Insights into the Effect of Trans-to-Cis Photoisomerization of a Co-coordinated Stilbene Derivative on the Luminescence of Di-beta-diketonate Lanthanide Complexes

Five lanthanide complexes constructed from a stilbene derivative, (E)-N',N'-bis(pyridin-2-ylmethyl)-4-styrylbenzoyl hydrazide (HL), and two beta-diketonates (2-thenoyltrifluoroacetonate, tta), with or without a trifluoroacetate anion (CF3CO2-), namely, [Ln(tta)(2)(HL) (CF3CO2)] [LnC(45)H(32)F(9)N(4)O(7)S(2), Ln = La (1), Nd (2), Eu (3), or Gd (4)] and [Yb(tta)(2)(L)] (YbC43H31F6N4O5S2 (5), L = deprotonated HL), were synthesized and characterized. Crystals of these five complexes were obtained and analyzed by single-crystal X-ray diffraction. These complexes all belonged to the monoclinic P2(1)/c space group. For La3+, Nd3+, Eu3+, and Gd3+, the central lanthanide ion was nine-coordinate with a monocapped twisted square antiprism polyhedron geometry. The central Yb3+ ion of complex 5 was eight-coordinate with a distorted double-capped triangular prism polyhedron geometry. Among the five complexes, trans-to-cis photoisomerization of the stilbene group in gadolinium complex 4 showed the largest quantum yield. Complexes 2, 3, and 4 showed dual luminescence and photoisomerization functions. The luminescence change of complex 3 was reversible upon the trans-to-cis photoisomerization process. The sensitization efficiencies of luminescent europium complex 3 in acetonitrile solutions and in the solid state were 49.9 and 42.6%, respectively. These medium sensitization efficiencies led to the observation of simultaneous photoisomerization and luminescence, which further confirmed our previous report that photoisomerization of the stilbene group within complexes was related to the lanthanide ion energy level and whether a ligand-to-metal center or ligand-to-ligand charge-transfer process was present. In complexes 1-5, in addition to the intramolecular absorption transition of the ligand itself (IL, pi HL-pi HL* and pi(tta)-pi(tta)*), the presence of a ligand-to-ligand charge-transfer transition between tta and HL (LLCT, pi(tta)-pi(HL)* or pi(HL)-pi(tta)*) indicated whether the triplet-state energy of HL was able to transfer to the excited energy level of the lanthanide ions, leading to different extents of HL photoisomerization. These results provide an important route for the design of new dual-function lanthanide-based optical switching materials.