in solution and solid state.
abstract: Novel azobenzene-derived β-diketonates (4,4,5,5,6,6,6-heptafluoro-1-azobenzene-1,3-hexanedione (LA), 4,4,5,5,6,6,6-heptafluoro-1-(4-dimethylamino)azobenzene-1,3-hexanedione (LB)) were designed and their complexes with lanthanide cations (La(3+), Eu(3+), Gd(3+), Yb(3+)) were prepared and characterized by (1)H NMR, FT-IR, and elemental analysis. Three of the complexes were crystallized successfully and identified by X-ray diffraction. It was significant to find that LA showed remarkably reversible trans-to-cis isomerization properties, however, LB, bearing an electron donor compared with LA, slowed down the isomerization to an extent. The presence of Ln(iii) enhanced the reversible trans-to-cis isomerization properties of both LA and LB a little upon photoirradiation in organic solvents, and amazingly increased the fatigue resistance. In addition, the complexes doped in polymethyl methacrylate (PMMA) films produced a similar phenomenon as well as when in solution. Theoretical calculations based on time dependent density functional theory (TD-DFT) were performed for geometry optimization and to determine the excitation energies of LA and LB to gain further insight into the electronic structure of the complexes, and the data were consistent with the experimental results. The excellent reversible photoisomerization properties of the newly designed Ln(iii) complexes can offer important advantages that will help with the further study of these materials to reach their full potential in applications such as molecular switching devices.
authors.affiliation: Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. China. linlr@xmu.edu.cn.
authors.forename: Li-Rong
authors.initials: LR
authors.lastname: Lin
authors.forename: Xuan
authors.initials: X
authors.lastname: Wang
authors.forename: Gao-Ning
authors.initials: GN
authors.lastname: Wei
authors.forename: Hui-Hui
authors.initials: HH
authors.lastname: Tang
authors.forename: Hui
authors.initials: H
authors.lastname: Zhang
authors.forename: Li-Hua
authors.initials: LH
authors.lastname: Ma